U.S. patent application number 09/152585 was filed with the patent office on 2001-06-21 for olefin(co-) polymer compositions and method for producing the same andcatalyst for olefin (co-) polymerization and method for producing the same.
This patent application is currently assigned to CHISSO CORPORATION. Invention is credited to KIKUKAWA, SHINGO, NOBUHARA, HIDEO, SAITO, JUN, SATO, HITOSHI, YAMAUCHI, AKIRA.
Application Number | 20010004657 09/152585 |
Document ID | / |
Family ID | 27573467 |
Filed Date | 2001-06-21 |
United States Patent
Application |
20010004657 |
Kind Code |
A1 |
SAITO, JUN ; et al. |
June 21, 2001 |
OLEFIN(CO-) POLYMER COMPOSITIONS AND METHOD FOR PRODUCING THE SAME
ANDCATALYST FOR OLEFIN (CO-) POLYMERIZATION AND METHOD FOR
PRODUCING THE SAME
Abstract
An olefin (co-)polymer composition including 0.01 to 5.0 weight
parts of high molecular weight polyethylene which is an ethylene
homopolymer or an ethylene-olefin copolymer containing 50 weight %
or more of an ethylene polymerization unit; and 100 weight parts of
an olefin (co-)polymer other than the high molecular weight
polyethylene, wherein said high molecular weight polyethylene has
an intrinsic viscosity [.eta..sub.E] of 15 to 100 dl/g measured in
tetralin at 135.degree. C. or more, and said high molecular weight
polyethylene exists as dispersed fine particles having a numerical
average particle size of 1 to 5000 nm.
Inventors: |
SAITO, JUN; (CHIBA, JP)
; NOBUHARA, HIDEO; (KUMAMOTO, JP) ; KIKUKAWA,
SHINGO; (CHIBA, JP) ; SATO, HITOSHI; (CHIBA,
JP) ; YAMAUCHI, AKIRA; (CHIBA, JP) |
Correspondence
Address: |
MERCHANT & GOULD
P O BOX 2903
MINNEAPOLIS
MN
55402-0903
US
|
Assignee: |
CHISSO CORPORATION
OSAKA
JP
|
Family ID: |
27573467 |
Appl. No.: |
09/152585 |
Filed: |
September 14, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09152585 |
Sep 14, 1998 |
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08809863 |
Apr 2, 1997 |
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6156845 |
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Current U.S.
Class: |
525/240 ;
502/108; 502/109; 525/322; 526/124.5; 526/124.6; 526/904 |
Current CPC
Class: |
C08F 210/06 20130101;
C08L 2314/02 20130101; C08F 110/06 20130101; C08L 23/04 20130101;
Y10S 526/904 20130101; C08L 23/02 20130101; C08F 10/00 20130101;
C08F 10/06 20130101; C08F 110/02 20130101; C08L 23/10 20130101;
C08F 10/00 20130101; C08F 4/6492 20130101; C08L 23/02 20130101;
C08L 2666/02 20130101; C08L 23/04 20130101; C08L 2666/04 20130101;
C08L 23/10 20130101; C08L 2666/04 20130101; C08F 110/02 20130101;
C08F 2500/01 20130101; C08F 110/06 20130101; C08F 2500/17 20130101;
C08F 210/06 20130101; C08F 210/08 20130101; C08F 210/16 20130101;
C08F 2500/17 20130101; C08F 210/06 20130101; C08F 210/16 20130101;
C08F 2500/17 20130101 |
Class at
Publication: |
525/240 ;
525/322; 526/124.5; 526/124.6; 526/904; 502/108; 502/109 |
International
Class: |
C08L 023/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 18, 1995 |
JP |
7-269920 |
Oct 18, 1995 |
JP |
7-269921 |
Oct 18, 1995 |
JP |
7-269922 |
Oct 18, 1995 |
JP |
7-269923 |
Oct 18, 1995 |
JP |
7-269924 |
Oct 18, 1995 |
JP |
7-269925 |
Aug 9, 1996 |
JP |
8-210888 |
Aug 9, 1996 |
JP |
8-210889 |
Claims
1. An olefin (co-)polymer composition comprising: 0.01 to 5.0
weight parts of high molecular weight polyethylene which is an
ethylene homopolymer or an ethylene-olefin copolymer containing 50
weight % or more of an ethylene polymerization unit; and 100 weight
parts of an olefin (co-)polymer other than the high molecular
weight polyethylene, wherein said high molecular weight
polyethylene has an intrinsic viscosity [.eta..sub.E] of 15 to 100
dl/g measured in tetralin at 135.degree.C. or more, and said high
molecular weight polyethylene exists as dispersed fine particles
having a numerical average particle size of 1 to 5000 nm.
2. The olefin (co-)polymer composition as claimed in claim 1,
wherein the numerical average particle size of the high molecular
weight polyethylene is 10 to 500 nm.
3. The olefin (co-)polymer composition as claimed in claim 1,
wherein the intrinsic viscosity [.eta.] of the olefin (co-) polymer
composition which is measured in tetralin at 135.degree. C. is 0.2
to 10 dl/g.
4. The olefin (co-)polymer composition as claimed in claim 1,
wherein the olefin (co-)polymer other than the high molecular
weight polyethylene is at least one selected from the group
consisting of a propylene homopolymer and a propylene-olefin
copolymer containing 50 weight % or more of a propylene
polymerization unit.
5. The olefin (co-)polymer composition as claimed in claim 1,
wherein the following relationship is satisfied in a bulk state of
where a rubber component or an inorganic filler is not contained as
expressed by the following formula:log (G'(.omega.=10.sup.0))-log
(G'(.omega.=10.sup.-2))&- lt;2, a storage modulus being
G'(.omega.=10.sup.0) with a frequency of .omega.=10.sup.0 of a
molten product of 230.degree. C. and a storage modulus being
G'(.omega.-10.sup.-2) with a frequency of .omega.=10.sup.-2
6. The olefin (co-)polymer composition as claimed in claim 1,
wherein the following relationship is satisfied in a state where
electron beam radiation is not performed:log (N.sub.1)>-log
(MFR)+5 a first normal stress difference being expressed by N.sub.1
with a shear rate of 4.times.10.sup.-1 (sec ) at 190.degree. C.,
230.degree. C. and 250.degree.C., a metal flow rate being expressed
by MFR.
7. The olefin (co-)polymer composition as claimed in claim 1,
wherein the following relationship is satisfied at 190.degree.C.
and 250.degree.
C.:(N.sub.1(190.degree.C.)-N.sub.1(250.degree.C.))/N.sub.1(190.degree.C.)-
<0.6 a first normal stress difference being expressed by N.sub.1
(190.degree.C.) and N.sub.1(250.degree. C.) with a shear rate of
4.times.10.sup.-1 (sec.sup.-1).
8. The olefin (co-)polymer composition as claimed in claim 1 ,
wherein the following relationship is satisfied at 190.degree. C.
and 250.degree.C.:(MS(190.degree. C.)-MS(250.degree.
C.))/MS(190.degree. C.)<3.1 a melt tension being expressed by MS
(190.degree.C.) and MS(250.degree.C.) with a shear rate of
3.times.10.sup.-1 (sec.sup.-1).
9. The olefin (co-)polymer composition as claimed in claim 1,
wherein the following relationship is
satisfied:(G(t=10)-G(t=300))/G(t=10)<1 a relaxation elastic
modulus being expressed by G(t=10) with t=10 (sec), and a
relaxation elastic modulus being expressed by G(t=300) with t=300
(sec) on the condition of 500% of a strain of the molten product at
230.degree. C.
10. The olefin (co-)polymer composition as claimed in claim 1,
wherein an elongational viscosity is increased in a large
deformation region when molten and stretched to show strain
hardening property.
11. The olefin (co-)polymer composition as claimed in claim 1,
wherein said high molecular weight polyethylene fine particles are
added before or during olefin (co-)polymerization.
12. The olefin (co-)polymer composition as claimed in claim 1,
wherein the olefin (co-)polymer is a propylene homopolymer or a
propylene-olefin copolymer containing 50 weight % or more of a
propylene polymerization unit, and said olefin (co-)polymer
composition satisfies the following relationship between a melt
tension (MS) at 230.degree. C. and an intrinsic viscosity
[.eta..sub.E] measured in tetralin at 135.degree. C.:log
(MS)>4.24.times.log [.eta..sub.T]1.20.
13. The olefin (co-)polymer composition as claimed in claim 1,
wherein the olefin (co-)polymer is a propylene homopolymer or a
propylene-olefin copolymer containing 50 weight % or more of a
propylene polymerization unit, and said olefin (co-)polymer
composition satisfies the following relationship between a melt
tension (MS) at 230.degree.C. and an intrinsic viscosity
[.eta..sub.E] measured in tetralin at 135.degree. C.:4.24.times.log
[.eta..sub.T]+0.24>4.24.times.log [.eta..sub.T]-1.10.
14. The olefin (co-)polymer composition as claimed in claim 1,
wherein the olefin (co-)polymer is an ethylene homopolymer or an
ethylene-olefin copolymer containing 50 weight % of an ethylene
polymerization unit.
15. The olefin (co-)polymer composition as claimed in claim 1,
wherein 0.001 to 2 weight parts of at least one stabilizer selected
from the group consisting of a phenol antioxidant and a phosphoric
antioxidant is added to 100 weight parts of the olefin (co-)polymer
composition.
16. The olefin (co-)polymer composition as claimed in claim 1,
wherein the olefin (co-)polymer other than high molecular
polyethylene is a propylene homopolymer or a propylene-olefin
copolymer containing 50 weight % or more of a propylene
polymerization unit, the olefin (co-)polymer other than high
molecular polyethylene is produced by polymerizing propylene or by
copolymerizing propylene and another olefin having 2 to 12 carbon
atoms in the presence of a preactivated catalyst comprising an
olefin producing catalyst and a polyethylene supported by the
olefin producing catalyst, and said olefin producing catalyst is
formed by the combination of a transition metal compound catalytic
component containing at least a titanium compound, 0.01 to 1000 mol
of an organic metal compound (AL1) selected from the group
consisting of a metal that belongs to group I, group II, group XII
and group XIII of the periodic table published in 1991 with respect
to 1 mol of the transition metal atom, and 0 to 500 mol of an
electron donor (E1) with respect to 1 mol of the transition metal
atom.
17. The olefin (co-)polymer composition as claimed in claim 16,
wherein the composition is obtained by polymerizing or
copolymerizing either propylene alone or a combination of propylene
and an olefin having 2 to 12 carbon atoms in the presence of the
preactivated catalyst, wherein the preactivated catalyst further
comprises an organic metal compound (AL2) and an electron donor
(E2), said organic metal compound (AL2) is a compound of a metal
selected from the group consisting of metals belonging to Groups I
, II, XII and XIII according to the period table issued in 1991,
the content of the organic metal compounds (AL1) and (AL2) is 0.05
to 5000 mole per mole of the transition metal atom in the
preactivated catalyst, and the content of the electron donors (E1)
and (E2) is 0 to 3000 mole per mole of the transition metal atom in
the preactivated catalyst.
18. The olefin (co-)polymer composition as claimed in claim 16 or
17, wherein the preactivated catalyst supports 0.01 to 5000 g of
polyethylene with an intrinsic viscosity [.eta..sub.A] of 15 to 100
dl/g measured in tetralin at 135.degree. C. for 1 g of the
transition metal compound catalytic component.
19. The olefin (co-)polymer composition as claimed in claim 16 or
17, wherein the preactivated catalyst supports 0.01 to 100 g of
polypropylene (B) and 0.01 to 5000g of polyethylene (A) per gram of
the transition metal compound catalytic component, said
polypropylene (B) has an intrinsic viscosity [.eta..sub.B] of less
than 15 dl/g measured in tetralin at 135.degree. C., and is a
propylene homopolymer or a propylene-olefin copolymer comprising a
propylene polymerization unit at the rate of 50 weight % or more,
and said polyethylene (A) has an intrinsic viscosity [.eta..sub.A]
of 15 to 100 dl/g measured in tetralin at 135.degree. C.
20. The olefin (co-)polymer composition as claimed in claim 16 or
17, wherein the olefin (co-)polymer other than high molecular
polyethylene is produced by using 0.01 to 1000 mmol of catalyst
converted into a transition metal atom in a catalyst for 1 liter of
(co-)polymerization volume of propylene or another olefin.
21. The olefin (co-)polymer composition as claimed in claim 1,
wherein the olefin (co-)polymer other than high molecular
polyethylene is produced by mixing a) a propylene homopolymer or a
propylene-olefin copolymer which contains 50 weight % or more of a
propylene polymerization unit, said propylene homopolymer or
propylene-olefin copolymer is produced by polymerizing only
propylene or by polymerizing or copolymerizing propylene and
another olefin having 2 to 12 carbon atoms in the presence of a
preactivated catalyst containing an olefin producing catalyst and
polyethylene supported by the olefin producing catalyst, said
olefin producing catalyst is formed by the combination of a
transition metal compound catalytic component containing at least a
titanium compound, 0.01 to 1000 mol of an organic metal compound
(AL1) selected from a group consisting of metals that belong to
group I, group II, group XII and group XIII of the periodic table
published in 1991 with respect to 1 mol of the transition metal
atom, and 0 to 500 mol of an electron donor (E1) with respect to 1
mol of the transition metal atom, and b) a propylene homopolymer or
a propylene-olefin copolymer which contains 50 weight % of a
propylene polymerization unit.
22. A method for producing an olefin (co-)polymer composition
comprising the step of polymerizing or copolymerizing olefin in the
presence of a preactivated catalyst comprising a polyolefin
preparing catalyst and a polyethylene to form an olefin
(co-)polymer, wherein said polyolefin preparing catalyst comprises
(i) a transition metal compound catalytic component including at
least a titanium compound, (ii) an organic metal compound (AL1) and
(iii) an electron donor (E1), said organic metal compound (AL1) is
a compound of a metal selected from the group consisting of metals
pertaining to Groups I, II, XII and XIII according to the period
table issued in 1991, the content of the metal organic compound
(AL1) is 0.01 to 1000 mole per mole of the transition metal atom,
the content of the electron donor (E1) is 0 to 500 mole per mole of
the transition metal atom, and wherein said polyethylene is
supported by the polyolefin preparing catalyst and comprises an
ethylene homopolymer or an ethylene-olefin copolymer comprising an
ethylene polymerization unit at the rate of 50 weight % or more,
the content of polyethylene supported is 0.01 to 5000 g per gram of
the transition metal compound catalytic component, and said
polyethylene has an intrinsic viscosity [.eta.] of 15 to 100 dl/g
measured in tetralin at 135.degree. C.
23. The method for producing an olefin (co-)polymer composition as
claimed in claim 22, wherein the olefin to be polymerized or
copolymerized is propylene or an olefin having 2 to 12 carbon
atoms, and said olefin (co-)polymer is a propylene homopolymer or a
propylene-olefin copolymer comprising 50 weight % or more of a
propylene polymerization unit and an olefin having 2 to 12 carbon
atoms.
24. The method for producing an olefin (co-)polymer composition as
claimed in claim 22, further comprising a step of adding an organic
aluminum compound and an electron donor (E2) to the preactivated
catalyst, wherein the content of the organic aluminum compound
(AL1) and said organic aluminum compound in the preactivated
catalyst is 0.05 to 5000 molar parts with respect to 1 mol of
titanium atom, and the content of the electron donors (E1) and (E2)
in the preactivated catalyst is 0 to 3000 molar parts with respect
to 1 mol of titanium atom in the preactivated catalyst.
25. The method for producing an olefin (co-)polymer composition as
claimed in claim 22, wherein the amount of titanium atom in the
catalyst is 0.01 to 1000 mmol for 1 liter of olefin
(co-)polymerization volume.
26. The method for producing an olefin (co-)polymer composition as
claimed in claim 22, wherein the preactivated catalyst comprises
0.01 to 100 g of polypropylene (B) per gram of the transition metal
compound catalytic component, and said polypropylene (B) has an
intrinsic viscosity [.eta..sub.B] of less than 15 dl/g measured in
tetralin at 135.degree. C., and is a propylene homopolymer or a
propylene-olefin copolymer comprising a propylene polymerization
unit at the rate of 50 weight % or more.
27. The method for producing an olefin (co-)polymer composition as
claimed in claim 26, wherein the amount of the transition metal in
the catalyst is 0.01 to 1000 mmol for 1 liter of olefin
(co-)polymerization volume.
28. The method for producing an olefin (co-)polymer composition as
claimed in claim 22, wherein the method comprises the steps of: (a)
a preliminary (co-)polymerization process comprising polymerizing
or copolymerizing olefin in the presence of a polyolefin preparing
catalyst to form 0.01 to 100 g of polyolefin (B) having an
intrinsic viscosity [.eta.] of less than 15 dl/g measured in
tetralin at 135.degree. C. per gram of the transition metal
compound catalytic component, said polyolefin preparing catalyst
comprises (i) a transition metal compound catalytic component
including at least a titanium compound, (ii) an organic metal
compound (AL1) and (iii) an electron donor (E1), said organic metal
compound (AL1) is a compound of a metal selected from the group
consisting of metals belonging to Groups I, II, XII and XIII
according to the period table issued in 1991, the content of the
metal organic compound (AL1) is 0.01 to 1000 mole per mole of the
transition metal atom, the content of the electron donor (E1) is 0
to 500 mole per mole of the transition metal atom; (b) a
preliminary activation (co-)polymerization process comprising
polymerizing or copolymerizing olefin to form 0.01 to 100 g of
polyolefin (A) having an intrinsic viscosity [.eta.] of 15 to 100
dl/g measured in tetralin at 135.degree. C. per gram of the
transition metal compound catalytic component; and (c) a main
(co-)polymerization process comprising polymerizing olefin having 2
to 12 carbon atoms in the presence of a preactivated catalyst for
polymerizing olefin, said preactivated catalyst is obtained by
letting the transition metal compound catalytic component support
polyolefins (B) and (A).
29. The method for producing an olefin (co-)polymer composition as
claimed in claim 22, wherein the method comprises the step of
polymerizing or copolymerizing olefin in the presence of: (a) a
preactivated catalyst for polymerizing or copolymerizing olefin
which is obtained by a method for letting the transition metal
compound catalytic component support polyolefins (B) and (A)
comprising the steps of: a preliminary (co-)polymerization process
comprising polymerizing or copolymerizing olefin in the presence of
a polyolefin preparing catalyst to form 0.01 to 100 g of polyolefin
(B) having an intrinsic viscosity [.eta.] of less than 15 dl/g
measured in tetralin at 135.degree. C. per gram of the transition
metal compound catalytic component, said polyolefin preparing
catalyst comprises (i) a transition metal compound catalytic
component including at least a titanium compound, (ii) an organic
metal compound (AL1) and (iii) an electron donor (E1), said organic
metal compound (AL1) is a compound of a metal selected from the
group consisting of metals belonging to Groups I, II, XII and XIII
according to the period table issued in 1991, the content of the
metal organic compound (AL1) is 0.01 to 1000 mole per mole of the
transition metal atom, the content of the electron donor (E1) is 0
to 500 mole per mole of the transition metal atom; and a
preliminary activation (co-)polymerization process comprising
polymerizing or copolymerizing olefin to form 0.01 to 100 g of
polyolefin (A) having an intrinsic viscosity [.eta.] of 15 to 100
dl/g measured in tetralin at 135.degree. C. per gram of the
transition metal compound catalytic component; (b) an organic metal
compound (AL2) which is a compound of a metal selected from the
group consisting of metals belonging to Groups I, II, XII and XIII
according to the period table issued in 1991, the content of the
metal organic compounds (AL1) and (AL2) is 0.05 to 5000 mole per
mole of the transition metal atom in the preactivated catalyst; and
(c) an electron donor (E2), the content of the electron donors (E1)
and (E2) is 0 to 3000 mole per mole of the transition metal
atom.
30. The method for producing an olefin (co-)polymer composition as
claimed in claim 22, further comprising a step of adding 0.001 to 2
weight parts of at least one stabilizer selected from the group
consisting of a phenolic antioxidant and a phosphoric antioxidant
to the olefin (co-)polymer after (co-) polymerizing an olefin.
31. A method for producing an olefin (co-)polymer, comprising a
step of adding 0 to 2000 weight parts of an olefin (co-)polymer
obtained by a known method to 100 weight parts of an olefin
(co-)polymer composition obtained by the method as claimed in claim
22.
32. A catalyst for olefin (co-)polymerization comprising a
transition metal compound catalyst which contains at least a
titanium compound and an olefin (co-)polymer (A) supported by the
catalyst, wherein said olefin (co-)polymer (A) has an intrinsic
viscosity [.eta.] of 15 dl/g to 100 dl/g measured in tetralin at
135.degree. C. and the content of said olefin (co-)polymer (A) is
0.01 to 5000 g for 1 g of a titanium containing solid catalytic
component.
33. The catalyst for olefin (co-)polymerization as claimed in claim
32, wherein the transition metal compound catalytic component is
obtained by the combination of 0.01 to 1000 mol of an organic metal
compound (AL1) selected from group I, group II, group XII and group
XIII of the periodic table published in 1991 with respect to 1 mol
of the transition metal atom and 0 to 500 mol of an electron donor
(E1) with respect to 1 mol of the transition metal atom.
34. The catalyst for olefin (co-)polymerization as claimed in claim
32, wherein the olefin (co-)polymer (A) is an ethylene homopolymer
or an ethylene-olefin copolymer which contains 50 weight % or more
of an ethylene polymerization unit.
35. The catalyst for olefin (co-)polymerization as claimed in claim
32, further comprising an organic aluminum compound (AL1) and an
electron donor (E1), wherein the content of said organic aluminum
compound (AL1) is 0.01 to 1000 mole per mole of titanium atom in
the catalyst, and the content of said electron donor (E1) is 0 to
500 mole per mole of titanium atom in the catalyst.
36. The catalyst for olefin (co-)polymerization as claimed in claim
32, wherein a polyolefin (B) to be (co-)polymerized is formed on a
layer which is lower than said polyolefin (A) to be
(co-)polymerized, polyolefin (B) has an intrinsic viscosity [.eta.]
of less than 15 dl/g measured in tetralin at 135.degree. C. and the
content of said polyolefin (B) is 0.01 to 100 g for 1 g of a
transition metal compound component.
37. The catalyst for olefin (co-)polymerization as claimed in claim
32, wherein the transition metal compound catalytic component is a
titanium containing solid catalytic component whose main component
is a titanium trichloride composition or titanium
tetrachloride.
38. The catalyst for olefin (co-)polymerization as claimed in claim
32, wherein the organic metal compound (AL1) is an organic aluminum
compound.
39. The catalyst for olefin (co-)polymerization as claimed in claim
33, wherein the electron donor (E1) is an organic compound
containing oxygen, nitrogen, phosphorus or sulfur in a molecule, or
an organic silicon compound having Si--O--C bonding in a
molecule.
40. The catalyst for olefin (co-)polymerization as claimed in claim
32, wherein the polyolefin (B) is a homopolymer or copolymer of an
olefin having 2 to 12 carbon atoms.
41. The catalyst for olefin (co-)polymerization as claimed in claim
33, further comprising an electron donor (E2), wherein the content
of said electron donors (E1) and (E2) is 0 to 3000 mole per mole of
the transition metal atom in the catalyst.
42. The catalyst for olefin (co-)polymerization as claimed in claim
41, wherein the electron donor (E2) is an organic compound
containing oxygen, nitrogen, phosphorus or sulfur in a molecule, or
an organic silicon compound having Si--O--C bonding in a
molecule.
43. The catalyst for olefin (co-)polymerization as claimed in claim
33, further comprising an organic metal compound (AL2) and an
electron donor (E2), wherein said organic metal compound (AL2)
comprises a metal selected from the group consisting of metals that
belong to group I, group II, group XII and group XIII of the
periodic table published in 1991, the content of the organic metal
compounds (AL1) and (AL2) is 0.05 to 5000 mole with respect to 1
mole of a transition metal atom in the preactivated catalyst, and
the content of the electron donors (E1) and (E2) is 0 to 3000 mole
with respect to 1 mole of a transition metal atom in the
preactivated catalyst.
44. A method for producing a catalyst for olefin (co-)
polymerization, comprising the step of polymerizing or
copolymerizing olefin in the presence of a polyolefin preparing
catalyst to form olefin (co-)polymer (A) having an intrinsic
viscosity [.eta.] of 15 to 100 dl/g measured in tetralin at
135.degree. C. and to let a titanium containing solid catalytic
component support 0.01 to 5000 g of said olefin (co-)polymer (A)
per gram titanium containing solid catalytic component, wherein
said polyolefin preparing catalyst comprises (i) a transition metal
compound catalytic component including at least a titanium
compound, (ii) an organic metal compound (AL1) and (iii) an
electron donor (E1), the content of said organic metal compound
(AL1) is 0.01 to 1000 mole per mole of titanium atom, and the
content of said electron donor (E1) is 0 to 500 mole per mole of
titanium atom.
45. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 44, wherein the transition metal
compound catalytic component is obtained by the combination of 0.01
to 1000 mol of an organic metal compound (AL1) and 0 to 500 mol of
an electron donor (E1) with respect to 1 mol of the transition
metal atom, and said organic metal compound (AL1) comprises a metal
selected from group I, group II, group XII and group XIII of the
periodic table published in 1991.
46. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 44, wherein the olefin (co-)
polymer (A) is an ethylene homopolymer or an ethylene-olefin
copolymer which contains 50 weight % or more of an ethylene
polymerization unit.
47. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 44, further comprising a step of
forming a polyolefin (B) to be (co-)polymerized on a layer which is
lower than a polyolefin (A) to be (co-)polymerized, wherein said
polyolefin (B) to be (co-)polymerized has an intrinsic viscosity
[.eta.] of less than 15 dl/g measured in tetralin at 135.degree.
C., and the content of said polyolefin (B) is 0.01 to 100 g per
gram of the transition metal compound catalytic component.
48. The method for producing catalyst for olefin (co-)
polymerization as claimed in claim 44, wherein the transition metal
compound catalytic component is a titanium containing solid
catalytic component whose main component is a titanium trichloride
composition or titanium tetrachloride.
49. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 44, wherein the organic metal
compound (AL1) is an organic aluminum compound.
50. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 44, wherein the electron donor
(E1) is an organic compound containing oxygen, nitrogen, phosphorus
or sulfur in a molecule, or an organic silicon compound having
Si--O--C bonding in a molecule.
51. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 44, wherein the polyolefin (B)
is a homopolymer or copolymer of an olefin having 2 to 12 carbon
atoms.
52. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 44, further comprising a step of
adding an electron donor (E2) to the catalyst, wherein the content
of the electron donors (E1) and (E2) is 0 to 3000 mol with respect
to 1 mol of a transition metal atom in the catalyst.
53. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 52, wherein the electron donor
(E2) is an organic compound containing oxygen, nitrogen, phosphorus
or sulfur in a molecule, or an organic silicon compound having
SI--O--C bonding in a molecule.
54. The method for producing a catalyst for olefin (co-)
polymerization as claimed in claim 44, further comprising a step of
adding an organic metal compound (AL2) and an electron donor (E2)
to the catalyst, wherein said organic metal compound (AL2)
comprises a metal selected from the group consisting of metals that
belong to group I, group II, group XII and group XIII of the
periodic table published in 1991, the content of the organic metal
compounds (AL1) and (AL2) is 0.05 to 5000 mole with respect to 1
mole of a transition metal atom in the preactivated catalyst, and
the content of the electron donors (E1) and (E2) is 0 to 3000 mole
with respect to 1 mole of a transition metal atom in the
preactivated catalyst.
Description
TECHNICAL FIELD
[0001] The present invention relates to an olefin (co-)polymer
composition and a method for producing the same, and to a catalyst
for olefin (co-)polymer polymerization and a method for producing
the same. More particularly, the present invention relates to a
preliminarily activated catalyst for olefin (co-) polymerization
which is obtained by causing a catalyst for producing polyolefin
having, as a main component, a transitional metal compound catalyst
component containing at least a titanium compound to support
polyolefin to be polymerized and polyolefin having a high degree of
polymerization and a method for producing the preliminarily
activated catalyst for olefin (co-) polymerization, and to a
catalyst for olefin (co-)polymerization having the preliminarily
activated catalyst as a main component, and a polyolefin
composition having high melt tension and high crystallization
temperature which uses the catalyst for olefin (co-)polymerization,
and a method for producing the same.
BACKGROUND OF THE INVENTION
[0002] Since a polyolefin such as polypropyrene, high-density
polyethylene, straight chain low-density polyethylene or the like
is excellent in mechanical properties, chemical resistance and the
like and is very useful in respect of a balance of economy, it has
been widely utilized in every molding field. However, the
polyolefin has small melt tension and a low crystallization
temperature. For this reason, molding properties such as hollow
molding, foam molding, extrusion molding and the like are poor and
the high-speed productivity of a mold has limitations in various
molding methods.
[0003] A method for causing polypropylene to react with organic
peroxide and a crosslinking auxiliary agent in the melting state
(Japanese Unexamined Patent Publication Nos. 59-93711, 61-152754
and the like), a method in which a low decomposition temperature
peroxide is caused to react with semicrystalline polypropylene in
the absence of oxygen to produce polypropylene which has free end
long chain branch and does not contain gel (Japanese Unexamined
Patent Publication No. 2-298536) and the like have been disclosed
as a method for increasing the melt tension and crystallization
temperature of polypropylene.
[0004] A composition in which polyethylene having different
intrinsic viscosity or molecular weight or polypropylene are
blended and a method for producing the same composition by
multistep polymerization have been proposed as another method for
enhancing melt viscoelasticity such as melt tension or the
like.
[0005] There have been disclosed a method for adding 2 to 30 weight
parts of superhigh molecular weight polypropylene to 100 weight
parts of ordinary polypropylene and extruding a product at a
temperature which is equal to or higher than a melting point and
equal to or lower than 210.degree. C. (Japanese Examined Patent
Publication No. 61-28694), a method of preparing an extrusion sheet
made of polypropylene which is obtained by a multistep polymerizing
method and contains 2 components having the limiting viscosity
ratio of 2 or more and different molecular weights (Japanese
Examined Patent Publication No. 1-12770), a method for producing a
polyethylene composition which contains 1 to 10 weight % of
polyethylene having high viscosity-average molecular weight and
comprises three kinds of polyethylene having different
viscosity-average molecular weights by a melting and kneading
method or a multistep polymerizing method (Japanese Examined Patent
Publication No. 62-61057), a method for polymerizing superhigh
molecular weight polyethylene having a limiting viscosity of 20
dl/g or more with 0.05 to less than 1 weight % according to a
multistep polymerizing method using an active titanium-vanadium
solid catalyst component (Japanese Examined Patent Publication No.
5-79683), a method for polymerizing 0.1 to 5 weight % of superhigh
molecular weight polyethylene having a limiting viscosity of 15
dl/g or more by using an active titanium catalyst component which
has preliminarily been polymerized with 1-butene or
4-methyl-l-pentene according to a multistep polymerizing method
using a polymerization container having a special arrangement
(Japanese Examined Patent Publication No. 7-8890) and the like.
[0006] Furthermore, there have been disclosed a method for
producing polypropylene having high melt tension in which propylene
is polymerized with a support type titanium-containing solid
catalyst component and an organic aluminum compound catalyst
component by using a preliminary polymerization catalyst which is
prepared by preliminarily polymerizing ethylene and a polyene
compound (Japanese Unexamined Patent Publication No. 5-222122), and
a method for producing an ethylene-.alpha.-olefin copolymer having
high melt tension by using an ethylene containing a preliminary
polymerization catalyst which contains polyethylene having a
limiting viscosity of 20 dl/g or more that is obtained by
preliminarily polymerizing only ethylene using the same catalyst
component (Japanese Unexamined Patent Publication No. 4-55410).
[0007] According to various compositions and producing methods
which have been proposed in the prior art, the melt tension can be
enhanced to some extent but the residual odor of a crosslinking
auxiliary agent, crystallization temperature, thermal stability and
the like should be improved.
[0008] The process for manufacturing high molecular weight
polyolefin should be modified for the following reasons. More
specifically, it is hard to precisely control the amount of olefin
(co-)polymerization in order to generate a small amount of
polyolefin having a high molecular weight in the multistep
polymerizing method which is to be incorporated into the ordinary
olefin (co-)polymerizing step for polymerization. In addition, the
polymerization temperature should be lowered to generate polyolefin
having a molecular weight which is sufficiently great. Furthermore,
the productivity of the final polyolefin composition is
lowered.
[0009] In the method for preliminarily polymerizing a polyene
compound, it is necessary to prepare a polyene compound separately.
In the method for preliminarily polymerizing polyethylene, the
dispersibility of the preliminarily polymerized polyethylene to the
polyolefin which is finally obtained is non-uniform. Consequently,
further improvement should be required in respect of the stability
of the polyolefin composition.
[0010] According to the prior art, the melt tension and the
crystallization temperature of polyolefin are insufficiently
enhanced as described above. In addition, there are problems to be
solved with respect to odor and thermal stability. Furthermore, it
is necessary to enhance the productivity of such polyolefin.
SUMMARY OF THE INVENTION
[0011] It is an object of the present invention to provide a
polyolefin compound having high melt tension and high
crystallization temperature which is suitable for hollow molding,
foam molding and extrusion molding and can show high speed
production for various molding processes, and a method for
producing the same polyolefin composition.
[0012] It is another object of the present invention to provide a
catalyst for olefin (co-)polymerization to be used for producing
the polyolefin composition, and a method for producing the same
catalyst.
[0013] As a result of investigation to accomplish the
above-mentioned objects, the present inventors have found that
olefin is (co-)polymerized by using a preactivated catalyst by
causing a catalyst for producing polyolefin to support a small
amount of polyolefin having a specific intrinsic viscosity to be
(co-) polymerized and a small amount of polyolefin having a
specific high intrinsic viscosity so that a polyolefin composition
having high melt tension and high crystallization temperature is
obtained. Thus, the present invention has been completed.
[0014] A first aspect of the invention is an olefin (co-)polymer
composition comprising: 0.01 to 5.0 weight parts of high molecular
weight polyethylene which is an ethylene homopolymer or an
ethylene-olefin copolymer containing 50 weight % or more of an
ethylene polymerization unit; and 100 weight parts of an olefin
(co-)polymer other than the high molecular weight polyethylene,
wherein the high molecular weight polyethylene has an intrinsic
viscosity [.eta..sub.E] of 15 to 100 dl/g measured in tetralin at
135.degree.C. or more, and the high molecular weight polyethylene
exists as dispersed fine particles having a numerical average
particle size of 1 to 5000 nm.
[0015] It is preferable that the intrinsic viscosity [.eta..sub.E]
is 15 to 50 dl/g, and more preferably, 17 to 50 dl/g. It is
preferable that the amount of the high molecular weight
polyethylene is 0.02 to 2.0 weight parts, and more preferably, 0.05
to 1.0 weight part. It is preferable that the numerical average
particle size of the high molecular weight polyethylene is 1 to
1000 nm, and more preferably, 10 to 500 nm.
[0016] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the intrinsic viscosity
[.eta..sub.r] of the olefin (co-)polymer composition that is
measured in tetralin at 135.degree.C. is 0.2 to 10 dl/g. It is
preferable that the intrinsic viscosity [.eta..sub.r] is 0.2 to 8
dl/g, and more preferably 0.7 to 5 dl/g.
[0017] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the olefin (co-)polymer
other than the high molecular weight polyethylene is at least one
selected from the group consisting of a propylene homopolymer and a
propylene-olefin copolymer containing of 50 weight % or more of a
propylene polymerization unit.
[0018] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the following relationship
is satisfied in the bulk state where no rubber component or
inorganic filler is present, as expressed by the following
formula:
log (G'(.omega.=10.sup.0))-log (G'(.omega.=10.sup.-2))<2,
[0019] a storage modulus being G'(.omega.=10.sup.0) with a
frequency of .omega.=10.sup.0 for a molten product of 230.degree.
C. and a storage modulus is G'(.omega.-10.sup.-2) with a frequency
of .omega.=10.sup.-2
[0020] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the following relationship
is satisfied in the state where electron beam radiation is not
performed:
log (N.sub.1)>-log (MFR)+5
[0021] a first normal stress difference being expressed by N.sub.1
with a shear rate of 4.times.10.sup.-1 (sec.sup.-1) at 190.degree.
C., 230.degree. C. and 250.degree. C., a metal flow rate (unit:
g/10 min) being expressed by MFR.
[0022] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the following relationship
is satisfied at 190.degree. C. and 250.degree.C.:
(N.sub.1(190.degree. C.)-N.sub.1(250.degree.
C.))/N.sub.1(190.degree. C.)<0.6
[0023] a first normal stress difference being expressed by N.sub.1
(190.degree.C.) and N.sub.1(250.degree. C.) with a shear rate of
4.times.10.sup.-1 (sec.sup.-1).
[0024] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the following relationship
is satisfied at 190.degree. C. and 250.degree. C.:
(MS(190.degree.C.)-MS(250.degree.C.))/MS(190.degree.C.)<3.1
[0025] a melt tension being expressed by MS (190.degree.C.) and
MS(250.degree. C.) with a shear rate of 3.times.10.sup.-1 (sec
).
[0026] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the following relationship
is satisfied:
(G(t=10)-G(t=300))/G(t=10)<1
[0027] a relaxation elastic modulus being expressed by G (t=10)
with t=10 (sec), and a relaxation elastic modulus being expressed
by G (t=300) with t=300 (sec) on the condition of 500% of a strain
of the molten product at 230.degree. C.
[0028] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that an elongational viscosity
is increased in a large deformation region when molten and
stretched to show strain hardening property. The term "large
deformation region" means more than certain value in stress where
the stress-strain relation is no longer linear. The stress in the
large deformation region is so large that strain is not
proportional to the stress.
[0029] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the high molecular weight
polyethylene fine particles are added before or during olefin
(co-)polymerization.
[0030] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the olefin (co-)polymer is
a propylene homopolymer or a propylene-olefin copolymer containing
50 weight % or more of a propylene polymerization unit, and the
olefin (co-)polymer composition satisfies the following
relationship between a melt tension (MS) at 230.degree. C. and an
intrinsic viscosity [.eta..sub.E] measured in tetralin at
135.degree.C.:
log (MS)>4.24.times.log [.eta..sub.E]-1.20.
[0031] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the olefin (co-)polymer is
a propylene homopolymer or a propylene-olefin copolymer containing
50 weight % or more of a propylene polymerization unit, and the
olefin (co-)polymer composition satisfies the following
relationship between a melt tension (MS) at 230.degree.C. and an
intrinsic viscosity [.eta..sub.E] measured in tetralin at
135.degree.C.:
4.24.times.log [.eta..sub.T+0.24>4.24.times.log
[.eta..sub.T]-1.10.
[0032] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the olefin (co-)polymer is
an ethylene homopolymer or an ethylene-olefin copolymer containing
50 weight % of an ethylene polymerization unit.
[0033] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that 0.001 to 2 weight parts of
at least one stabilizer selected from the group consisting of a
phenol antioxidant and a phosphoric antioxidant is added to 100
weight parts of the olefin (co-)polymer composition.
[0034] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the olefin (co-)polymer
other than high molecular polyethylene is a propylene homopolymer
or a propylene-olefin copolymer containing 50 weight % or more of a
propylene polymerization unit, the olefin (co-)polymer other than
high molecular polyethylene is produced by polymerizing propylene
or by copolymerizing propylene and another olefin having 2 to 12
carbon atoms in the presence of a preactivated catalyst comprising
an olefin producing catalyst and a polyethylene supported by the
olefin producing catalyst, and the olefin producing catalyst is
formed by the combination of a transitional metal compound catalyst
component containing at least a titanium compound, 0.01 to 1000 mol
of an organic metal compound (AL1) selected from the group
consisting of a metal that belongs to group I, group II, group XII
and group XIII of the periodic table published in 1991 with respect
to 1 mol of the transitional metal atom, and 0 to 500 mol of an
electron donor (E1) with respect to 1 mol of the transitional metal
atom.
[0035] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the composition is
obtained by polymerizing or copolymerizing either propylene alone
or a combination of propylene and an olefin having 2 to 12 carbons
in the presence of the preactivated catalyst, that the preactivated
catalyst further comprises an organic metal compound (AL2) and an
electron donor (E2), the organic metal compound (AL2) is a compound
of a metal selected from the group consisting of metals belonging
to Groups I , II, XII and XIII of the periodic table issued in
1991, the content of the organic metal compounds (AL1) and (AL2) is
0.05 to 5000 mole per mole of the transitional metal atom in the
preactivated catalyst, and the content of the electron donors (E1)
and (E2) is 0 to 3000 mole per mole of the transitional metal atom
in the preactivated catalyst.
[0036] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the preactivated catalyst
supports 0.01 to 5,000 g of polyethylene with an intrinsic
viscosity [.eta..sub.A] of 15 to 100 dl/g measured in tetralin at
135.degree.C. for 1 g of the transitional metal compound catalyst
component. It is preferable that the amount of polyethylene
supported for 1 g of the transitional metal compound catalyst
component is 0.05 to 2000 g, and more preferably, 0.1 to 1000
g.
[0037] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the preactivated catalyst
supports 0.01 to 100 g of polypropylene (B) and 0.01 to 5000 g of
polyethylene (A) per gram of the transitional metal compound
catalyst component, the polypropylene (B) has an intrinsic
viscosity [.eta..sub.B] of less than 15 dl/g measured in tetralin
at 135.degree. C., and is a propylene homopolymer or a
propylene-olefin copolymer comprising a propylene polymerization
unit at the rate of 50wt % or more, and the polyethylene (A) has an
intrinsic viscosity [.eta..sub.A] to 100 dl/g measured in tetralin
at 135.degree.C. It is preferable that the intrinsic viscosity
[.eta..sub.B] of the preliminarily polymerized polypropylene is 0.2
to 8 dl/g, and more preferably, 0.5 to 8 dl/g. The amount of the
preliminarily polymerized polypropylene for 1 g of the transitional
metal compound catalyst component is 0.01 to 50 g, and more
preferably, 0.5 to 50 g. Furthermore, it is preferable that the
content of the preliminarily polymerized polypropylene is 0.001 to
2 weight %, and more preferably 0.005 to 1.5 weight %, and most
preferably 0.001 to 1 weight %.
[0038] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the olefin (co-)polymer
other than high molecular polyethylene is produced by using 0.01 to
1,000 mmol of catalyst converted into a transitional metal atom in
a catalyst for 1 liter of (co-)polymerization volume of propylene
or another olefin.
[0039] In the first aspect of the invention, it is preferable in
the olefin (co-)polymer composition that the olefin (co-)polymer
other than high molecular polyethylene is produced by mixing a) a
propylene homopolymer or a propylene-olefin copolymer which
contains 50 weight % or more of a propylene polymerization unit,
the propylene homopolymer or propylene-olefin copolymer is produced
by polymerizing only propylene or by polymerizing or copolymerizing
propylene and another olefin having 2 to 12 carbon atoms in the
presence of a preactivated catalyst containing an olefin producing
catalyst and polyethylene supported by the olefin producing
catalyst, the olefin producing catalyst is formed by the
combination of a transitional metal compound catalyst component
containing at least a titanium compound, 0.01 to 1.000 mol of an
organic metal compound (AL1) selected from a group consisting of
metals that belong to group I, group II, group XII and group XIII
of the periodic table published in 1991 with respect to 1 mol of
the transitional metal atom, and 0 to 500 mol of an electron donor
(E1) with respect to 1 mol of the transitional metal atom, and b) a
propylene homopolymer or a propylene-olefin copolymer which
contains 50 weight % of a propylene polymerization unit.
[0040] The second aspect of the invention is a method for producing
an olefin (co-)polymer composition comprising the step of
polymerizing or copolymerizing olefin in the presence of a
preactivated catalyst comprising a polyolefin preparing catalyst
and a polyethylene to form an olefin (co-)polymer, wherein the
polyolefin preparing catalyst comprises (i) a transitional metal
compound catalytic component including at least a titanium
compound, (ii) an organic metal compound (AL1) and (iii) an
electron donor (E1), the organic metal compound (AL1) is a compound
of a metal selected from the group consisting of metals belonging
to Groups I , II, X II and X III according to the periodic table
issued in 1991, the content of the metal organic compound (AL1) is
0.01 to 1000 mole per mole of the transitional metal atom, the
content of the electron donor (E1) is 0 to 500 mole per mole of the
transition metal atom, and wherein the polyethylene is supported by
the polyolefin preparing catalyst and comprises ethylene
homopolymer or a ethylene-olefin copolymer comprising an ethylene
polymerization unit at the rate of 50wt % or more, the content of
polyethylene supported is 0.01 to 5000 g per gram of the
transitional metal compound catalytic component, and the
polyethylene has an intrinsic viscosity [.eta.] of 15 to 100 dl/g
measured in tetralin at 135.degree.C .
[0041] In the second aspect of the invention, it is preferable in
the method for producing an olefin (co-)polymer composition that
the olefin to be polymerized or copolymerized is propylene or an
olefin having 2 to 12 carbon atoms, and the olefin (co-)polymer is
a propylene homopolymer or a propylene-olefin copolymer comprising
50 weight % or more of a propylene polymerization unit and an
olefin having 2 to 12 carbon atoms.
[0042] In the second aspect of the invention, it is preferable that
the method for producing an olefin (co-)polymer composition further
comprises a step of adding an organic aluminum compound and an
electron donor (E2) to the preactivated catalyst, that the content
of the organic metal compound (AL1) and the organic aluminum
compound (AL2) in the preactivated catalyst is 0.05 to 5,000 molar
parts with respect to 1 mol of titanium atom, and the content of
the electron donors (E1) and (E2) in the preactivated catalyst is 0
to 3,000 molar parts with respect to 1 mol of titanium atom in the
preactivated catalyst.
[0043] In the second aspect of the invention, it is preferable in
the method for producing an olefin (co-)polymer composition that
the amount of titanium atom in the catalyst is 0.01 to 1,000 mmol
for 1 liter of olefin (co-)polymerization volume.
[0044] In the second aspect of the invention, it is preferable in
the method for producing an olefin (co-)polymer composition that
the preactivated catalyst comprises 0.01 to 100 g of polypropylene
(B) per gram of the transitional metal compound catalyst component,
and the polypropylene (B) has an intrinsic viscosity [.eta..sub.B]
of less than 15 dl/g measured in tetralin at 135.degree. C., and is
a propylene homopolymer or a propylene-olefin copolymer comprising
a propylene polymerization unit at the rate of 50 wt % or more.
[0045] In the second aspect of the invention, it is preferable in
the method for producing an olefin (co-)polymer composition that
the amount of the transitional metal atom in the catalyst is 0.01
to 1,000 mmol for 1 liter of olefin (co-)polymerization volume.
[0046] In the second aspect of the invention, it is preferable in
the method for producing an olefin (co-)polymer composition that
the method comprises the steps of: (a) a preliminary (co-)
polymerization process comprising polymerizing or copolymerizing
olefin in the presence of a polyolefin preparing catalyst to form
0.01 to 100 g of polyolefin (B) having an intrinsic viscosity
[.eta.] of less than 15 dl/g measured in tetralin at 135.degree.C.
per gram of the transition metal compound catalyst component, the
polyolefin preparing catalyst comprises (i) a transitional metal
compound catalytic component including at least a titanium
compound, (ii) an organic metal compound (AL1) and (iii) an
electron donor (E1), the organic metal compound (AL1) is a compound
of a metal selected from the group consisting of metals belonging
to Groups I, II, XII and XIII according to the periodic table
issued in 1991, the content of the metal organic compound (AL1) is
0.01 to 1000 mol per mol of the transitional metal atom, the
content of the electron donor (E1) is 0 to 500 mole per mole of the
transitional metal atom; (b) a preliminary activation (co-)
polymerization process comprising polymerizing or copolymerizing
olefin to form 0.01 to 100 g of polyolefin (A) having an intrinsic
viscosity [.eta.] of 15 to 100 dl/g measured in tetralin at
135.degree. C. per gram of the transitional metal compound catalyst
component; and (c) a main (co-)polymerization process comprising
polymerizing olefin having 2 to 12 carbons in the presence of a
preactivated catalyst for polymerizing olefin, the preactivated
catalyst is obtained by letting the transitional metal compound
catalyst component support polyolefins (B) and (A).
[0047] In the second aspect of the invention, it is preferable in
the method for producing an olefin (co-)polymer composition that
the method comprises the step of polymerizing or copolymerizing
olefin in the presence of: (a) a preactivated catalyst for
polymerizing or copolymerizing olefin which is obtained by a method
for letting the transitional metal compound catalyst component
support polyolefins (B) and (A) comprising the steps of: a
preliminary (co-)polymerization process comprising polymerizing or
copolymerizing olefin in the presence of a polyolefin preparing
catalyst to form 0.01 to 100 g of polyolefin (B) having an
intrinsic viscosity [.eta.] of less than 15 dl/g measured in
tetralin at 135.degree.C. per gram of the transitional metal
compound catalyst component, the polyolefin preparing catalyst
comprising (i) a transitional metal compound catalytic component
including at least a titanium compound, (ii) an organic metal
compound (AL1) and (iii) an electron donor (E1), the organic metal
compound (AL1) is a compound of a metal selected from the group
consisting of metals belonging to Groups I, II, XII and XIII
according to the periodic table issued in 1991, the content of the
metal organic compound (AL1) being 0.01 to 1000 mole per mole of
the transitional metal atom, the content of the electron donor (E1)
being 0 to 500 mole per mole of the transitional metal atom; and a
preliminary activation (co-)polymerization process comprising
polymerizing or copolymerizing olefin to form 0.01 to 100 g of
polyolefin (A) having an intrinsic viscosity [.eta.] of 15 to 100
dl/g measured in tetralin at 135.degree. C. per gram of the
transitional metal compound catalyst component, (b) an organic
metal compound (AL2) which is a compound of a metal selected from
the group consisting of metals belonging to Groups I, II, XII and
XIII according to the periodic table issued in 1991, the content of
the metal organic compounds (AL1) and (AL2) is 0.05 to 5000 mole
per mol of the transitional metal atom in the preactivated
catalyst, and (c) an electron donor (E2), the content of the
electron donors (E1) and (E2) being 0 to 3000 mole per mol of the
transitional metal atom.
[0048] In the second aspect of the invention, it is preferable that
the method for producing an olefin (co-)polymer composition further
comprises a step of adding 0.001 to 2 weight parts of at least one
stabilizer selected from the group consisting of a phenolic
antioxidant and a phosphoric antioxidant to the olefin (co-)polymer
after (co-)polymerizing an olefin.
[0049] In the second aspect of the invention, it is preferable to
produce an olefin (co-)polymer, comprising a step of adding 0 to
10,000 weight parts of an olefin (co-)polymer obtained by a known
method to 100 weight parts of an olefin (co-)polymer composition
obtained by the method as defined in the second aspect of the
invention, preferably 0 to 5,000 weight parts, and more preferably
0 to 2,000 weight parts.
[0050] The third aspect of the invention is a catalyst for olefin
(co-)polymerization comprising a transitional metal compound
catalyst which contains at least a titanium compound and an olefin
(co-)polymer (A) supported by the catalyst, wherein the olefin
(co-)polymer (A) has an intrinsic viscosity [.eta.] of 15 dl/g to
100 dl/g measured in tetralin at 135.degree.C., and the content of
the olefin (co-)polymer (A) is 0.01 to 5,000 g for 1 g of a
titanium containing solid catalyst component.
[0051] The forth aspect of the invention is a method for producing
a catalyst for olefin (co-)polymerization, comprising the step of
polymerizing or copolymerizing olefin in the presence of a
polyolefin preparing catalyst to form olefin (co-)polymer (A)
having an intrinsic viscosity [.eta.] of 15 to 100 dl/g measured in
tetralin at 135.degree.C. and to let a titanium containing solid
catalytic component support 0.01 to 5000 g of the olefin (co-)
polymer (A) per gram of titanium containing solid catalytic
component, wherein the polyolefin preparing catalyst comprises (i)
a transitional metal compound catalytic component including at
least a titanium compound, (ii) an organic metal compound (AL1) and
(iii) an electron donor (E1), the content of the organic metal
compound (AL1) is 0.01 to 1000 mole per mol of titanium atom, and
the content of the electron donor (E1) is 0 to 500 mole per mol of
titanium atom.
[0052] In the third and fourth aspects of the invention, it is
preferable in the catalyst for olefin (co-)polymerization that the
transitional metal compound catalyst component is obtained by the
combination of 0.01 to 1,000 mol of an organic metal compound (AL1)
selected from group I, group II, group XII and group XIII of the
periodic table published in 1991 with respect to 1 mol of the
transitional metal atom and 0 to 500 mol of an electron donor (E1)
with respect to 1 mol of the transitional metal atom.
[0053] In the third and fourth aspects of the invention, it is
preferable in the catalyst for olefin (co-)polymerization that the
olefin (co-)polymer (A) is an ethylene homopolymer or an
ethylene-olefin copolymer which contains 50 % or more of an
ethylene polymerization unit.
[0054] In the third and fourth aspects of the invention, it is
preferable that the catalyst for olefin (co-)polymerization further
comprises an organic aluminum compound and an electron donor (E1),
that the content of the organic aluminum compound is 0.01 to 1,000
mole per mol of titanium atom in the catalyst, and the content of
the electron donor (E1) is 0 to 500 mole per mol of titanium atom
in the catalyst.
[0055] In the third and fourth aspects of the invention, it is
preferable in the catalyst for olefin (co-)polymerization that a
polyolefin (B) to be (co-)polymerized is formed on a layer which is
lower than the polyolefin (A) to be (co-)polymerized, polyolefin
(B) has an intrinsic viscosity [.eta.] of less than 15 dl/g
measured in tetralin at 135.degree.C. and the content of the
polyolefin (B) is 0.01 to 100 g for 1 g of a transitional metal
compound component.
[0056] In the third and fourth aspects of the invention, it is
preferable in the catalyst for olefin (co-)polymerization that the
transitional metal compound catalyst component is a titanium
containing solid catalyst component whose main component is a
titanium trichloride composition or titanium tetrachloride.
[0057] In the third and fourth aspects of the invention, it is
preferable in the catalyst for olefin (co-)polymerization that the
organic metal compound (AL1) is an organic aluminum compound.
[0058] In the third and fourth aspects of the invention, it is
preferable in the catalyst for olefin (co-)polymerization that the
electron donor (E1) is an organic compound containing oxygen,
nitrogen, phosphorus or sulfur in a molecule, or an organic silicon
compound having Si--O--C bonding in a molecule.
[0059] In the third and fourth aspects of the invention, it is
preferable in the catalyst for olefin (co-)polymerization that the
polyolefin (B) is a homopolymer or copolymer of an olefin having 2
to 12 carbon atoms.
[0060] In the third and fourth aspects of the invention, it is
preferable that the catalyst for olefin (co-)polymerization further
comprises an electron donor (E2), that the content of the electron
donors (E1) and (E2) is 0 to 3,000 mole per mol of the transitional
metal atom in the catalyst.
[0061] In the third and fourth aspects of the invention, it is
preferable in the catalyst for olefin (co-)polymerization that the
electron donor (E2) is an organic compound containing oxygen,
nitrogen, phosphorus or sulfur in a molecule, or an organic silicon
compound having Si--O--C bonding in a molecule.
[0062] In the third and fourth aspects of the invention, it is
preferable that the catalyst for olefin (co-)polymerization further
comprises an organic metal compound (AL2) and an electron donor
(E2), that the organic metal compound (AL2) comprises a metal
selected from the group consisting of metals that belong to group
I, group II, group XII and group XIII of the periodic table
published in 1991, the content of the organic metal compounds (AL1)
and (AL2) is 0.05 to 5,000 mole with respect to 1 mole of a
transitional metal atom in the preactivated catalyst, and the
content of the electron donors (E1) and (E2) is 0 to 3000 mole with
respect to 1 mole of a transitional metal atom in the preactivated
catalyst.
BRIEF DESCRIPTION OF THE DRAWINGS
[0063] FIG. 1 is a photograph at 75000.times. magnification that is
obtained by observing a polymer composition according to Example 26
of the present invention by means of a transmission electron
microscope (TEM);
[0064] FIG. 2 is a traced diagram explaining the photograph of FIG.
1;
[0065] FIG. 3 is a TEM photograph of polypropylene that has
generally been known;
[0066] FIG. 4 is a traced diagram for explaining the photograph of
FIG. 3;
[0067] FIGS. 5 to 7 are charts showing the rheology behavior of the
polymer composition according to Example 26 of the present
invention and the relationship between a storage elastic modulus G'
and a frequency .omega.;
[0068] FIGS. 8 and 9 are charts showing the rheology behavior of
the polymer composition according to Example 26 of the present
invention and the relationship between a first normal stress
difference N.sub.1 and a shearing rate .gamma.;
[0069] FIGS. 10 and 11 are charts showing the rheology behavior of
the polymer composition according to Example 26 of the present
invention and the relationship between a relaxation elastic modulus
G(t) and time; and
[0070] FIGS. 12 and 13 are charts showing the rheology behavior of
the polymer composition according to Example 26 of the present
invention and the relationship between an elongational viscosity
and time.
PREFERRED EMBODIMENTS OF THE INVENTION
[0071] In the specification, the term "polyolefins" refers to
olefin polymers including (i) olefin homopolymers comprising olefin
monomers having 2 to 12 carbon atoms, (ii) olefin random copolymers
comprising at least 2 olefin monomers, and (iii) olefin block
copolymers comprising at least 2 olefin monomers. The terms
"polyethylenes", "ethylene polymers" and "ethylene-copolymers" are
meant to include ethylene polymers and ethylene copolymers
including (i) ethylene homopolymers, (ii) ethylene-olefin random
copolymers containing ethylene monomers at the rate of 50 wt % or
more, and (iii) ethylene-olefin block copolymers containing
ethylene monomers at the rate of 50 wt % or more. The term
"polypropylenes" refers to (i) polypropylene homopolymers, (ii)
propylene-olefin random copolymers containing propylene monomers at
the rate of 50 wt %, and (iii) propylene-olefin block copolymers
containing propylene monomers at the rate of 50 wt %. The term
"polyolefin composition" refers to a mixture of polyolefins
different from each other in the kind of monomers, the molecular
weight, the randomness, the blocking unit and the like. The term
"preliminary activation" means activation of a polyolefin-preparing
catalyst in activity prior to polymerization or copolymerization of
olefin. The preliminary activation is performed by polymerizing or
copolymerizing olefin in the presence of a polyolefin-preparing
catalyst to preliminarily activate for making the catalyst support
a polymerized or copolymerized olefin. The term "preactivated
catalyst" means a catalyst comprising a conventional
polyolefin-preparing catalyst and a small amount of at least two
polyolefins. Those two polyolefins are a polyolefin to polymerize
having a specific intrinsic viscosity and a polyolefin having a
specific and high intrinsic viscosity. The preactivated catalyst is
preliminarily activated by making the polyolefin-preparing catalyst
support the above two polyolefins. The conventional
polyolefin-preparing catalyst is a catalyst for conventional use in
preparing a polyolefin, and the conventional polyolefin-preparing
catalyst comprises a catalytic component of a transitional metal
compound including at least a titanium compound, an organic metal
compound, and if required, an electron donor. The catalytic
component of a transitional metal compound can be any known
polyolefin-preparing catalytic component containing a catalytic
component of a transitional metal compound including at least a
titanium compound as a main component. A titanium-containing solid
catalytic component is preferably used from among the known
catalytic components in terms of manufacture. The
titanium-containing solid catalytic component can be any from among
titanium-containing solid catalytic components containing a
titanium trichloride composition. Examples of the
titanium-containing solid catalytic components include those
proposed in Japanese Examined Patent Publication Nos. 56-3356,
59-28573, 63-66323 and the like, a titanium-containing supported
catalytic component including titanium, magnesium, halogen and
electron donor as essential components where a magnesium compound
supports titanium tetrachloride proposed in Japanese Unexamined
Patent Publication Nos. 62-104810, 62-104811, 62-104812, 57-63310,
57-63311, 58-83006, 58-138712 and the like.
[0072] The organic metal compound can be a compound having an
organic group (a ligand) of a metal selected from the group
consisting of Group I metals, Group II metals, Group XII metals and
Group XIII metals in terms of the periodic table issued in 1991.
Examples of the compound having an organic group (a ligand) of a
metal include organic lithium compounds, organic sodium compounds,
organic magnesium compounds, organic zinc compounds and organic
aluminum compounds. The organic metal compound can be used in
combination with the above-mentioned catalytic components of a
transitional metal compound. From among the examples, it is
preferable to use organic aluminum compounds represented by a
formula
AlR.sup.1.sub.pR.sup.2.sub.qX.sub.(3-(p+q))
[0073] wherein R.sup.1 and R.sup.2 each represent a hydrocarbon
group such as alkyl group, cycloalkyl group or aryl group, or an
alkoxy group, X represents a halogen atom, and p and q are a
positive integer satisfying a formula 0<p+q .ltoreq.3.
[0074] Examples of organic aluminum compounds include trialkyl
aluminums such as trimethyl aluminum, triethyl aluminum,
tri-n-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum,
tri-n-hexyl aluminum, tri-i-hexyl aluminum or tri-n-octyl aluminum;
dialkyl aluminum monohalides such as diethyl aluminum chloride,
di-n-propyl aluminum chloride, di-i-butyl aluminum chloride,
diethyl aluminum bromide or diethyl aluminum iodide; dialkyl
aluminum hydrides such as diethyl aluminum hydride; alkyl aluminum
sesquihalide such as ethyl aluminum sesquichloride; monoalkyl
aluminum dihalide such as ethyl aluminum dichloride; and
alkoxyalkyl aluminum such as diethoxy monoethyl aluminum,
preferably trialkyl aluminum or dialkyl aluminum monohalide. Those
organic aluminum compounds can be used either alone or in
combination.
[0075] The electron donor is, if required, used to control the
preparation rate and/or stereoregularity of the polyolefin.
Examples of the electron donor include organic compounds having any
of oxygen, nitrogen, sulfur and phosphorus in the molecule, such as
ethers, alcohols, esters, aldehydes, fatty acids, ketones,
nitriles, amines, amides, urea, isourea, isothiourea, isocyanates,
azo-compounds, phosphines, phosphites, hydrogen sulfide,
thioethers, neoalcohols, silanols and organic silicon compounds
containing an Si--O--C bond in molecule.
[0076] Examples of ethers include dimethyl ether, diethyl ether,
di-n-propyl ether, di-n-butyl ether, di-i-amyl ether, di-n-pentyl
ether, di-n-hexyl ether, di-i-hexyl ether, di-n-octyl ether,
di-i-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene
glycol monoethyl ether, diethylene glycol dimethyl ether and
tetrahydrofuran.
[0077] Examples of alcohols include methanol, ethanol, propanol,
butanol, pentanol, hexanol, octanol, 2-ethyl hexanol, allyl
alcohol, benzyl alcohol, ethylene glycol and glycerin.
[0078] Examples of phenols include phenol, cresol, xylenol, ethyl
phenol and naphthol.
[0079] Examples of esters include monocarboxylic acid esters such
as methyl methacrylate, methyl formate, methyl acetate, methyl
butyrate, ethyl acetate, vinyl acetate, propyl-n-acetate,
propyl-i-acetate, butyl formate, amyl acetate, butyl-n-acetate,
octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate,
ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate,
2-ethylhexyl benzoate, toluic acid methyl ester, toluic acid ethyl
ester, anisic acid methyl ester, anisic acid propyl ester, anisic
acid phenyl ester, ethyl cinnamate, naphthoic acid methyl ester,
naphthoic acid ethyl ester, naphthoic acid propyl ester, naphthoic
acid methyl ester, 2-ethylhexyl naphthoic acid, or ethyl
phenylacetate; aliphatic polycarboxylic acid esters such as diethyl
succinate, methylmalonic acid diethyl ester, butylmalonic acid
diethyl ester, dibutyl maleate or diethyl butylmaleic acid; and
aromatic polycarboxylic acid esters such as monomethyl phthalate,
dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate,
mono-n-butyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,
di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl
phthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl
isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate,
dipropyl terephthalate, dibutyl terephthalate or
naphthalenedicarboxylic acid diisobutylester.
[0080] Examples of aldehydes include acetaldehyde, propionaldehyde
and benzaldehyde. Examples of carboxylic acids include
monocarboxylic acids such as formic acid, acetic acid, propionic
acid, butyric acid, oxalic acid, succinic acid, acrylic acid,
maleic acid, valeric acid or benzoic acid; and acid anhydrides such
as benzoic anhydride, phthalic anhydride or tetrahydrophthalic
anhydride. Examples of ketones include acetone, methylethyl ketone,
methylisobutyl ketone and benzophenone.
[0081] Examples of nitrogen containing organic compounds include
nitriles such as acetonitrile or benzonitrile; amines such as
methyl amine, diethyl amine, tributyl amine, triethanol amine,
.beta.-(N,N-dimethylamin- o)ethanol, pyridine, quinoline,
.alpha.-picoline, 2,4,6-trimethyl pyridine, 2,2,5,6-tetramethyl
piperidine, 2,2,5,5-tetramethyl pyrrolidine, N,N,N',N-tetramethyl
ethylenediamine, aniline or dimethyl aniline; amides such as
formaldehyde, hexamethyl phosphoric acid triamide,
N,N,N',N',N'-pentamethyl-N'-.beta.-dimethylaminomethyl phosphoric
acid triamide or octamethyl pyrophosphoryl amide; ureas such as
N,N,N',N'-tetramethyl urea; isocyanates such as phenyl isocyanate
or toluyl isocyanate; azo compounds such as azobenzene.
[0082] Examples of the phosphorus containing compounds include
phosphines such as ethyl phosphine, triethyl phosphine, di-n-octyl
phosphine, tri-n-octyl phosphine, triphenyl phosphine or triphenyl
phosphine oxide; phosphites such as dimethyl phosphite, di-n-octyl
phosphite, triethyl phosphite, tri-n-butyl phosphite or triphenyl
phosphite.
[0083] Examples of the sulfur containing compounds include
thioethers such as diethyl thioether, diphenyl thioether or methyl
phenyl thioether; and thioalcohols such as ethyl thioalcohol,
n-propyl thioalcohol or thiophenol.
[0084] Examples of the organic silicon compounds include silanols
such as trimethyl silanol, triethyl silanol or triphenyl silanol;
and organic silicon compounds having a Si--O--C bond, such as
trimethyl methoxysilane, dimethyl dimethoxysilane, methylphenyl
dimethoxysilane, diphenyl dimethoxysilane, methyltrimethoxysilane,
vinyltrimethoxysilane, phenyltrimethoxysilane, trimethyl
ethoxysilane, dimethyl diethoxysilane, diisopropyl dimethoxysilane,
diisobutyl dimethoxysilane, diphenyl diethoxysilane, methyl
triethoxysilane, ethyl triethoxysilane, vinyl triethoxysilane,
cyclopentyl methyl dimethoxysilane, cyclopentyl trimethoxysilane,
dicyclopentyl dimethoxysilane, cyclohexyl methyl dimethoxysilane,
cyclohexyl trimethoxysilane, dicyclohexyl dimethoxysilane or
2-norbornyl methyl diethoxysilane.
[0085] The above electron donors can be used either alone or in
combination.
[0086] In the preactivated catalysts for olefin polymerization, a
polyolefin (A) has an intrinsic viscosity [.eta.] in the range of
15 to 100 dl/g, preferably 17 to 50 dl/g. The intrinsic viscosity
[.eta.] is to be measured in tetralin at 135.degree.C. The
polyolefin (A) is a monopolymer or copolymer comprising olefin
having 2 to 12 carbon atoms, preferably a monopolymer comprising
ethylene or propylene, or an ethylene- or propylene-olefin
copolymer comprising ethylene or propylene monomer at the rate of
50 wt % or more, preferably at least 70 wt %, further preferably at
least 90 wt %. Further, the polyolefin (A) is more preferably
ethylene monopolymer or ethylene-olefin copolymer comprising
ethylene monomer at the rate of 50 wt % or more, preferably at
least 70 wt %, further preferably at least 90 wt %.
[0087] A too small intrinsic viscosity [.eta.] of polyolefin (A)
can hardly provide a sufficient melting tension and a sufficient
crystallization temperature for the intended polyolefin composition
as a final product. The upper limit for the intrinsic viscosity
[.eta.] is not particularly specified. However, a preferable upper
limit can be about 100 dl/g in view of manufacturing efficiency and
the following reason; when the intrinsic viscosity [.eta.] of
polyolefin (A) is too different from that of the intended
polyolefin composition as a final product, polyolefin (A) cannot be
dispersed in the polyolefin composition, causing the melting
tension to be insufficient. Further, the intrinsic viscosity
[.eta.] of polyolefin (A) measured in tetralin at 135.degree. C.
has to be raised up to 15 dl/g to provide the final product with a
high molecular weight. For this reason, ethylene monopolymer or
ethylene-olefin copolymer comprising ethylene monomer at the rate
of 50 wt % or more is preferable in view of polymerization
efficiency.
[0088] Though the density of polyolefin (A) is not particularly
specified, a density of 880 to 980 g/l is preferred.
[0089] The amount of polyolefin (A) for a catalytic component of a
transitional metal compound to support is 0.01 to 5000 g per gram
of the catalytic component, preferably 0.05 to 2000 g, further
preferably 0.1 to 1000 g. Less than 0.01 g of polyolefin (A) per
gram of the catalytic component cannot provide the intended
polyolefin composition as a final product with a sufficient melting
tension and a sufficient crystallization temperature. More than
5000 g of polyolefin (A) per gram of the catalytic component is not
effective and can deteriorate the homogeneity of a final
product.
[0090] Examples of preferable olefin monomers for polyolefin (A)
include ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
1-octene, 1-decene, 4-methyl-1-pentene and 3-methyl-1-pentene. From
among those, ethylene, propylene, 1-butene and 4-methyl-1-pentene
are particularly preferable.
[0091] Polyolefin (B) is the same as the polyolefin to be
polymerized having an intrinsic viscosity [.eta.] of less than 15
dl/g measured in tetralin at 135.degree. C. Polyolefin (B) provides
polyolefin (A) contained in a polyolefin composition as a final
product with good dispersion in the composition. The intrinsic
viscosity [.eta.] of polyolefin (B) is preferred to be lower than
that of polyolefin (A) and be higher than that of a polyolefin
composition as a final product.
[0092] The amount of polyolefin (B) for use to let a catalytic
component of a transitional metal compound support is preferably
0.01 to 100 g per gram of the catalytic component. In other words,
the amount is preferred to be 0.001 to 1 wt % in terms of a
polyolefin composition as a final product. A too small amount of
polyolefin (B) prevents polyolefin (A) from dispersing in the
polyolefin composition as a final product. A too large amount of
polyolefin (B) makes preparation of the preactivated catalysts for
olefin polymerization less effective because the dispersibility is
saturated easily.
[0093] The preactivated catalysts for olefin polymerization are
prepared by a preliminary activation treatment which lets a
catalytic component of a transitional metal compound support
polyolefins (B) and (A). The preliminary activation treatment
comprises steps of a preliminary polymerization and a preliminary
activation polymerization in the presence of a polyolefin-preparing
catalyst. The preliminary polymerization preliminarily polymerizes
olefin to form polyolefin (B). The preliminary activation
polymerization polymerizes olefin to form polyolefin (A). The
polyolefin-preparing catalyst is a combination of a catalytic
component of a transitional metal compound containing at least a
titanium compound, an organic metal compound and, if required, an
electron donor.
[0094] In the polyolefin-preparing catalyst for the preliminary
activation treatment, the organic metal compound is 0.01 to 1000
molar parts, preferably 0.05 to 500 molar parts, and the electron
donor is 0 to 500 molar parts, preferably 0 to 100 molar parts per
molar part of the transitional metal contained in the catalytic
component of a transitional metal compound containing at least a
titanium compound.
[0095] The following method lets the catalytic component of a
transitional metal compound support polyolefins (B) and (A). First,
polyolefin (B) of 0.01 to 100 g per gram of a catalytic component
of a transitional metal compound is formed by preliminary
polymerization using 0.01 to 500 g of olefin to be polymerized in
the presence of the polyolefin-preparing catalyst of 0.001 to 5000
mmol, preferably 0.01 to 1000 mmol, in terms of transitional metal
atom in the catalyst component per liter of olefin polymerization
volume. In this process, no solvent or a solvent of at most 500 g
per gram of a catalytic component of a transitional metal compound
is used. Then polyolefin (A) of 0.01 to 5000 g per gram of a
catalytic component of a transitional metal compound is formed by
polymerization using 0.01 to 10000 g of olefin. The term
"polymerization volume" refers to a volume of liquid phase in a
polymerization container for liquid phase polymerization or a
volume of gas phase in a polymerization container for gas phase
polymerization.
[0096] The amount of the catalytic component of a transitional
metal compound for use is preferably within the above-mentioned
range in view of efficient and controlled polymerization of
polyolefin (A). A too small amount of the organic metal compound
for use makes polymerization inappropriately slow down. A too large
amount of the organic metal compound is not efficient because the
obtained polyolefin composition as a final product is apt to
contain much residue of the organic metal compound. A too large
amount of the electron donor for use makes polymerization
inappropriately slow down. A too large amount of the solvent for
use requires a large reactor and makes it difficult to efficiently
control polymerization.
[0097] The preliminary activation treatment is performed in liquid
phase using solvents. Examples of the solvents include aliphatic
hydrocarbons such as butane, pentane, hexane, heptane, octane,
isooctane, decane or dodecane; alicyclic hydrocarbons such as
cyclopentane, cyclohexane or methyl cyclohexane; aromatic
hydrocarbons such as toluene, xylene or ethylbenzene; inert
solvents such as gasoline fraction or hydrogenized diesel oil
fraction; and olefins. The preliminary activation treatment is also
performed in gas phase using no solvent.
[0098] To form a polyolefin (A) having a high molecular weight and
an intrinsic viscosity [.eta.] of 15 to 100 dl/g, the preliminary
activation treatment is preferably performed without using
hydrogen, though the treatment can be performed in the presence of
hydrogen.
[0099] The preliminary polymerization for polyolefin to be
polymerized is performed at a condition for forming polyolefin (B)
of 0.01 to 100 g per gram of a catalytic component of a
transitional metal compound, usually at -40 to 100.degree. C. and
0.1 to 5 MPa for lmin to 24 hr. The preliminary activation
polymerization is performed at a condition for forming 0.01 to 5000
g of polyolefin (A), preferably 0.05 to 2000 g, further preferably
0.1 to 100 g per gram of a catalytic component of a transitional
metal compound. That condition is usually at a low temperature such
as -40 to 40.degree. C., preferably -40 to 30.degree. C. , further
preferably -40 to 20.degree. C., and 0.1 to 5 MPa, preferably 0.2
to 5 MPa, further preferably 0.3 to 5 MPa for lmin to 24 hr,
preferably 5 min to 18 hr, further preferably 10 min to 12 hr.
[0100] After the preliminary activation is performed, an addition
polymerization can be performed by using 0.01 to 100 g of olefin to
be polymerized per gram of a catalytic component of a transitional
metal compound. The addition polymerization keeps an activity in
polymerization by the preliminary activation high. The amount of
the organic metal compound, electron donor, solvent and olefin is
within the same range as mentioned for the preliminary activation,
preferably an electron donor of 0.005 to 10 mol, preferably 0.01 to
5 mol. The addition polymerization is preferably performed at -40
to 100.degree. C. and 0.1 to 5 MPa for 1 min to 24 hr. The kind of
organic metal compounds, electron donors and solvents for the
addition polymerization can be the same as that in preliminary
activation polymerization. The kind of olefin for addition
polymerization is identical to the olefin to be polymerized.
[0101] The intrinsic viscosity [.eta.] of polyolefin obtained by
addition polymerization is at most within the range of intrinsic
viscosity [.eta.] of polyolefin (A). The intrinsic viscosity
[.eta.] of polyolefin obtained by addition polymerization is
incorporated in the final polyolefin.
[0102] To provide the intended polyolefin composition, the
preactivated catalyst can be used for main polymerization using
olefin having 2 to 12 carbon atoms, either alone or in combination
with an organic metal compound (AL2) and an electron donor
(E2).
[0103] The olefin main-polymerization catalyst comprises the
above-mentioned preactivated catalyst, organic metal compound (AL2)
and electron donor (E2). The total amount of the organic metal
compounds (AL1) and (AL2) for the polyolefin-preparing catalyst is
0.05 to 3000 mol, preferably 0.1 to 1000 mol per mol of the
transitional metal atom contained in the preactivated catalyst. The
total amount of the electron donors (E1) and (E2) for the
polyolefin-preparing catalyst is 0 to 5000 mol, preferably 0 to
3000 mol per mol of the transitional metal atom contained in the
preactivated catalyst.
[0104] When the total amount of the organic metal compounds (AL1)
and (AL2) is too small, a reaction rate in main polymerization of
olefin gets too slow. A too large amount of the organic metal
compounds (AL1) and (AL2) is not efficient and unpreferably makes
much residue of the organic metal compound in the obtained
polyolefin composition as a final product. A too large amount of
the electron donors (E1) and (E2) for the polyolefin-preparing
catalyst makes a reaction rate in main polymerization of olefin
extremely slow.
[0105] The kind of organic metal compound (AL2) and electron donor
(E2) to prepare an olefin main-polymerization catalyst is the same
as that of organic metal compound (AL1) and electron donor (E1).
The organic metal compound (AL1) and electron donor (E1) can each
be used either alone or in combination. The kind of organic metal
compound (AL2) and electron donor (E2) can be the same as that for
use in the preliminary activation treatment or be different from
that for use in the preliminary activation treatment.
[0106] The olefin main-polymerization catalyst can be a combination
of a powdery precipitate, organic metal compound (AL2) and, if
required electron donor (E2). The powdery precipitate can be mixed
with a solvent as a suspension. The powdery precipitate is formed
by removing the solvent, unreacted olefin, unreacted organic metal
compound (AL1) and electron donor (E1) from the preactivated
catalyst by filtration or decantation. The olefin
main-polymerization catalyst can also be a combination of another
powdery precipitate, organic metal compound (AL2) and, if required
electron donor (E2). This powdery precipitate is formed by
evaporating and removing the solvent and unreacted olefin from the
preactivated catalyst by reduced pressure distillation or inert gas
flow.
[0107] The polyolefin composition of the invention is prepared as
follows. Olefin is polymerized in the presence of a preactivated
catalyst or an olefin main-polymerization catalyst. The amount of
the preactivated catalyst or olefin main-polymerization catalyst
for use is 0.001 to 1000 mmol, preferably 0.005 to 500 mmol per
liter of polymerization volume in terms of a transitional metal
atom in the preactivated catalyst. The above-defined range of the
catalytic component of a transitional metal compound enables
efficient control of olefin polymerization.
[0108] The olefin main-polymerization can be performed by a known
polymerization process, such as slurry polymerization, bulk
polymerization, gas phase polymerization, liquid polymerization, or
a combination thereof. With slurry polymerization, olefin is
polymerized in solvents such as aliphatic hydrocarbon including
propane, butane, pentane, hexane, heptane, octane, isooctane,
decane or dodecane, alicyclic hydrocarbons including cyclopentane,
cyclohexane or methyl cyclohexane; aromatic hydrocarbons such as
toluene, xylene or ethylbenzene; inert solvents such as gasoline
fraction or hydrogenized diesel oil fraction; and olefins. With
bulk polymerization, olefin works as a solvent. With gas phase
polymerization, olefin is polymerized in a gas phase. With liquid
polymerization, polyolefin formed by polymerization is in a liquid
state. An example of preferable polymerization conditions for the
above processes is a temperature of 20 to 120.degree. C.,
preferably 30 to 100.degree. C., further preferably 40 to
100.degree. C., a pressure of 0.1 to 5 MPa, preferably 0.3 to 5 MPa
of continuous, semi-continuous or batch polymerization, and a
polymerization time of 5 min to 24 hr. This condition efficiently
forms polyolefin.
[0109] The polymerization condition is set to form polyolefin
formed in the main polymerization and a polyolefin composition as a
final product with an intrinsic viscosity [.eta.] of 0.2 to 10
dl/g, preferably 0.7 to 5 dl/g and to adjust polyolefin (A) derived
from the used preactivated catalyst to 0.01 to 5 wt % of the
composition. Similarly to known olefin polymerization, the
molecular weight of polymer is adjusted by the use of hydrogen in
polymerizing.
[0110] Less than 0.2 dl/g for the intrinsic viscosity [.eta.] for
the intended polyolefin composition results in deteriorated
mechanical properties of a final molded polyolefin product. More
than 10 dl/g for the intrinsic viscosity [.eta.] deteriorates
molding properties.
[0111] When the content of polyolefin (A) derived from the
preactivated catalyst is less than 0.01 wt % of the intended
polyolefin composition, the melting tension and crystallization
temperature for the polyolefin composition are not sufficiently
improved. More than 5 wt % of polyolefin (A) in the intended
polyolefin composition is not efficient, and the content value can
deteriorate homogeneity of the polyolefin composition.
[0112] Olefin having 2 to 12 carbon atoms is preferable to
polymerize in preparing the polyolefin composition of the
invention. Examples of preferred olefin include ethylene,
propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,
4-methyl-1-pentene and 3-methyl-1-pentene. From among those,
ethylene, propylene, 1-butene and 4-methyl-l-pentene are
particularly preferable. Those olefins can be used either alone or
in combination.
[0113] The polyolefin formed by main-polymerization can be olefin
homopolymer, or olefin-random or olefin-block copolymer comprising
olefin monomer at the rate of 50 wt % or more. The polyolefin is
preferably olefin homopolymer, olefin-random copolymer comprising
olefin monomer at the rate of 90 wt % or more or olefin-block
copolymer comprising olefin monomer at the rate of 70 wt %.
[0114] After main-polymerization of olefin, known processes such as
catalyst inactivation treatment, catalyst removing treatment and
drying are performed if required. Then the intended polyolefin
composition is finally provided. The intended polyolefin
composition has a high melting tension and a high crystallization
temperature.
[0115] The preliminary activation process provides polyolefin (A)
having a high molecular weight, and polyolefin (A) is evenly
dispersed in the polyolefin composition as a final product. Because
the invention uses the above process, the necessary amount of
preactivated catalyst can be prepared at a time. Further,
main-polymerization is performed by a conventional olefin
polymerization process. Therefore, similar productivity for
polyolefin is achieved, compared to conventional polyolefin
production.
[0116] The polyolefin composition prepared using the preactivated
catalyst in the invention has a high melting tension. When
polypropylene was used as olefin, a melting tension (MS) of the
obtained polypropylene composition has the following relation with
an intrinsic viscosity [.eta.] of the obtained polypropylene
composition, measured in tetralin at 135.degree.C.:
log(MS)>4.24.times.log[.eta.]-1.05
[0117] A too large melting tension deteriorates molding properties
of the obtained polyolefin composition. Therefore, a preferable
range for the invention is
4.24.times.log[.eta.]+0.05>log(MS)>4.24.times.log[.eta-
.]-1.05, preferably
4.24.times.log[.eta.]+0.24>log(MS)>4.24.times.lo-
g[.eta.]-1.05, more preferably
4.24.times.log[.eta.]+0.24>log(MS)>4.-
24.times.log[.eta.]0.93.
[0118] The term melting tension at 230.degree. C. refers to a
tension (cN) of a filament of a polyolefin measured in the
following condition: polyolefin is heated up to 230.degree. C., and
with a device named MELT TENSION II produced by TOYO SEIKI
SEIKAKU-SHO Ltd., melting polyolefin is extruded into air through a
nozzle having a diameter of 2.095 mm at a rate of 200 mm/min to
form a strand, and finally a tension of the filament of the
polyolefin is measured while the obtained strand is wound up at a
rate of 3.14 m/min.
[0119] After main-polymerization, known processes such as catalyst
inactivation treatment, catalyst removing treatment and drying are
performed if required. Then the intended polypropylene composition
is finally provided. The following explanation is an example of
polypropylene (PP) composition.
[0120] Phenol stabilizers are added to the composition to improve
thermal stability, melting tension and crystallization temperature
of the composition. The amount of the stabilizer for use is 0.001
to 2 weight parts, preferably 0.005 to 1.5 weight parts, further
preferably 0.01 to 1 weight part with respect to 100 weight parts
of polypropylene (PP) composition. The range for the amount
realizes effects of the stabilizer without inhibiting properties of
the composition as polyolefin (A). The range defined above is also
preferable in view of cost.
[0121] The phenol stabilizers can be any of known phenol
stabilizers having a phenol structure. Examples are
2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol,
2,6-dicyclohexyl-p-cresol, 2,6-diisopropyl-4-ethylphenol,
2,6-di-t-amyl-p-cresol, 2,6-di-t-octyl-4-n-propylphenol,
2,6-dicyclohexyl-4-n-octylphenol,
2-isopropyl-4-methyl-6-t-butylphenol,
2-t-butyl-4-ethyl-6-t-octylphenol,
2-isobutyl-4-ethyl-6-t-hexylphenol,
2-cyclohexyl-4-n-butyl-6-isopropylphe- nol,
2-t-butyl-6-(3'-t-butyl)-5'-methyl-2'hydroxybenzyl)-4-methylphenylacr-
ylate, t-butylhydroquinone,
2,2'-methylenebis(4-methyl-6-t-butylphenol),
4,4'-butylidenebis(3-methyl-6-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-b- utylphenol),
2,2'-thiobis(4-methyl-6-t-butylphenol),
4,4'-methylenebis(2,6-di-t-butylphenol),
2,2'-methylenebis[6-(1-methylcyc- lohexyl)-p-cresol],
2,2'-ethylidenebis(4,6-di-t-butylphenol),
2,2'-butylidenebis(2-t-butyl-p-cresol),
1,1,3-tris(2-methyl-4-hydroxy-5-t- -butylphenyl)butane,
triethyleneglycol-bis[3-(3-t-butyl-5-metyl-4-hydroxyp-
henyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)pr- opionate],
2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-
ate], n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate,
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide),
3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethylester,
1,3,5-tris(2,6-dimetyl-3-hydroxy-4-t-butylbenzyl)isocyanurate,
1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propyonyloxyethyl]isocyanurate-
,
2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,
bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl)calcium,
bis(3,5-di-t-butyl-4-hydroxybenzylphosphoric acid ethyl)nickel,
N,N'-bis[3,5-di-t-butyl-4-hydroxyphenyl)propyonyl]hydrazine,
2,2'-methylenebis(4-methyl-6-t-butylphenol)terephthalate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
3,9-bis[l,1-dimethyl-2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionylox-
y}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane,
2,2-bis[4-{2-(3,5-di-t-butyl-
-4-hydroxyhydrocinnamoyloxy)}ethoxyphenyl]propane,
.beta.-(3,5-di-t-butyl-- 4-hydroxyphenyl)propionate alkylester, and
the like.
[0122] In particular, preferred examples are
2,6-di-t-butyl-p-cresol,
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,
n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate,
2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylat-
e, 2,2'-ethylidenebis(4,6-di-t-butylphenyl), and the like. A
phenolic stabilizer can be solely used, or two or more kinds of
phenolic stabilizers can be combined for use.
[0123] In the present invention, a phosphoric antioxidant is
blended as a component which displays high melt tension, high
crystallization temperature of a polypropylene composition which
should be obtained during molding, heat resistant oxidation
properties, weather resistance, and coloring prevention.
[0124] The blending amount is 0.001 to 2 weight parts, more
preferably 0.005 to 1.5 weight parts, most preferably 0.01 to 1
weight part with respect to 100 weight parts of a polypropylene
composition (PP) of a component A) with respect to the display of
performance of the polypropylene composition according to the
present invention and the cost of the antioxidant.
[0125] The phosphoric antioxidant which is used for the
polypropylene composition according to the prior art can be
utilized without restriction. More specifically, examples are as
follows. The phosphoric antioxidant can be solely used, or two or
more kinds of phosphoric antioxidants can be used together.
[0126] Examples of biphenylene-di-phosphonate are
tetrakis(2,4-di-t-butylp- henyl)-4,4'-biphenylene-di-phosphonate,
tetrakis(2,4-di-t-amylphenyl)-4,4'- -biphenylene-di-phosphonate,
tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'--
biphenylene-di-phosphonate,
tetrakis(2,6-di-t-butyl-4-methylphenyl)-4,4'-b-
iphenylene-di-phosphonate,
tetrakis(2,6-di-t-butyl-4-n-octadecyloxycarbony-
lethyl-phenyl)-4,4'-biphenylene-di-phosphonate,
tetrakis[2,6-di-t-butyl-4--
(2',4'-di-t-butylphenoxycarbonyl)-phenyl]-4,4'-biphenylene-di-phosphonate,
tetrakis(2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl)-4,4'-biphenylene-
-di-phosphonate,
bis[2,2'-methylene-bis(4-methyl-6-t-butylphenyl)]-4,4'-bi-
phenylene-di-phosphonate,
bis[2,2'-methylene-bis(4,6)-di-t-butylphenyl)]-4-
,4'-biphenylene-di-phosphonate,
bis(2,2'-ethylidene-bis(4-methyl-6-t-butyl-
phenyl)]-4,4'-biphenylene-di-phosphonate,
bis[2,2'-ethylidene-bis(4,6-di-t-
-butylphenyl)]-4,4'-biphenylene-d-phosphonate, and the like.
[0127] Examples are catecyl-2,6-di-t-butyl-4-methylphenylphosphite,
catecyl-2,4,6-tri-t-butylphenylphosphite,
.alpha.-naphthylcatecylphosphit- e,
2,2'-methylenebis(4-methyl-6-t-butylphenyl)-2-naphthylphosphite,
4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecylphosphite),
1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane,
trilauryltrithiophosphite, tricetyltrithiophosphite,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
triphenylphosphite, tris(nonylphenyl)phosphite,
tris(2,4-di-nonylphenyl)p- hosphite, tris(mono-, or
di-nonylphenyl)phosphite, tris(2,4-di-t-butylphen- yl)phosphite,
tris(2,6-di-t-butyl-4-methylphenyl)phosphite, and the like.
[0128] Examples of pentaerythritol-diphosphite are
distearyl-pentaerythrit- ol-diphosphite,
diphenyl-pentaerythritol-diphosphite,
bis(nonylphenyl)-pentaerythritol-diphosphite,
bis(2,4-di-t-butylphenyl)pe- ntaerythritol-diphosphite,
bis(2,4-di-t-amylphenyl)pentaerythritol-diphosp- hite,
bis(2,4-dicumylphenyl)pentaerythritol-diphosphite,
bis(2,4-di-t-butyl-5-methylphenyl)-pentaerythritol-diphosphite,
bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-diphosphite,
bis(2,6-di-t-butyl-4-s-butylphenyl)pentaerythritol-diphosphite,
bis(2,4,6-tri-t-butylphenyl)pentaerythritol-diphosphite,
bis(2,4,6-tri-t-amylphenyl)pentaerythritol-diphosphite,
bis(2,4,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl)pentaerythritol-
-diphosphite,
bis[2,6-di-t-butyl-4-(2',4'-di-t-butylphenoxycarbonyl)-pheny-
l]pentaerythritol-diphosphite,
bis(2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-
-phenyl)pentaerythritol-diphosphite, and the like.
[0129] Examples of tetraoxaspiro[5.5]undecane-diphosphite are
tetrakis(2,4-di-t-butylphenyl)-3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8-
,10-tetraoxaspiro[5.5]undecane-diphosphite,
tetrakis(2,4-di-t-amylphenyl)--
3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane-d-
iphosphite,
tetrakis(2,6-di-t-butyl-4-methylphenyl)-3,9-bis(1,1-dimethyl-2-
-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane-diphosphite,
tetrakis(2,4,6-tri-t-butylphenyl)-3,9-bis(l,l-dimethyl-2-hydroxyethyl)-2,-
4,8,10-tetraoxaspiro[5.5]undecane-diphosphite,
tetrakis(2,4,6-tri-t-amylph-
enyl)-3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-diphosphite,
tetrakis(2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-ph-
enyl)-3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-diphosphite,
tetrakis[2,6-di-t-butyl-4-(2',4'-di-t-butylphenoxycarbon-
yl-phenyl]-3,9-bis(1,l-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5-
]undecane-diphosphite,
tetrakis(2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-ph-
enyl)-3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-diphosphite,
bis[2,2'-methylene-bis(4-methyl-6-t-butylphenyl)]-3,9-bi-
s(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane-diphosp-
hite,
bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)]-3,9-bis(1,1-dimethyl-2-
-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane-diphosphite,
bis[2,2'-methylene-bis(4,6-di-t-amylphenyl)]-3,9-bis(l,l-dimethyl-2-hydro-
xyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane-diphosphite,
bis[2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)]-3,9-bis(1,1-dimetyl-2--
hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane-diphosphite,
bis[2,2'-ethylidene-bis(4,6-di-t-butylphenyl)]-3,9-bis(1,1-dimethyl-2-hyd-
roxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane-diphosphite,
bis[2,2'-ethylidene-bis(4,6-di-t-amylphenyl)]-3,9-bis(1,1-dimethyl-2-hydr-
oxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-diphosphite, and the
like.
[0130] Examples of 2,2'-bis(4,6-di-t-butylphenyl)phosphite are
2,2'-bis(4,6-di-t-butylphenyl)octylphosphite,
2,2'-bis(4,6-di-t-butylphen- yl)nonylphosphite,
2,2'-bis(4,6-di-t-butylphenyl)laurylphosphite,
2,2'-bis(4,6-di-t-butylphenyl)tridecylphosphite,
2,2'-bis(4,6-di-t-butylp- henyl)myristylphosphite,
2,2'-bis(4,6-di-t-butylphenyl) stearylphosphite,
2,2'-bis(4,6-di-t-butylphenyl)(2,4-di-t-butylphenyl)phosphite,
2,2'-bis(4,6-di-t-butylphenyl)(2,6-di-t-butyl-4-methylphenyl)phosphite,
2,2'-bis(4,6-di-t-butylphenyl)(2,4,6-tri-t-butylphenyl)phosphite,
2,2'-bis(4,6-di-t-butylphenyl)(2,6-di-t-butyl-4-n-octadecyloxycarbonyleth-
yl-phenyl)phosphite,
2,2'-bis(4,6-di-t-butylphenyl)[2,6-di-t-butyl-4-(2',4-
'-di-t-butylphenoxycarbonyl)-phenyl]phosphite,
2,2'-bis(4,6-di-t-butylphen-
yl)(2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl)phosphite, and
the like.
[0131] Examples of
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)phosphite are
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)octylphosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)nonylphosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)laurylphosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)tridecylphosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)myristylphosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)stearylphosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)(2,4-di-t-butylphenyl)phosphi-
te,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)(2,6-di-t-butyl-4-methylph-
enyl)phosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)(2,4,6-tri-t-b-
utylphenyl)phosphite,
2,2'-methylene-bis(4-methyl-6-t-buthylphenyl)(2,6-di-
-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl)phosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)[2,6-di-t-butyl-4-(2',4'-di-t-
-butylphenoxycarbonyl)-phenyl]phosphite,
2,2'-methylene-bis(4-methyl-6-t-b-
utylphenyl)(2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl)phosphite,
and the like.
[0132] Examples of
2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphite are
2,2'-methylene-bis(4,6-di-t-butylphenyl)octylphosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)nonylphosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)laurylphosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)tridecylphosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)myristylphosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)stearylphosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)(2,4-di-t-butylphenyl)phosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)(2,6-di-t-butyl-4-methylphenyl)ph-
osphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)(2,4,6-tri-t-butylphenyl)-
phosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)(2,6-di-t-butyl-4-n-oct-
adecyloxycarbonylethyl-phenyl)phosphite,
2,2'-methylene-bis(4,6-di-t-butyl-
phenyl)[2,6-di-t-butyl-4-(2',4'-di-t-butylphenoxycarbonyl)-phenyl]phosphit-
e,
2,2'-methylene-bis(4,6-di-t-butylphenyl)(2,6-di-t-butyl-4-n-hexadecylox-
ycarbonyl-phenyl)phosphite, and the like.
[0133] Examples of 2,2'-methylene-bis(4,6-di-t-amylphenyl)phosphite
are 2,2'-methylene-bis(4,6-di-t-amylphenyl)octylphosphite,
2,2'-methylene-bis( 4,6-di-t-amylphenyl)stearylphosphite, 2,
2'-methylene-bis(4,6-di-t-amylphenyl) (2,
4-di-t-butylphenyl)phosphite,
2,2'-methylene-bis(4,6-di-t-amylphenyl)
(2,6-di-t-butyl-4-methylphenyl)ph- osphite,
2,2'-methylene-bis(4,6-di-t-amylphenyl) (2,4,6-tri-t-amylphenyl)p-
hosphite, 2,2'-methylene-bis(4,6-di-t-amylphenyl)
(2,6-di-t-butyl-4-n-octa- decyloxycarbonylethyl-phenyl)phosphite,
2,2'-methylene-bis(4,6-di-t-amylph-
enyl)[2,6-di-t-butyl-4-(2',4'-di-t-butylphenoxycarbonyl)-phenyl]phosphite,
2,2'-methylene-bis(4,6-di-t-amylphenyl
(2,6-di-t-butyl-4-n-hexadecyloxyca- rbonyl-phenyl)phosphite, and
the like.
[0134] Examples of
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)phosphite are
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)octylphosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)nonylphosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)laurylphosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)tridecylphosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)myristylphosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)stearylphosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)(2,4-di-t-butylphenyl)phosph-
ite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)(2,6-di-t-butyl-4-methyl-
phenyl)phosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)(2,4,6-tri--
t-butylphenyl)phosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)(2,6-
-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl)phosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)[2,6-di-t-butyl-4-(2',4'-di--
t-butylphenoxycarbonyl)-phenyl]phosphite,
2,2'-ethylidene-bis(4-methyl-6-t-
-butylphenyl)(2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl)phosphite,
and the like.
[0135] Examples of
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)phosphite are
2,2-ethylidene-bis(4,6-di-t-butylphenyl)octylphosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)nonylphosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)laurylphosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)tridecylphosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)myristylphosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)stearylphosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)(2,4-di-t-butylphenyl)phosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)(2,6-di-t-butyl-4-methylphenyl)p-
hosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)(2,4,6-tri-t-butylpheny-
l)phosphite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)(2,6-di-t-butyl-4-n--
octadecyloxycarbonylethyl-phenyl)phosphite,
2,2'-ethylidene-bis(4,6-di-t-b-
utylphenyl)[2,6-di-t-butyl-4-(2',4'-di-t-butylphenoxycarbonyl)-phenyl]phos-
phite,
2,2'-ethylidene-bis(4,6-di-t-butylphenyl)(2,6-di-t-butyl-4-n-hexade-
cyloxycarbonyl-phenyl)phosphite, and the like.
[0136] Examples of
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)phosphite are
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)octylphosphite,
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)stearylphosphite,
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)(2,4-di-t-amylphenyl)phosphite,
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)(2,4,6-tri-t-amylphenyl)phosphite-
, 2,2'-ethylidene-bis(4,6-di-t-amylphenyl)
(2,6-di-t-butyl-4-n-octadecylox- ycarbonylethyl-phenyl)phosphite,
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)[-
2,6-di-t-butyl-4-(2',4'-di-t-butylphenoxycarbonyl)-phenyl]phosphite,
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)
(2,6-di-t-butyl-4-n-hexadecyloxy- carbonyl-phenyl)phosphite, and
the like.
[0137] Examples of 2,2'-thio-bis(4-methyl-6-t-butylphenyl)phosphite
are 2,2'-thio-bis(4-methyl-6-t-butylphenyl)octylphosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)nonylphosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)laurylphosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)tridecylphosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)myristylphosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)stearylphosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)
(2,4-di-t-butylphenyl)phosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)
(2,6-di-t-butyl-4-methylphenyl)ph- osphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)(2,4,6-tri-t-butylphenyl)p-
hosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)(2,6-di-t-butyl-4-n-octad-
ecyloxycarbonylethyl-phenyl)phosphite,
2,2'-thio-bis(4-methyl-6-t-butylphe-
nyl)[2,6-di-t-butyl-4-(2',4'-di-t-butylphenoxycarbonyl-phenyl]phosphite,
2,2'-thio-bis(4-methyl-6-t-butylphenyl)(2,6-di-t-butyl-4-n-hexadecyloxyca-
rbonyl-phenyl)phosphite, and the like.
[0138] Examples of fluorophosphite are
2,2'-bis(4,6-di-t-butylphenyl)fluor- ophosphite,
2,2'-bis(4-methyl-6-t-butylphenyl)fluorophosphite,
2,2'-bis(4-t-amyl-6-methylphenyl)fluorophosphite,
2,2'-bis(4-s-eicosylphe- nyl)fluorophosphite,
2,2'-methylene-bis(4-methyl-6-t-butylphenyl)fluoropho- sphite,
2,2'-methylene-bis(4-ethyl-6-t-butylphenyl)fluorophosphite,
2,2'-methylene-bis(4-methyl-6-nonylphenyl)fluorophosphite,
2,2'-methylene-bis(4,6-dinonylphenyl)fluorophosphite,
2,2'-methylene-bis(4-methyl-6-cyclohexylphenyl)fluorophosphite,
2,2'-methylene-bis(4-methyl-6-(1'-methylcyclohexyl)phenyl)fluorophosphite-
, 2,2'-i-propylidene-bis(4-nonylphenyl)fluorophosphite,
2,2'-butylidene-bis(4,6-dimethylphenyl)fluorophosphite,
2,2'-methylene-bis(4,6-di-t-butylphenyl)fluorophosphite,
2,2'-methylene-bis(4,6-di-t-amylphenyl)fluorophosphite,
2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)fluorophosphite,
2,2'-ethylidene-bis(4-ethyl-6-t-butylphenyl)fluorophosphite,
2,2'-ethylidene-bis(4-s-butyl-6-t-butylphenyl)fluorophosphite,
2,2'-ethylidene-bis(4, 6-di-t-butylphenyl)fluorophosphite,
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)fluorophosphite,
2,2'-methylene-bis(4-methyl-6-t-octylphenyl)fluorophosphite,
2,2'-butylidene-bis(4-methyl-6-1'-methylcyclohexyl)phenyl)fluorophosphite-
, 2,2 '-methylene -bis (4,6-dimethylphenyl)fluorophosphite, 2, 2'-
thio-bis(4-t-octylphenyl)fluorophosphite,
2,2'-thio-bis(4,6-di-s-amylphen- yl)fluorophosphite,
2,2'-thio-bis(4,6-di-i-octylphenyl)fluorophosphite,
2,2'-thio-bis((5-t-butylphenyl)fluorophosphite,
2,2'-thio-bis(4-methyl-6-- t-butylphenyl)fluorophosphite,
2,2'-thio-bis(4-methyl-6-.alpha.-methylbenz-
ylphenyl)fluorophosphite, 2,2 '-thio
-bis(3-methyl-4,6-di-t-butylphenyl)fl- uorophosphite,
2,2'-thio-bis(4-t-amylphenyl)fluorophosphite, and the like:
[0139] Examples of diphosphite are
bis[2,2'-methylene-bis(4,6-di-t-butylph-
enyl)]-ethyleneglycol-diphosphite,
bis[2,2'-methylene-bis(4,6-di-t-butylph-
enyl)]-1,4-butanediol-diphosphite,
bis[2,2'-methylene-bis(4,6-di-t-butylph-
enyl)]-1,6-hexanediol-diphosphite,
bis[2,2'-methylene-bis(4-methyl-6-t-but-
ylphenyl)]-3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5-
]undecane-diphosphite,
bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)]-3',9--
bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-dipho-
sphite,
bis[2,2'-methylene-bis(4,6-di-t-amylphenyl)]-3,9-bis(1,1-dimethyl--
2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-diphosphite,
bis[2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)]-3,9-bis(1,1-dimethyl-2-
-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-diphosphite,
bis[2,2'-ethylidene-bis(4,6-di-t-butylphenyl)]-3,9-bis(1,1-dimethyl-2-hyd-
roxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-diphosphite,
bis[2,2'-ethylidene-bis(4,6-di-t-amylphenyl)]-3,9-bis(1,1-dimethyl-2-hydr-
oxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-diphosphite, and
bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)]-N,N'-bis(2-hydroxyethyl)oxa-
mide-diphosphite, and the like.
[0140] Examples of triphosphite are
tris[2,2'-methylene-bis(4,6-di-t-butyl-
phenyl)]-glycerin-triphosphite,
tris[2,2'-methylene-bis(4,6-di-t-butylphen-
yl)]-trimethylolethane-triphosphite,
tris[2,2'-methylene-bis(4,6-di-t-buty-
lphenyl)]-trimethylolpropane-triphosphite,
tris[2,2'-bis(4,6-di-t-butylphe-
nyl)]-triethanolamine-triphosphite,
tris[2,2'-bis(4,6-di-t-amylphenyl)]-tr- iethanolamine-triphosphite,
tris[2,2'-methylene-bis(4,6-di-t-butylphenyl)]-
-triethanolamine-triphosphite,
tris[2,2'-methylene-bis(4,6-di-t-amylphenyl-
)]-triethanolamine-triphosphite,
tris[2,2'-ethylidene-bis(4,6-di-t-butylph-
enyl)]-triethanolamine-triphosphite,
tris[2,2'-ethylidene-bis(4,6-di-t-amy-
lphenyl)]-triethanolamine-triphosphite,
tris[2,2'-methylene-bis(4,6-di-t-b-
utylphenyl)]-N,N',N"-tris(2-hydroxyethyl)isocyanurate-triphosphite,
and the like.
[0141] Examples of the phosphoric antioxidant are
tetrakis[2,2'-methylene--
bis(4,6-di-t-butylphenyl)]-erythritol-tetraphosphite,
tetrakis[2,2'-methylene-bis(4,6-di-t-butylphenyl)]-pentaerythritol-tetrap-
hosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethylphosphite,
bis(2,4-di-t-butyl-6-methylphenyl)-2-ethylhexylphosphite,
bis(2,4-di-t-butyl-6-methylphenyl)stearylphosphite,
2,4,6-tri-t-butylphenyl-2-ethyl-2-butyl-1,3-propanediolphosphite,
and the like.
[0142] For the compositions according to the present invention,
antioxidants other than the phosphoric antioxidants can be used so
as to accomplish the objects of the present invention.
[0143] Examples of the antioxidant are the well-known phenolic
antioxidants and thio antioxidants which are used for polypropylene
compositions. Examples of the thio antioxidant include
dimyristylthiodipropionate, distearylthiodipropionate,
laurylstearylthiodipropionate, dilaurylstearylthiodipropionate,
pentaerythritol-tetrakis(3-laurylthiopropionate),
dioctadecyldisulfide, distearylthiodibutylate, and the like.
[0144] These phenolic and thio antioxidants can be used solely or
in combination with two or more kinds of phenolic antioxidants.
[0145] The content of those antioxidants for use is each 0.001 to
1.5 weight parts to 100 weight parts of the polypropylene
composition, preferably 0.005 to 1 weight part, particularly
preferably 0.01 to 0.5 weight part.
[0146] For the compositions according to the present invention,
stabilizers other than the above can be used so as to accomplish
the objects of the present invention.
[0147] Examples of the stabilizers include a halogen scavenger. The
halogen scavenger works to capture halogen remaining as a residue
of the catalyst in polypropylene contained in the composition. The
use of the halogen scavenger improves the compositions of the
invention in terms of thermal stability, odors, hue, corrosion
resistance, weather resistance and the like.
[0148] The halogen scavengers can be any of fatty acid metal salts,
alkanoyl lactic acid metal salts, aliphatic hydroxy acid metal
salts, hydrotalcites, lithium aluminum complex hydroxide salts,
metal oxides, metal hydroxides, metal carbonates, metal aliphatic
phosphates, epoxy compounds, aliphatic amines, aliphatic amides,
hindered amine compounds, aminotriazine compounds, and the
like.
[0149] Examples of the halogen scavengers include metal salts of
aliphatic acids such as acetic acid, propionic acid, butyric acid,
valeric acid, .alpha.-methyl butyric acid, hexanoic acid, sorbic
acid, octanoic acid, 2-ethyl hexanoic acid, nonanoic acid, decanoic
acid, 9-decenic acid, undecanoic acid, undecylenic acid, lauric
acid, linderic acid, myristic acid, physeteric acid, myristoleic
acid, palmitic acid, palmitoleic acid, hiragoic acid, stearic acid,
petroselinic acid, oleic acid, elaidic acid, cis-11-octadecenic
acid, vaccenic acid, linolic acid, .alpha.-eleostearic acid,
.beta.-eleostearic acid, punicic acid, linolenic acid,
.gamma.-linolenic acid, moroctic acid, stearidonic acid, stearolic
acid, arachic acid, gadoleic acid, cis-11-eicosenic acid,
arachidonic acid, behenic acid, cetoleic acid, erucic acid,
brassidic acid, clupanodonic acid, lignoceric acid, selacholeic
acid, 4,8,12,15,18,21-tetracohexanic acid, cerotic acid, ximeric
acid, montanic acid, melissic acid, lumequeic acid; metal salts of
alkanoyl lactic acids such as dodecanoyl lactic acid,
tetradodecanoyl lactic acid, octadecanoyl lactic acid; metal salts
of aliphatic hydroxy acids such as glycollic acid, lactic acid,
hydracrylic acid, .alpha.-hydroxybutyric tartronic acid, glyceric
acid, malic acid, tartaric acid, methotartaric acid, racemic acid,
citric acid, 2-hydroxytetradecanoic acid, ipurolic acid,
2-hydroxyhexadecanoic acid, jalapinolic acid, juniperic acid,
ambrettolic acid, 9,10,16-trihydroxyhexadecenic acid,
2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid,
18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid,
ricinoleic acid, kamlolenic acid, licanic acid, 22-hydroxydocosanic
acid or cerebronic acid; metal alicyclic carboxylates such as metal
naphthenates; metal aromatic carboxylates derived from aromatic
carboxylic acids such as benzoic acid or p-t-butyl-benzoic acid;
metal alicyclic hydroxylates derived from alicyclic hydroxy acids
such as hydroxy naphthenic acid; metal aromatic hydroxylates
derived from aromatic hydroxylic acid such as salicylic acid,
m-hydroxy benzoic acid, p-hydroxy benzoic acid or
3,5-di-t-butyl-4-hydroxy benzoic acid; a variety of metal amino
carboxylates; lithium aluminum complex hydroxide metal salts of
basic aluminum lithium hydroxy carbonate hydrate and basic aluminum
lithium hydroxy sulfate hydrate; metal oxides; metal hydroxides;
metal carbonates; and metal phosphates.
[0150] Examples of metal salt of aliphatic phosphate are (mono-, or
di-mixed)hexylphosphate, (mono, dimixed)octylphosphate, (mono-, or
di-mixed)2-ethylhexylphosphate, (mono-, or di-mixed)decylphosphate,
(mono-, or di-mixed)laurylphosphate, (mono-, or
di-mixed)myristylphosphat- e, (mono-, or
di-mixed)palmitylphosphate, (mono-, or di-mixed)stearylphosphate,
(mono-, or di-mixed)oleylphosphate, (mono-, or
di-mixed)linoleicphosphate, (mono-, or di-mixed)linoleylphosphate,
(mono-, or di-mixed)docosylphosphate, (mono-, or
di-mixed)erucylphosphate- , (mono-, or
di-mixed)tetracosylphosphate, (mono-, or
di-mixed)hexacosylphosphate, (mono-, or
di-mixed)octacosylphosphate, and the like.
[0151] Examples of metal salt of aromatic phosphate are
bis(p-t-butylphenyl)phosphate, mono(p-t-butylphenyl)phosphate,
2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate,
2,2'-methylene-bis(4,6-di-t-amylphenyl)phosphate,
2,2'-ethylidene-bis(4,6- -di-t-butylphenyl)phosphate,
2,2'-ethylidene-bis(4,6-di-t-amylphenyl)phosp- hate, and the
like.
[0152] Further examples are tribasic sulfate, hydrazone, alkene,
cyclic ester, organic metal compounds, benzhydrol, epoxy compounds
such as condensation product of epichlorohydrin and bisphenol A,
condensation product of 2-methylepichlorohydrin and bisphenol A,
triglycidylisocyanurate, epoxidation soybean oil, epoxidation
linseed oil, epoxidation castor oil and the like: and
hydroxylamine:
[0153] Examples of aliphatic amine are octylamine, laurylamine,
myristylamine, palmitylamine, stearylamine, oleylamine, cocoamine,
tallowamine, soyamine, N,N-dicocoamine, N,N-ditallowamine,
N,N-disoyamine, N-lauryl-N,N-dimethylamine,
N-myristyl-N,N-dimethylamine, N-palmityl-N,N-dimethylamine,
N-stearyl-N,N-dimethylamine, N-cocoa-N,N-dimethylamine,
N-tallow-N,N-dimethylamine, N-soy-N,N-dimethylamine,
N-methyl-N,N-ditallowamine, N-methyl-N,N-dicocoamine,
N-oleyl-1,3-diaminopropane, N-tallow-1,3-diaminopropane,
hexamethylenediamine, and the like.
[0154] Examples of ammonium chloride are
N-lauryl-N,N,N-trimethylammoniumc- hloride,
N-palmityl-N,N,N-trimethylammoniumchloride,
N-stearyl-N,N,N-trimethylammoniumchloride,
N-docosyl-N,N,N-trimethylammon- iumchloride,
N-cocoa-N,N,N-trimethylammoniumchloride,
N-tallow-N,N,N-trimethylammoniumchloride,
N-soy-N,N,N-trimethylammoniumch- loride,
N,N,N-triethyl-N-benzylammoniumchloride, N-lauryl-N,N-dimethyl-N-b-
enzylammoniumchloride, N-myristyl-N,
N-dimethyl-N-benzylammoniumchloride, N-stearyl-N,
N-dimethyl-N-benzylammoniumchloride, N-cocoa-N,N-dimethyl-N--
benzylammoniumchloride, N,N-dioleyl-N,N-dimethylammoniumchloride,
N,N-dicocoa-N,N-dimethylammoniumchloride,
N,N-ditallow-N,N-dimethylammoni- umchloride,
N,N-diiso-N,N-dimethylammoniumchloride, N,
N-bis(2-hydroxyethyl)-N-lauryl-N-methylammoniumchloride,
N,N-bis(2-hydroxyethyl)-N-stearyl-N-methylammoniumchloride,
N,N-bis(2-hydroxyethyl)-N-oleyl-N-methylammoniumchloride,
N,N-bis(2-hydroxyethyl)-N-cocoa-N-methylammoniumchloride,
N,N-bis(polyoxyethylene)-N-lauryl-N-methylammoniumchloride,
N,N-bis(polyoxyethylene)-N-stearyl-N-methylammoniumchloride,
N,N-bis(polyoxyethylene)-N-oleyl-N-methylammoniumchloride,
N,N-bis(polyoxyethylene)-N-cocoa-N-methylammoniumchloride, and the
like.
[0155] Examples of betaine are
N,N-bis(2-hydroxyethyl)laurylaminobetaine,
N,N-bis(2-hydroxyethyl)tridecylaminobetaine,
N,N-bis(2-hydroxyethyl)myris- tylaminobetaine,
N,N-bis(2-hydroxyethyl)pentadecylaminobetaine,
N,N-bis(2-hydroxyethyl)palmitylaminobetaine,
N,N-bis(2-hydroxyethyl)stear- ylaminobetaine,
N,N-bis(2-hydroxyethyl)oleylaminobetaine,
N,N-bis(2-hydroxyethyl)docosylaminobetaine,
N,N-bis(2-hydroxyethyl)octaco- sylaminobetaine,
N,N-bis(2-hydroxyethyl)cocoaminobetaine,
N,N-bis(2-hydroxyethyl)tallowaminobetaine, and the like.
hexamethylenetetramine: alkanolamine such as triethanolamine,
triisopropanolamine and the like. Examples of
N-(2-hydroxyethyl)amine are N-(2-hydroxyethyl)laurylamine,
N-(2-hydroxyethyl)tridecylamine, N-(2-hydroxyethyl)myristylamine,
N-(2-hydroxyethyl)pentadecylamine, N-(2-hydroxyethyl)palmitylamine,
N-(2-hydroxyethyl)pstearylamine, N-(2-hydroxyethyl)oleylamine,
N-(2-hydroxyethyl)docosylamine, N-(2-hydroxyethyl)octacosylamine,
N-(2-hydroxyethyl)cocoamine, N-(2-hydroxyethyl)tallowamine,
N-methyl-N-(2-hydroxyethyl)laurylamine,
N-methyl-N-(2-hydroxyethyl)tridecylamine,
N-methyl-N-(2-hydroxyethyl)myri- stylamine,
N-methyl-N-(2-hydroxyethyl)pentadecylamine,
N-methyl-N-(2-hydroxyethyl)palmitylamine,
N-methyl-N-(2-hydroxyethyl)stea- rylamine,
N-methyl-N-(2-hydroxyethyl)oleylamine, N-methyl-N-(2-hydroxyethy-
l)docosylamine, N-methyl-N-(2-hydroxyethyl)octacosylamine,
N-methyl-N-(2-hydroxyethyl)cocoamine,
N-methyl-N-(2-hydroxyethyl)tallowam- ine, and the like.
[0156] Examples of N,N-bis(2-hydroxyethyl)aliphatic amine are
N,N-bis(2-hydroxyethyl)laurylamine,
N,N-bis(2-hydroxyethyl)tridecylamine,
N,N-bis(2-hydroxyethyl)myristylamine,
N,N-bis(2-hydroxyethyl)pentadecylam- ine,
N,N-bis(2-hydroxyethyl)palmitylamine,
N,N-bis(2-hydroxyethyl)stearyla- mine,
N,N-bis(2-hydroxyethyl)oleylamine,
N,N-bis(2-hydroxyethyl)docosylami- ne,
N,N-bis(2-hydroxyethyl)octacosylamine,
N,N-bis(2-hydroxyethyl)cocoamin- e,
N,N-bis(2-hydroxyethyl)tallowamine, and the like. Mono- or di-ester
of N,N-bis(2-hydroxyethyl)aliphatic amine and aliphatic acid such
as lauric acid, myristic acid, palmitic acid, stearic acid, oleic
acid, behenic acid, erucic acid, and the like. Examples of
aminoether are polyoxyethylenelaurylaminoether,
polyoxyethylenestearylaminoether, polyoxyethyleneoleylaminoether,
polyoxyethylenecocoaminoether, polyoxyethylenetallowaminoether, and
the like. Examples of diaminoalkyl are
N,N,N',N'-tetra(2-hydroxyethyl)-1,3-diaminopropane,
N,N,N',N'-tetra(2-hydroxyethyl)-1,6-diaminohexane,
N-lauryl-N,N',N'-tris(2-hydroxyethyl)-1,3-diaminopropane,
N-stearyl-N,N',N'-tris(2-hydroxyethyl)-1,3-diaminopropane,
N-cocoa-N,N',N'-tris(2-hydroxyethyl)-1,3-diaminopropane,
N-tallow-N,N',N'-tris(2-hydroxyethyl)-1,3-diaminopropane,
N,N-dicocoa-N',N'-bis(2-hydroxyethyl)-1,3-diaminopropane,
N,N-ditallow-N',N'-bis(2-hydroxyethyl)-1,3-diaminopropane,
N-coco-N,N',N'-tris(2-hydroxyethyl)-1,6-diaminohexane,
N-tallow-N,N',N'-tris(2-hydroxyethyl)-1,6-diaminohexane,
N,N-dicocoa-N',N'-bis(2-hydroxyethyl)-1,6-diaminohexane,
N,N-ditallow-N',N'-bis(2-hydroxyethyl)-1, 6-diaminohexane, and the
like.
[0157] Examples of aliphatic amide are oleic acid amide, stearic
acid amide, erucic acid amide, behenic acid amide, montanic acid
amide, N-stearylstearic acid amide, N-oleyloleyic acid amide,
N-stearyloleic acid amide, N-oleylstearic acid amide,
N-stearylerucic acid amide, N-oleylpalmitic acid amide,
N,N'-methylene-bis-lauric acid amide, N,N'-methylene-bis-myristic
acid amide, N,N'-methylene-bis-palmitic acid amide,
N,N'-methylene-bis-palmitoleic acid amide, N,N'-methylene-bis-stea-
ramide, N,N'-methylene-bis-12-hydroxystearic acid amide,
N,N'-methylene-bis-oleic acid amide, N,N'-methylene-bis-behenic
acid amide, N,N'-methylene-bis-erucic acid amide,
N,N'-methylene-bis-montanic acid amide, N,N'-ethylene-bis-lauric
acid amide, N,N'-ethylene-bis-myrist- ic acid amide,
N,N'-ethylene-bis-palmitic acid amide,
N,N'-ethylene-bis-palmitoleic acid amide, N,N'-ethylene-bis stearic
acid amide, N,N'-ethylene-bis-12-hydroxystearic acid amide,
N,N'-ethylene-bis-oleic acid amide, N,N'-ethylene-bis-behenic acid
amide, N,N'-ethylene-bis-erucic acid amide,
N,N'-ethylene-bis-montanic acid amide,
N,N'-hexamethylene-bis-stearamide, N,N'-hexamethylene-bis-oleic
acid amide, N,N'-hexamethylene-bis-behenic acid amide,
N,N'-distearyloxalic acid amide, N,N'-dioleyloxalic acid amide,
N,N'-distearylsuccinic acid amide, N,N'-dioleylsuccinic acid amide,
N,N'-distearyladipic acid amide, N,N'-dioleyladipic acid amide,
N,N'-distearylsebacic acid amide, N,N'-dioleylsebacic acid amide,
and the like.
[0158] Examples of aliphatic amide are
N,N-bis(2-hydroxyethyl)laurylamide,
N,N-bis(2-hydroxyethyl)tridecylamide,
N,N-bis(2-hydroxyethyl)myristyl amide,
N,N-bis(2-hydroxyethyl)pentadecylamide, N,N-bis(2-hydroxyethyl)pal-
mitylamide, N,N-bis(2-hydroxyethyl)stearylamide,
N,N-bis(2-hydroxyethyl)ol- eylamide,
N,N-bis(2-hydroxyethyl)dococylamide, N,N-bis(2-hydroxyethyl)octa-
cocylamide, N,N'-bis(2-hydroxyethyl)cocoamide, N,N-bis(2-
hydroxyethyl)tallowamide, and the like. Examples of polyoxyalkylene
of aliphatic amide are polyoxyethylenelaurylamideether,
polyoxyethylenestearylamideether, polyoxyethyleneoleylamideether,
polyoxyethylenecocoamideether, polyoxydethylenetallowamideether,
and the like.
[0159] Examples of a hindered amine compound are
4-hydroxy-2,2,6,6-tetrame- thylpiperidine,
1-aryl-4-hydroxy-2,2,6,6-tetramethylpiperidine,
1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,
1-(4-t-butyl-2-butenyl)- -4-hydroxy-2,2,6,6-tetramethylpiperidine,
4-stearoyloxy-2,2,6,6-tetramethy- lpiperidine,
4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine,
1-benzyl-2,2,6,6-tetramethyl-4-piperidylmaleate,
bis(2,2,6,6-tetramethyl-- 4-piperidyl)succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)succinate,
bis(2,2,6,6-tetramethyl-4-piperidyl)adipate,
bis(2,2,6,6-tetramethyl-4-pi- peridyl)cevacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)fumarate,
bis(1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl)cevacate,
bis(1-aryl-2,2,6,6-tetramethyl-4-piperidyl)phthalate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)cevacate,
1,1'-(1,2-ethanediyl)bis(- 3,3,5,5-tetramethylpiperiazinone),
2-methyl-2-(2,2,6,6-tetramethyl-4-piper-
idyl)imino-N-(2,2,6,6-tetramethyl-4-piperidyl)propioneamide,
2-methyl-2-(1,2,2,6,6-pentametyl-4-peperidyl)imino-N-(1,2,2,6,6-pentameth-
yl-4-piperidyl)propioneamide,
1-propargyl-4-.beta.-cyanoethyloxy-2,2,6,6-t- etramethylpiperidine,
1-acetyl-2,2,6,6-tetramethyl-4-piperidyl-acetate, trimellitic
acid-tris(2,2,6,6-tetramethyl-4-piperidyl)ester,
1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)dibutylmalonate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)dibenzyl-malonate,
bis(1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl)dibenzyl-malonate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-
-2-n-butylmalonate, and the like.
[0160] Examples of a hindered amine compound are
bis(2,2,6,6-tetramethyl-4-
-piperidyl)-1,5-dioxaspiro[5.5]undecane-3,3-dicarboxylate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,5-dioxaspiro[5.5]undecane-3,3-di-
carboxylate,
bis(1-acetyl-2,2,6,6-tetramethyl-4-piperidyl)-1,5-dioxaspiro[-
5.5]undecane-3,3-dicarboxylate,
1,3-bis[2,2'-[bis(2,2,6,6-tetramethyl-4-pi-
peridyl)-1,3-dioxacyclohexane-5,5-dicarboxylate)],
bis(2,2,6,6-tetramethyl-
-4-piperidyl)-2-[1-methylethyl[1,3-dioxacyclohexane-5,5-dicarboxylate]],
1,2-bis[2,2'-[bis(2,2,6,6-tetramethyl-4-piperidyl)-2-methyl-1,3-dioxacycl-
ohexane-5,5-dicarboxylate]],
bis(2,2,6,6-tetramethyl-4-piperidyl)-2-[2-(3,-
5-di-t-butyl-4-hydroxyphenyl)]ethyl-2-methyl-1,3-dioxacyclohexane-5,5-dica-
rboxylate,
bis(2,2,6,6-tetramethyl-4-piperidyl)-1,5-dioxaspiro[5.11]heptad-
ecane-3,3-dicarboxylate, and the like.
[0161] Examples of a hindered amine compound are
hexane-1',6'-bis-(4-carba-
moyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine),
toluene-2',4'-bis(4-carb-
amoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperydine),
dimethyl-bis(2,2,6,6-te- tramethylpiperidine-4-oxy)-silane,
phenyl-tris(2,2,6,6-tetramethylpiperidi- ne-4-oxy)-silane,
tris(1-propyl-2,2,6,6-tetramethyl-4-piperidyl)-phosphite- ,
tris(1-propyl-2,2,6,6-tetramethyl-4-piperidyl)-phosphate,
phenyl-[bis(1,2,2,6,6-pentamethyl-4-piperidyl)]-phosphonate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylat-
e,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylic
acid amide,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetr-
acarbonamide, and the like.
[0162] Examples of a hindered amine compound are
2-dibutylamino-4,6-bis(9--
aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]-3-undecylmethoxy)-s--
triazine,
2-dibutylamino-4,6-bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-
-dioxaspiro[5.5]-3-undecylmethoxy)-s-triazine,
tetrakis(9-aza-3-ethyl-8,8,-
10,10-tetramethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl)-1,2,3,4-butanetetra-
carboxylate,
tetrakis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro-
[5.5]-3-undecylmethyl)-1,2,3,4-butanetetracarboxylate,
tridecyl'tris(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-
butanetetracarboxylate, tridecyl'tris (1,2,2,6,
6-pentamethyl-4-piperidyl- ) 1,2,3, 4-butanetetracarboxylate, di
(tridecyl)'bis (2, 2,6, 6-tetramethyl-4-piperidyl) 1,
2,3,4-butanetetracarboxylate, di
(tridecyl)'bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,
4-butanetetracarboxylate, 2,2,4,
4-tetramethyl-7-oxa-3,20-diazadispiro[5.-
1.11.2]heneicosane-21-one, 3,9-bis[1,1-dimethyl-2-{tris (2,
2,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-
-tetraoxaspiro[5.5]undecane, 3,
9-bis[1,1-dimethyl-2-{tris(1,2,2,6,6-penta-
methyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspi-
ro[5.5]undecane, and the like.
[0163] Examples of a hindered amine compound are
poly(2,2,6,6-tetramethyl-- 4-piperidylacrylate),
poly(1,2,2,6,6-pentamethyl-4-piperidylacrylate),
poly(2,2,6,6-tetramethyl-4-piperidylmethacrylate),
poly(1,2,2,6,6-pentamethyl-4-piperidylmethacrylate),
poly[[bis(2,2,6,6-tetramethyl-4-piperidyl)itaconate][vinylbutylether]],
poly[[bis(1,2,2,6,6-pentamethyl-4-piperidyl)itaconate][(vinylbutylether]]-
, poly[[bis
(2,2,6,6-tetramethyl-4-piperidyl)itaconate][vinyloctylether]],
poly[[bis(1,2,2,6,6-pentamethyl-4-piperidyl)itaconate][vinyloctylether]],
dimethylsuccinate-2-(4-hydroxy-2,2,6,6-tetramethylpiperidyl)ethanol
condensation products, and the like.
[0164] Examples of a hindered amine compound are
poly[hexamethylene[(2,2,6- ,6-tetramethyl-4-piperidyl)imino]],
poly[ethylene[[2,2,6,6-tetramethyl-4-p-
iperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]],
poly[[1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]]he-
xamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]],
poly[[6-(diethylimino)-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-pi-
peridyl)imino]hexamethylene[[2,2,6,6-tetramethyl-4-piperidyl)imino]],
poly[[6-[(2-ethylhexyl)imino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetrameth-
yl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]-
],
poly[[6-[(1,1,3,3-tetramethylbutyl)imino]-1,3,5-triazine-2,4-diyl][(2,2-
,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-pi-
peridyl)imino]],
poly[[6-(cyclohexylimino)-1,3,5-triazine-2,4-diyl][(2,2,6-
,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-pipe-
ridyl)imino]],
poly[[6-morpholino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetram-
ethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imi-
no]],
poly[[6-(butoxyimino)-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl--
4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]],
poly[[1,1,3,3-tetramethylbutyl)oxy]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tet-
ramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)-
imino]], and the like.
[0165] Examples of a hindered amine compound are
poly[oxy[6-[(1-piperidyl)-
-1,3,5-triazine-2,4-diyloxy-1,2-ethanediyl][(2,2,6,6-tetramethyl-3-oxo-1,4-
-piperidyl)-1,2-ethanediyl][(3,3,5,5-tetramethyl-2-oxo-1,4-piperidyl)-1,2--
ethanediyl]],
poly[oxy[6-[1,1,3,3-tetramethylbutyl)imino]-1,3,5-triazine-2-
,4-diyloxy-1,2-ethanediyl][(2,2,6,6-tetramethyl-3-oxo-1,4-piperidyl)-1,2-e-
thanediyl][(3,3,5,5-tetramethyl-2-oxo-1,4-piperidyl)-1,2-ethanediyl]],
poly[[6-[(ethylacetyl)imino]-1,3,5-triazine-2,4-diyl][(2,
2,6,6-tetramethyl-4-piperidyl) imino)hexamethylene[(2,2,6,
6-tetramethyl-4-piperidyl)imino]],
poly[[6-[(2,2,6,6-tetramethyl-4-piperi-
dyl)butylimino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)-
imino]hexamethylene[(2,2,6, 6-tetramethyl-4-piperidyl)imino]], and
the like.
[0166] Examples of a hindered amine compound are
1,6,11-tris[{4,6-bis (N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)
amino)-1,3,5-triazine-2-yl}a- mino]undecane,
1,6,11-tris[{4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-pip-
eridyl)amino-1,3,5-triazine-2-yl}amino]undecane,
1,6,11-tris[{4,6-bis(N-oc-
tyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazine-2-yl}amino]un-
decane,
1,6,11-tris[{4,6-bis(N-octyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)-
amino)-1,3,5-triazine-2-yl}amino]undecane,
1,5,8,12-tetrakis[4,6-bis(N-(2,-
2,6-6-tetramethyl-4-piperidyl)-butylamino)-1,3,5-triazine-2-yl]-1,5,8,12-t-
etraazadodecane,
1,5,8,12-tetrakis[4,6-bis(N-(1,2,2,6,6-pentamethyl-4-pipe-
ridyl)-butylamino)-1,3,5-triazine-2-yl]-1,5,8,12-tetraazadodecane,
and the like.
[0167] Examples of an aminotriazine compound are
2,4,6-triamino-1,3,5-tria- zine,
2,4-diamino-6-methyl-1,3,5-triazine,
2,4-diamino-6-phenyl-1,3,5-tria- zine,
1,4-bis(3,5-diamino-2,4,6-triazinyl)butane,
3,9-bis[2-(3,5-diamino-2-
,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and
the like.
[0168] Examples of metals for the above metal salts include
lithium, sodium, potassium, magnesium, calcium, strontium, barium,
zinc or aluminum. Those metal salts can exist as a normal salt or
basic salt. Examples of preferred metal salts include fatty acid
metal salts, alkanoyl lactic acid metal salts, aliphatic hydroxy
acid metal salts, hydrotalcites, lithium aluminum complex hydroxide
salts, metal oxides, metal hydroxides, metal carbonates, metal
aliphatic phosphates, epoxy compounds, aliphatic amines, aliphatic
amides, hindered amine compounds, aminotriazine compounds or a
mixture thereof. Those halogen scavengers can be either alone or in
combinations of two kinds or more.
[0169] The amount of the halogen scavengers for addition is 0.001
to 2 weight parts to 100 weight parts of the polypropylene
composition (PP) as a component A, preferably 0.005 to 1.5 weight
parts, particularly preferably 0.01 to 1 weight part.
[0170] For the compositions according to the present invention,
additives for polypropylene, other than the above halogen
scavengers, can be used so as to accomplish the objects of the
present invention. Examples of the additives include light
stabilizers, metal deactivators, clarifiers, nucleating agents,
lubricants, antistatic agents, anti-fogging agents, anti-blocking
agents, anti-dropping agents, radical generators such as peroxide,
flame retardants, flame retardant assistants, pigments, organic or
inorganic anti-bacterial agents, inorganic fillers such as talc,
mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite,
diatomaceous earth, asbestos, silicon dioxide, titanium dioxide,
zinc sulfate, barium sulfate, magnesium sulfate, calcium silicate,
aluminum silicate, glass fiber, potassium titanate, carbon fiber,
carbon black, graphite or metal fiber, coupling agents such as
silane-based, titanate-based, boron-based, aluminate-based or zirco
aluminate-based coupling agents, inorganic fillers treated with a
surface active agent such as a coupling agent and organic fillers
such as wood meal, pulp, recycled paper, synthetic fiber or natural
fiber.
[0171] The obtained polypropylene compositions can be mixed with a
variety of additives or synthetic fiber if required. Examples of
the additives include antioxidants, ultraviolet absorbers,
antistatic agents, nucleating agents, lubricants, flame retardants,
anti-blocking agents, colors, organic or inorganic fillers.
Afterward, the compositions are usually subjected to heat
treatment, melting and kneading. Further, the compositions are
shaped to granulated-cut pellets and supplied to produce a variety
of molded products.
EXAMPLES
[0172] Hereinafter the present invention will be explained in
further details with reference to examples and comparative
examples.
[0173] Definitions of the terms and measurement methods used in the
examples and comparative examples are as follows. Further, in the
following examples and comparative examples, polypropylene may be
abbreviated as PP, and polyethylene as PE.
[0174] (1) Intrinsic viscosity [.eta.]: values of the limiting
viscosity in tetralin at 135.degree.C. measured with an Ostwald's
viscometer produced by Mitsui Toatsu Chemicals Inc.
(unit:dl/g).
[0175] (2) Melt tension (MS): values measured with a Melt Tension
II produced by Toyo Seiki Seisaku-sho, Ltd. (unit:cN).
[0176] (3) Crystallization temperature (Tc): values measured with a
Differential Scanning Calorimetry VII produced by Perkin-Elmer,
Ltd. of the temperature indicating the maximum value of the heat
absorption at the crystallization of a polypropylene composition
after raising the temperature from room temperature to
230.degree.C. in the temperature rising condition of 30.degree.
C./minute, maintaining the same temperature for 10 minutes,
lowering the temperature to -20C. in the condition of -20.degree.
C./minute, maintaining the same temperature for 10 minutes, raising
the temperature to 230.degree.C. in the temperature rising
condition of 20.degree. C./minute, maintaining the same temperature
for 10 minutes, lowering the temperature to 150.degree. C. in the
condition of -180.degree. C./minute, and further lowering the
temperature by -5.degree. C./minute (unit:.degree. C.).
[0177] (4) Thermal stability pellets of a polyolefin composition
were prepared by mixing 0.1 weight part of 2,6-di-t-butyl-p-cresol
and 0.1 weight part of calcium stearate to 100 weight parts of
polyolefin composition, and melting and mixing and then pelletizing
the mixture at 230.degree. C. with an extruder having a screw
diameter of 40 mm.
[0178] Melt flow rates (MFR) (unit:g/10 minutes) of the pellets
obtained in the above mentioned operation and the pellets obtained
by further processing by the above mentioned melting and kneading,
and pelletizing with the extruder two more times were measured
based on the condition 14 of Table 1 of the JIS K 7210. The
difference between the MFRs of the pellets finally obtained and the
pellets initially obtained (final pellets' MFR-initial pellets'
MFR=A MFR) was calculated as the thermal stability.
[0179] A smaller difference (AMFR) indicates a better thermal
stability.
[0180] (5) Coloring-preventing property: Using the same pellets
used in measuring the above mentioned thermal stability, the
yellowness index (YI) of the pellets obtained initially and the
pellets finally obtained by further processing by the pelletization
of two more times were measured based on the JIS K7103, and the
difference between the yellowness index of the pellets finally
obtained and the pellets initially obtained (.DELTA.YI=final
pellets' YI-initial pellets' YI) was calculated.
[0181] A smaller difference (YI) indicates a better
coloring-preventing property.
Example 1
[0182] (1) Preparation of catalyst composition including transition
metal compound
[0183] 0.3 liter of decane, 48 g of magnesium chloride anhydride,
170 g of orthotitanate-n-butyl and 195 g of 2-ethyl-1-hexanol were
mixed in a stainless steel polymerization reactor with an agitator,
then dissolved by kneading at 130.degree. C. for one hour to form a
uniform solution. The uniform solution was heated to 70.degree. C.,
then 18 g of di-i-butyl phthalate was added thereto while kneading.
One hour later, 520 g of silicon tetrachloride was added over 2.5
hour to have a solid precipitated and further maintained at
70.degree. C. for one hour. The solid was separated from the
solution and washed with hexane to obtain a solid product.
[0184] All the solid product was mixed with 1.5 liters of titanium
tetrachloride dissolved in 1.5 liters of 1,2-dichloroethane. 36 g
of di-i-butyl phthalate was added thereto and the mixture was
reacted for two hours at 100.degree. C. while kneading. The liquid
phase portion was eliminated by decantation at the same
temperature, then 1.5 liters of 1,2-dichloroethane and 1.5 liters
of titanium tetrachloride were added and maintained at 100.degree.
C. for two hours while kneading. Then by washing with hexane and
drying, a supported titanium catalyst component (transitional metal
compound catalyst component) containing 2.8 weight % of titanium
was obtained.
[0185] (2) Preparation of preactivated catalyst
[0186] After providing a nitrogen gas atmosphere in a 5 liter
capacity stainless steel polymerization reactor having an
inclined-turbine agitator, 2.8 liters of n-hexane, 4 millimole of
triethyl aluminum (organic metal compound (AL1)) and 9.0 g of the
supported titanium catalyst component prepared as mentioned above
(5.26 millimole per 1 mole Ti atom) were added, and then 20 g of
propylene was supplied to conduct a preliminary polymerization for
10 minutes at -2.degree. C.
[0187] Polymer generated in a preliminary polymerization obtained
in the same conditions was analyzed and it was found that 2 g of
propylene became polypropylene (B) per 1 g of the supported
titanium catalyst component, and the intrinsic viscosity
[.eta..sub.B] of the polypropylene (B) measured in tetralin of
135.degree. C. was 2.8 dl/g.
[0188] After the reaction period, unreacted propylene was
discharged outside the reaction container. After substituting the
gas phase portion in the polymerization reactor with a nitrogen
gas, ethylene was supplied continuously for two hours so as to
maintain the inside pressure at 0.59 MPa with an inside temperature
of -1.degree. C. to conduct the preliminary activation.
[0189] Polymer generated in a preliminary activated polymerization
obtained in the same conditions was analyzed and it was found that
24 g of polymer existed per 1 g of the s pported titanium catalyst
component, and the intrinsic viscosity [.eta..sub.T2] measured in
tetralin at 135.degree.C. was 31.4 dl/g.
[0190] The amount (W.sub.2) of polyethylene (A) per 1 g of the
supported titanium catalyst component generated in the preliminary
activating polymerization with ethylene can b calculated as the
difference between the polymer generation amo nt (W.sub.T2) per 1 g
of the supported titanium catalyst component after the preliminary
activating treatment and the polypropylene (B) generation amount
(W1) per 1 g of the supported titanium catalyst component after the
preliminary polymerization by the following formula:
[0191] W.sub.2=W.sub.T2-W.sub.1.
[0192]
[0193] The intrinsic viscosity [.eta..sub.A] of polyethylene (A)
generated in the preliminary activating polymerization with
ethylene can be calculated from the intrinsic viscosity
[.eta..sub.B] of polypropylene (B) generated in the preliminary
polymerization and the intrinsic viscosity [.eta.T.sub.2] of the
polymer generated in the preliminary activating treatment by the
following formula:
[.eta..sub.A]=([.eta..sub.T2].times.W.sub.T2-[.eta..sub.B].times.W.sub.1)/-
(W.sub.T2-W.sub.1)=[.eta..sub.E].
[0194] According to the above mentioned formulae, the amount of the
polyethylene (A) generated in the preliminary activating
polymerization with ethylene was 22 g per 1 g of the supported
titanium catalyst component and the intrinsic viscosity
[.eta..sub.A] was 34.0 dl/g.
[0195] After the reaction period, unreacted ethylene was discharged
outside the polymerization reactor. After substituting the gas
phase portion of the polymerization reactor with a nitrogen gas and
adding 1.6 millimole of diisopropyldimethoxy silane (electron donor
(El)), 20 g of propylene was supplied and maintained for 10 minutes
at 1.degree.C. to conduct the addition polymerization after the
preliminary activating treatment.
[0196] Polymer generated in an addition polymerization obtained in
the same conditions was analyzed and it was found that 26 g of
polymer existed per 1 g of the supported titanium catalyst
component, and the intrinsic viscosity [.eta..sub.T3] measured in
tetralin at 135.degree. C. was 29.2 dl/g. The generation amount
(W.sub.3) of polypropylene generated in the addition polymerization
calculated as mentioned above was 2 g per 1 g of the supported
titanium catalyst component, and the intrinsic viscosity
[.eta..sub.C] was 2.8 dl/g.
[0197] After the reaction period, unreacted propylene was
discharged outside the polymerization reactor. The gas phase
portion of the polymerization reactor was substituted with a
nitrogen gas once to obtain the preactivated catalyst slurry of the
main (co-)polymerization.
[0198] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0199] After providing a nitrogen gas atmosphere in a 500 liter
capacity stainless steel polymerization reactor with an agitator,
240 liters of n-hexane, 780 millimole of triethyl aluminum (organic
metal compound (AL2)), 78 millimole of diisopropyldimethoxy silane
(electron donor (E2)) and 1/2amount of the preactivated catalyst
slurry obtained as mentioned above were added at 20.degree. C. Then
after introducing 55 liters of hydrogen into the polymerization
reactor and raising the temperature to 70.degree. C., propylene was
continuously supplied into the polymerization reactor so as to
maintain the pressure of the gas phase portion in the
polymerization reactor at 0.79 MPa for two hours in the condition
of the polymerization temperature of 70.degree. C. to conduct the
main polymerization of propylene.
[0200] After the polymerization duration, 1 liter of methanol was
introduced to the polymerization reactor and the catalyst
deactivation reaction was conducted at 70.degree. C. for 15
minutes. Then after discharging the unreacted gas, the solvent was
separated and the polymer was dried to obtain 40.1 kg of a polymer
having the intrinsic viscosity [.eta..sub.T] of 1.97 dl/g.
[0201] The obtained polymer was a polypropylene composition
containing 0.25 weight % of the polyethylene (A) according to the
preliminary activating polymerization as the (a) component and the
intrinsic viscosity [.eta..sub.P] of the polypropylene as the (b)
component was 1.89 dl/g.
[0202] 0.1 weight part of 2,6-di-t-butyl-p-cresol and 0.1 weight
part of calcium stearate were mixed to 100 weight parts of the
obtained polypropylene composition. The mixture was pelletized at
230.degree.C. with an extruder having a screw diameter of 40 mm to
have pellets. Various physical properties of the pellets were
measured and evaluated to find the MFR, the crystallization
temperature, and the melt tension (MS) to be 3.5 g/10 minutes,
122.5.degree. C. and 4.9 cN, respectively. Detailed physical
properties are shown in Table 1.
Example 2 and Comparative Example 1
[0203] Polypropylene compositions were produced using the same
conditions as in example 1 except that the preliminary activating
polymerization conditions with ethylene were changed to change the
generated amount of polyethylene (A) to prepare the evaluation
specimens of example 2 and comparative example 1.
[0204] Various physical properties of the obtained polypropylene
compositions are shown in Table 1.
Comparative Example 2
[0205] A polypropylene composition was produced using the same
conditions as in example 1 (2) except that the preliminary
activating polymerization with ethylene was replaced by the
procedure that the 220 g of propylene was supplied into the
polymerization reactor in three steps; 80 g at initiating the
preliminary activating polymerization, 80 g at 30 minutes after the
initiation and 60 g at one hour after the initiation to prepare the
evaluation specimen of comparative example 2.
[0206] Various physical properties of the obtained polypropylene
composition are shown in Table 1.
Comparative Example 3
[0207] A polypropylene composition was produced using the same
conditions as in example 1 except that the preliminarily activated
polymerization with ethylene of the supported catalyst component
containing titanium was not conducted.
[0208] Various physical properties of the obtained polypropylene
compositions are shown in Table 1.
Comparative Example 4
[0209] After providing a nitrogen gas atmosphere in a stainless
steel polymerization reactor having an inclined-turbine agitator,
10 kg of propylene homopolymer powders having an intrinsic
viscosity [.eta..sub.T] of 1.67 dl/g and an average particle size
of 150 .mu.m obtained by the slurry polymerization of propylene in
n-hexane using a catalyst prepared by combining a catalyst titanium
component comprising a titanium trichloride composition, diethyl
aluminum chloride and diethylene glycol dimethyl ether as the third
component were added. Then after repeating 10 times the operation
to have a vacuum inside the polymerization reactor and supplying a
nitrogen gas to the atmospheric pressure, a 70 weight %
concentration toluene solution of 0.35 mole of di-2-ethyl hexyl
peroxydicarbonate (reforming agent) was added and mixed in the
nitrogen gas atmosphere at 25.degree. C. while kneading. The
temperature in the polymerization reactor was raised to 120.degree.
C. and maintained for 30 minutes for reaction. After the reaction
period, the temperature in the polymerization reactor was raised to
135.degree.C. and the after-treatment was conducted at the same
temperature for 30 minutes. After the after-treatment, the
polymerization reactor was cooled to the room temperature and then
opened to obtain polypropylene.
[0210] 0.1 weight part of 2,6-di-t-butyl-p-cresol and 0.1 weight
part of calcium stearate were mixed to 100 weight parts of the
obtained polypropylene composition. The mixture was pelletized at
230.degree.C. with an extruder having a screw diameter of 40 mm to
form pellets to prepare the evaluation specimen of comparative
example 4.
[0211] Various physical properties of the pellets obtained in the
examples 1-2 and the comparative examples 1-4 were evaluated and
the results are shown in Table 1.
1 TABLE 1 Examples Comparative Examples 1 2 1 2.sup.3 3 4
Preliminary polymerization <polypropylene (B)> 2.8 2.8 2.8
2.8 2.8 -- Intrinsic viscosity [.eta..sub.B] (dl/g) Generated
amount .sup.1 (g/g) 2.0 2.0 2.0 2.0 2.0 -- Composition ratio .sup.2
(wt %) 0.02 0.02 0.02 0.02 0.02 -- Preliminary activation
<polyethylene (A)> 34.0 34.0 34.0 2.8 -- -- Intrinsic
viscosity [.eta..sub.A] (dl/g) Generated amount .sup.1 (g/g) 22.0
4.5 0.005 22.0 -- -- Composition ratio .sup.2 (wt %) 0.25 0.05
0.0001 0.25 -- -- Addition polymerization <polypropylene (C)>
2.8 2.8 2.8 2.8 2.8 -- Intrinsic viscosity [.eta..sub.C] (dl/g)
Generated amount .sup.1 (g/g) 2.0 2.0 2.0 2.0 2.0 -- Composition
ratio .sup.2 (wt %) 0.02 0.02 0.02 0.02 0.02 -- Polymerization
process Intrinsic viscosity [.eta..sub.D] 1.89 1.90 1.89 1.89 1.89
1.67 (dl/g) Composition ratio .sup.2 (wt %) 99.7 99.9 100 99.7 100
100 Propylene (co-) polymer Intrinsic viscosity [.eta..sub.P] 1.89
1.90 1.89 1.89 1.89 1.67 (dl/g) Propylene (co-)polymer composition
Intrinsic viscosity [.eta..sub.T] 1.97 1.92 1.89 1.89 1.89 1.67
(dl/g) Melt tension (MS) (cN) 4.9 2.0 1.0 0.8 0.8 7.2
Crystallization temperature 122.5 121.3 117.0 116.2 116.0 129.4
(.degree. C.) MFR (g/10 minutes) 3.5 4.1 4.5 4.5 4.5 9.2 initial
final (g/10 minutes) 3.6 4.3 4.6 4.6 4.6 17.5 .DELTA.MFR (g/10
minutes) 0.1 0.2 0.1 0.1 0.1 8.3 Note 1 Generated amount (g) per 1
g of transitional metal compound catalyst component Note 2
Composition ratio (wt %) in the propylene (co-) polymer composition
Note 3 Comparative example 2; propylene was used as the monomer for
the preliminary activation.
Example 3
[0212] (1) Preparation of catalyst composition including transition
metal compound
[0213] 37.5 liters of decane, 7.14 kg of magnesium chloride
anhydride, 35.1 liters of 2-ethyl-l-hexanol were mixed in a
stainless steel polymerization reactor with an agitator, then
dissolved by kneading at 140.degree. C. for 4 hours to provide a
uniform solution. To the uniform solution, 1.67 kg of phthalic
anhydride was added and further kneaded and mixed for one hour at
130.degree.C. to dissolve the phthalic anhydride into the uniform
solution.
[0214] After cooling all the obtained uniform solution to a room
temperature (23.degree. C.), all the uniform solution was dropped
into 200 liters of titanium tetrachloride maintained at -20.degree.
C. over three hours. After the dropping, the solution was heated to
110.degree. C. over four hours. When the temperature reached
110.degree. C., 5.03 liters of di-i-butyl phthalate was added and
kneaded for two hours at 110.degree. C. for reaction. After the two
hour reaction, the solid portion was collected by heat filtration.
The solid portion was resuspended with 275 liters of titanium
tetrachloride, and maintained at 110.degree. C. for two hours again
for reaction.
[0215] After the reaction, again the solid portion was collected by
heat filtration. The solid portion was washed with n-hexane
sufficiently so that titanium radicals are not detected in the
rinsing liquid. Subsequently, the solvent was separated by
filtration, and the solid portion was dried under a reduced
pressure to obtain a supported titanium catalyst component
(transitional metal compound catalyst component) containing 2.4
weight % of titanium.
[0216] (2) Preparation of preactivated catalyst
[0217] After substituting a 30 liter capacity stainless steel
polymerization reactor having an inclined-turbine agitator with a
nitrogen gas, 18 liters of n-hexane, 60 millimole of triethyl
aluminum (organic metal compound (AL1)) and 150 g of the supported
titanium catalyst component prepared as mentioned above (75.16
millimole per 1 mole titanium atom) were added, then 210 g of
propylene was supplied to conduct a preliminary polymerization for
20 minutes at -1.degree. C.
[0218] Polymer generated in a preliminary polymerization obtained
under the same conditions was analyzed and it was found that 1.2 g
of polypropylene (B) was generated per 1 g of the supported
titanium catalyst component, and the intrinsic viscosity
[.eta..sub.B] measured in tetralin at 135.degree. C. of
polypropylene (B) was 2.7 dl/g.
[0219] After the reaction period, unreacted propylene was
discharged outside the polymerization reactor. After substituting
the gas phase portion with a nitrogen gas once, ethylene was
supplied continuously for three hours to the polymerization reactor
so as to maintain the inside pressure at 0.59 MPa with the inside
temperature at -1.degree. C. to conduct the preliminary activating
polymerization.
[0220] Polymer generated in a preliminary activating polymerization
obtained in the same conditions was analyzed and it was found that
33.2 g of polymer existed per 1 g of the supported titanium
catalyst component, and the intrinsic viscosity [.eta..sub.T2]
measured in tetralin at 135.degree. C. was 29.2 dl/g.
[0221] The amount of polyethylene (A) generated in the preliminary
activating polymerization with ethylene per 1 g of the supported
catalyst component containing titanium and the intrinsic viscosity
[.eta..sub.A] were found to be 32 g per 1 g of the supported
titanium catalyst component and 30.2 dl/g, respectively.
[0222] After the reaction period, unreacted ethylene was discharged
outside the polymerization reactor. After substituting the gas
phase portion with a nitrogen gas once, and adding 22.5 millimole
of diisopropyldimethoxy silane (electron donor (E1)) into the
polymerization reactor, 385 g of propylene was supplied and
maintained for 20 minutes at 0.degree. C. to conduct the addition
polymerization after the preliminary activating treatment. After
the reaction period, unreacted propylene was discharged outside the
reaction container and the gas phase portion of the reaction
container was substituted with nitrogen to obtain a preactivated
catalyst slurry of the main (co-)polymerization.
[0223] Polymer generated in an addition polymerization obtained
using the same conditions was analyzed and it was found that 35.4 g
of polymer existed per 1 g of the supported titanium catalyst
component, and the intrinsic viscosity [.eta..sub.T3] of the
polymer measured in tetralin at 135.degree. C. was 27.6 dl/g.
[0224] From the above mentioned results, the amount of
polypropylene generated in the addition polymerization was 2.2 g
per 1 g of the supported titanium catalyst component, and the
intrinsic viscosity [.eta..sub.C] was 2.8 dl/g.
[0225] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0226] After providing a nitrogen gas atmosphere in a 110 liter
capacity continuous horizontal gas phase polymerization reactor
with an agitator (length/diameter=3.7), 25 kg of polypropylene
powders were introduced, and further 0.61 g/h of the preactivated
catalyst slurry as the supported titanium catalyst component and 15
weight % n-hexane solution of triethyl aluminum (organic metal
compound (AL2)) and diisopropyl dimethoxy silane (electron donor
(E2)) were continuously supplied so that the respective molar
ratios became 90 and 15 based on the titanium atoms in the
supported titanium catalyst component.
[0227] Further, under the condition of polymerization temperature
of 70.degree. C., hydrogen was supplied so as to have the
hydrogen/propylene ratio in the polymerization reactor became
0.006, and further, propylene was supplied so as to maintain the
pressure inside the polymerization reactor at 2.15 MPa to conduct
the gas phase polymerization of propylene continuously for 150
hours.
[0228] During the polymerization period, polymer was taken out from
the polymerization reactor at the rate of 11 kg/h so as to maintain
the polymer level in the polymerization reactor at 60 volume %.
[0229] The taken-out polymer was treated by contacting with a
nitrogen gas containing 5 volume % of water vapor at 100.degree. C.
for 30 minutes to obtain a polymer having an intrinsic viscosity
[.eta..sub.T] of 1.80 dl/g.
[0230] The ratio of polyethylene (A) generated by the preliminary
activating treatment in the polymer was 0.18 weight % and the
intrinsic viscosity [.eta..sub.P] of polypropylene was 1.75
dl/g.
[0231] Subsequently, using the same conditions as example 1,
polymer pellets were prepared with an extruder. Various physical
properties of the pellets were measured and evaluated to find the
MFR, the crystallization temperature, and the melt tension (MS) to
be 6.0 g/10 minutes, 122.0.degree. C. and 2.5 cN, respectively.
Example 4
[0232] A polypropylene composition was produced using the same
conditions as example 3 except that the hydrogen/propylene ratio in
the gas phase was altered to 0.008 to change the MFR in example 3
to prepare the evaluation specimen of example 4.
[0233] Various physical properties of the obtained polypropylene
composition are shown in Table 2.
Comparative Example 5
[0234] A polymer was produced using the same conditions as example
3 except that the preliminary activating polymerization with
ethylene was not conducted to prepare the evaluation specimen of
comparative example 5.
[0235] Various physical properties of the obtained polymer are
shown in Table 2.
Example 5
[0236] (1) Preparation of catalyst composition including transition
metal compound
[0237] Using the same conditions as example 3, a supported titanium
catalyst component was obtained.
[0238] (2) Preparation of preactivated catalyst
[0239] Using the same preliminary activating polymerization
conditions the same as example 3 (2) except that the reaction
temperature was 0.degree. C., 30 g of propylene was supplied in
addition to ethylene and the reaction temperature was 45 minutes, a
preactivated catalyst slurry was obtained.
[0240] A catalyst obtained by processing with the preliminary
activating treatment using the same conditions was analyzed and it
was found that 23.2 g of polymer existed per 1 g of the supported
titanium catalyst component, and the intrinsic viscosity
[.eta..sub.T2] of the polymer measured in tetralin at 135.degree.
C. was 21.5 dl/g and an ethylene-propylene random copolymer (A)
having an intrinsic viscosity [.eta..sub.A] of 22.5 dl/g and a
propylene polymerization unit containing ratio of 0.7 weight %
(constant by C-NMR) was generated in the amount of 22 g per 1 g of
the supported titanium catalyst component by the preliminary
activating treatment.
[0241] A polymer obtained by the addition polymerization after the
preliminary activating treatment using the same conditions was
analyzed and it was found that 25.3 g of polymer existed per 1 g of
the supported titanium catalyst component, and the intrinsic
viscosity [.eta..sub.T3] of the polymer measured in tetralin at
135.degree.C. was 19.9 dl/g and a polymer having an intrinsic
viscosity [.eta..sub.C] of 2.2 dl/g was generated in the amount of
2.1 g per 1 g of the supported titanium catalyst component by the
addition polymerization.
[0242] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0243] A polymer having an intrinsic viscosity [.eta..sub.T] of
1.54 dl/g and the ethylene polymerization unit of 0.8 weight % was
obtained at the rate of 11.6 kg/h by conducting the gas phase
polymerization for 150 hours continuously using the same conditions
as example 3 (3) except that the preactivated catalyst slurry
obtained in the above mentioned (2) was used as the preactivated
catalyst slurry, the hydrogen/propylene ratio in the gas phase was
0.012, and ethylene was supplied in addition to propylene so that
the ratio with respect to the propylene concentration in the
polymerization reactor is kept at 0.003 continuously.
[0244] The ratio of the ethylene-propylene random copolymer (A) in
the polymer generated in the preliminary activating treatment was
0.12 weight %, and the intrinsic viscosity [.eta..sub.P] of the
propylene-ethylene copolymer was 1.52 dl/g.
[0245] Subsequently, in the same conditions as example 1 (3),
polypropylene composition pellets were prepared with an extruder.
Various physical properties of the pellets were measured and
evaluated to find the MFR, the crystallization temperature, and the
melt tension (MS) to be 15.4 g/10 minutes, 121.2.degree. C. and 1.4
cN, respectively.
Comparative Example 6
[0246] A polymer was produced using the same conditions as example
5 except that the preliminary activating polymerization with
ethylene and propylene was not conducted to prepare the evaluation
specimen of comparative example 6.
[0247] Various physical properties of the obtained polymer are
shown in Table 2.
Comparative Example 7
[0248] Only the preliminary activating polymerization with ethylene
in example 1 (2) was conducted without the preliminary
polymerization with propylene nor the addition polymerization. 1
liter of methanol was added to the obtained preactivated catalyst
slurry to conduct the deactivation of the catalyst for one hour at
70.degree. C. After the reaction, polyethylene was separated from
the slurry by filtration, then dried under a reduced pressure to
obtain 200 g of polyethylene having an intrinsic viscosity
[.eta..sub.A] of 32.5 dl/g.
[0249] 20 kg of polypropylene obtained by the main polymerization
of propylene without the preliminary activating polymerization with
ethylene nor the addition polymerization with propylene in example
1 (2), and 50 g of the above mentioned prepared polyethylene were
mixed. Further, 20 g of 2,6-di-t-butyl-p-cresol and 20 g of calcium
stearate were added and mixed for 3 minutes in a 100 liter capacity
Henschel mixer. Then the mixture was pelletized with an extruder
having a screw diameter of 40 mm at 230.degree. C. to prepare the
evaluation specimen of comparative example 7.
[0250] Various physical properties of the obtained pellets include
an intrinsic viscosity [.eta..sub.T] of 1.97 dl/g, MFR of 3.5 g/10
minutes, the crystallization temperature of 116.2.degree. C. and
the melt tension (MS) of 1.0 cN.
2 TABLE 2 Comparative Examples Examples 3 4 5.sup.3 5 6 7.sup.4
Preliminary polymerization <polypropylene (B)> 2.7 2.7 2.7
2.7 2.7 -- Intrinsic viscosity [.eta..sub.B] (dl/g) Generated
amount .sup.1 (g/g) 1.2 1.2 1.2 1.2 1.2 -- Composition ratio .sup.2
(wt %) 0.01 0.01 0.01 0.01 0.01 -- Preliminary activation
<polyethylene (A)> 30.2 30.2 22.5 -- -- 32.5 Intrinsic
viscosity [.eta..sub.A] (dl/g) Generated amount .sup.1 (g/g) 32.0
32.0 22.0 -- -- -- Composition ratio .sup.2 (wt %) 0.18 0.17 0.12
-- -- 0.25 Addition polymerization <polypropylene (C)> 2.8
2.8 2.2 2.8 2.2 -- Intrinsic viscosity [.eta..sub.C] (dl/g)
Generated amount .sup.1 (g/g) 2.2 2.2 2.1 2.2 2.1 -- Composition
ratio .sup.2 (wt %) 0.01 0.01 0.01 0.01 0.01 -- Polymerization
process Intrinsic viscosity [.eta..sub.D] 1.75 1.63 1.52 1.75 1.52
1.89 (dl/g) Composition ratio .sup.2 (wt %) 99.8 99.8 99.9 100 100
99.7 Propylene (co-) polymer Intrinsic viscosity [.eta..sub.P] 1.75
1.63 1.52 1.75 1.52 1.89 (dl/g) Propylene (co-)polymer composition
Intrinsic viscosity [.eta..sub.T] 1.80 1.68 1.54 1.75 1.52 1.97
(dl/g) Melt tension (MS) (cN) 2.5 2.4 1.4 0.6 0.3 1.0
Crystallization temperature 122.0 122.7 121.2 116.1 115.2 116.2
(.degree. C.) MFR (g/10 minutes) 6.0 8.1 15.4 7.2 16.7 3.5 initial
final (g/10 minutes) 6.1 8.0 15.2 7.4 16.5 3.6 .DELTA.MFR (g/10
minutes) 0.1 -0.1 -0.2 0.2 -0.2 0.1 Note 1 Generated amount (g) per
1 g of transitional metal compound catalyst component Note 2
Composition ratio (wt %) in the propylene .alpha.-olefin (co-)
polymer composition Note 3 Comparative example 5; a gas mixture of
ethylene and propylene was used as the monomer for the preliminary
activation Note 4 Comparative example 7; mechanical simple mixing
of polyethylene and main polymerization polypropylene
Example 6
[0251] (1) Preparation of catalyst composition including transition
metal compound
[0252] Using the same conditions as example 3, a supported titanium
catalyst component was obtained.
[0253] (2) Preparation of preactivated catalyst
[0254] Using the same conditions as example 3, a preactivated
catalyst slurry was obtained.
[0255] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0256] Using the same conditions as example 3 except that hydrogen
was supplied so as to have the hydrogen/propylene ratio in the
polymerization reactor (I) at 0.002, and propylene was further
supplied to maintain the inside pressure of the polymerization
reactor at 1.77 MPa to implement the polymerization process
(I).
[0257] A polymer obtained by the polymerization process using the
same conditions was analyzed and it was found that the MFR was 1.1
g/10 minutes, the intrinsic viscosity [.eta..sub.T] of the polymer
measured in tetralin of 135.degree. C. was 2.39 dl/g. The intrinsic
viscosity [.eta..sub.P] of polypropylene in the polymerization
process (I) was 2.32 dl/g.
[0258] The polymer obtained in the above mentioned process was
continuously supplied to a polymerization reactor (II) of
60.degree. C. so as to maintain the hydrogen/propylene ratio and
the hydrogen/ethylene ratio in the polymerization reactor at 0.003
and 0.2, respectively, and to maintain the pressure inside the
polymerization reactor at 1.57 MPa to implement the polymerization
process (II).
[0259] During the polymerization period, polymer was taken out from
the polymerization reactor at the rate of 9.4 kg/h so as to
maintain the polymer level in the polymerization reactor at 60
volume %.
[0260] The taken-out polymer was treated by contacting with a
nitrogen gas containing 5 volume % of water vapor at 100.degree. C.
for 30 minutes to obtain a polymer having an intrinsic viscosity
[.eta..sub.T] of 2.69 dl/g.
[0261] The ratio of polyethylene (A) generated by the preliminary
activating treatment in the polymer was 0.21 weight % and the
intrinsic viscosity [.eta..sub.P] of the polypropylene'
.alpha.-olefin block copolymer composition (b) was 2.63 dl/g.
[0262] The polymerization ratio between the polymerization process
(I) and the polymerization process (II) was calculated by preparing
copolymers having different reaction amount ratios of
ethylene/propylene beforehand, and using this as the standard
sample to make a calibration curve with the infrared absorption
spectrum and find the ethylene/propylene reaction amount ratio in
the polymerization process (II), and further calculated from the
ethylene containing amount in the entire polymer. The results are
shown in Table 3.
[0263] Subsequently, using the same conditions as example 1,
polymer pellets were prepared with an extruder. Various physical
properties of the pellets were measured and evaluated to find the
MFR, the crystallization temperature, and the melt tension (MS) to
be 0.52 g/10 minutes, 121.9.degree. C. and 5.2 cN,
respectively.
Example 7
[0264] (1) Preparation of catalyst composition including transition
metal compound
[0265] Using the same conditions as example 1, a supported titanium
catalyst component was obtained.
[0266] (2) Preparation of preactivated catalyst
[0267] In the preliminary activating polymerization conditions the
same as example 1, a preactivated catalyst slurry was obtained.
[0268] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0269] After providing a nitrogen gas atmosphere in a 500 liter
capacity stainless steel polymerization reactor with an agitator,
240 liters of n-hexane, 780 millimole of triethyl aluminum (organic
metal compound (AL2)), 78 millimole of diisopropyldimethoxy silane
(electron donor (E2)) and 1/2amount of the preactivated catalyst
slurry obtained as mentioned above were added at 20.degree. C. Then
after introducing 100 liters of hydrogen into the polymerization
reactor and raising the temperature to 70.degree. C., propylene was
continuously supplied into the polymerization reactor so as to
maintain the pressure of the gas phase portion at 0.79 MPa for 90
minutes at the polymerization temperature of 70.degree. C. to
conduct the polymerization process (I). After the polymerization
process (I), supply of propylene was terminated and the temperature
inside the polymerization reactor was cooled to 30.degree. C., and
then hydrogen and unreacted propylene were discharged. A part of
the polymerized slurry was taken out for measuring the MFR, which
was found to be 7.5.
[0270] After raising the temperature inside the polymerization
reactor to 60.degree. C., 30 liters of hydrogen was introduced to
the polymerization container, and ethylene and propylene were
supplied so as to have the supply ratio of the ethylene become 35
weight % continuously for two hours. The entire supplied amount of
the ethylene was 7.5 kg.
[0271] After the polymerization period, 1 liter of methanol was
introduced to the polymerization reactor and the deactivation of
catalyst was conducted at 70.degree. C. for 15 minutes. Then after
discharging the unreacted gas, the solvent was separated and the
polymer was dried to obtain 40.5 kg of a polymer having an
intrinsic viscosity [.eta..sub.T] of 1.95 dl/g.
[0272] The obtained polymer was a propylene' .alpha.-block polymer
composition containing 0.26 weight % of polyethylene (A) according
to the preliminary activating polymerization as the (a) component
and the intrinsic viscosity [.eta..sub.P] of the propylene'
.alpha.-block polymer composition as the (b) component was 1.87
dl/g.
[0273] The polymerization ratio between the polymerization process
(I) and the polymerization process (II) was calculated by preparing
copolymers having different reaction amount ratios of
ethylene/propylene beforehand, and using this as the standard
sample to make a calibration curve with the infrared absorption
spectrum and find the ethylene/propylene reaction amount ratio in
the polymerization process (II), and further calculated from the
ethylene containing amount in the entire polymer. The results are
shown in Table 3.
[0274] Subsequently, using the same conditions as example 1,
polymer pellets were prepared with an extruder. Various physical
properties of the pellets were measured and evaluated to find the
MFR, the crystallization temperature, and the melt tension (MS) to
be 3.0 g/10 minutes, 121.5.degree. C. and 2.1 cN, respectively.
Example 8
[0275] The polymerization process (I) was conducted using the same
conditions as example 7 (3), except that the production conditions
of the main (co-)polymer composition were altered, that is, after
supplying so as to have the propylene/ethylene ratio at 0.3 in the
first stage, 50 liters of hydrogen was introduced inside the
polymerization reactor and the temperature was raised to 60.degree.
C., propylene was supplied continuously for 90 minutes under the
condition of the polymerization temperature of 60.degree. C. and
maintaining the gas phase pressure inside the polymerization
reactor at 0.79 MPa. After the polymerization process (I), supply
of propylene and ethylene was terminated and the temperature inside
the container was cooled to 30.degree. C., then hydrogen and
unreacted propylene were discharged. A part of the polymerized
slurry was taken out for measuring the MFR, which was found to be
3.0.
[0276] After raising the temperature inside the container to
60.degree.C., 50 liters of hydrogen was introduced to the
polymerization reactor, and ethylene and propylene were supplied so
as to have the supply ratio of the ethylene become 35 weight %
continuously for two hours. The entire supply amount of ethylene
was 8.2 kg.
[0277] After the polymerization period, 1 liter of methanol was
introduced to the polymerization reactor and the deactivation of
catalyst was conducted at 70.degree. C. for 15 minutes. Then after
discharging the unreacted gas, the solvent was separated and the
polymer was dried to obtain 40.5 kg of a polymer having an
intrinsic viscosity [.eta..sub.T] of 2.08 dl/g.
[0278] The obtained polymer was a propylene' .alpha.-olefin block
copolymer composition containing 0.24 weight % of polyethylene (A)
according to the preliminary activating polymerization as the (a)
component and the intrinsic viscosity [.eta..sub.P] of the
polypropylene' .alpha.-olefin block copolymer composition as the
(b) component was 2.00 dl/g.
[0279] The polymerization ratio between the polymerization process
(I) and the polymerization process (II) was calculated by preparing
copolymers having different reaction amount ratios of
ethylene/propylene beforehand, and using this as the standard
sample to make a calibration curve with the infrared absorption
spectrum and find the ethylene/propylene reaction amount ratio in
the polymerization process (II), and further calculated from the
ethylene containing amount in the entire polymer. The results are
shown in Table 3.
[0280] Subsequently, using the same conditions as example 1,
polymer pellets were prepared with an extruder. Various physical
properties of the pellets were measured and evaluated to find the
MFR, the crystallization temperature, and the melt tension (MS) to
be 2.0 g/10 minutes, 116.8.degree. C. and 2.5 cN, respectively.
Comparative Example 8
[0281] Using the same conditions as comparative example 5, a
supported titanium catalyst slurry was obtained. Using the
supported titanium catalyst slurry, a propylene' .alpha.-olefin
block copolymer composition was produced using the same conditions
as example 6 (3) to prepare an evaluation specimen of comparative
example 8.
[0282] Various physical properties of the obtained propylene'
.alpha.-olefin block copolymer composition are shown in Table
3.
Comparative Example 9
[0283] Using the same conditions as comparative example 3, a
supported titanium catalyst slurry was obtained. Using the
supported titanium catalyst slurry, a propylene' .alpha.-olefin
block copolymer composition was produced using the same conditions
as example 7 (3) to prepare an evaluation specimen of comparative
example 9.
[0284] Various physical properties of the obtained propylene'
.alpha.-olefin block copolymer composition are shown in Table
3.
Comparative Example 10
[0285] Using the same conditions as comparative example 3, a
supported titanium catalyst slurry was obtained. Using the
supported titanium catalyst slurry, a propylene' .alpha.-olefin
block copolymer composition was produced using the same conditions
as example 8 (3) to prepare an evaluation specimen of comparative
example 10.
[0286] Various physical properties of the obtained propylene'
.alpha.-olefin block copolymer composition are shown in Table
3.
3 TABLE 3 Comparative Examples Examples 6 7 8 8 9 10 Preliminary
polymerization <polypropylene (B)> 2.7 2.8 2.8 2.7 2.8 2.8
Intrinsic viscosity [.eta..sub.B] (dl/g) Generated amount .sup.1
(g/g) 1.2 2.0 2.0 1.2 2.0 2.0 Composition ratio .sup.2 (wt %) 0.01
0.02 0.02 0.01 0.02 0.02 Preliminary activation <polyethylene
(A)> 30.2 34.0 34.0 -- -- -- Intrinsic viscosity [.eta..sub.A]
(dl/g) Generated amount .sup.1 (g/g) 32.0 22.0 22.0 -- -- --
Composition ratio .sup.2 (wt %) 0.21 0.26 0.24 -- -- -- Addition
polymerization <polypropylene (C)> 2.8 2.8 2.8 2.8 2.8 2.8
Intrinsic viscosity [.eta..sub.C] (dl/g) Generated amount .sup.1
(g/g) 2.2 2.0 2.0 2.2 2.0 2.0 Composition ratio .sup.2 (wt %) 0.01
0.02 0.02 0.01 0.02 0.02 Polymerization process (I) 0 0 2.1 0 0 2.1
Ethylene (wt %) Intrinsic viscosity [.eta..sub.PP] 2.32 1.60 1.88
2.29 1.71 1.98 (dl/g) Composition ratio .sup.2 (wt %) 85.7 78.8
82.3 86.1 78.6 81.9 polymerization process (II) 57 65 81 56 66 80
Ethylene (wt %) Intrinsic viscosity [.eta..sub.RC] 4.84 3.22 2.96
5.29 2.97 2.70 (dl/g) Composition ratio .sup.2 (wt %) 14.1 20.9
17.4 13.9 21.4 18.1 Propylene (co-) polymer Intrinsic viscosity
[.eta..sub.P] 2.63 1.87 2.00 2.71 1.98 2.11 (dl/g) Propylene (co-)
polymer 8.2 13.8 14.3 7.8 14.1 14.5 composition Ethylene (wt %)
Intrinsic viscosity [.eta..sub.T] 2.69 1.95 2.08 2.71 1.98 2.11
(dl/g) Melt tension (MS) (cN) 5.2 2.1 2.5 3.3 0.8 1.1
Crystallization temperature 121.9 121.5 116.8 116.0 115.8 110.3
(.degree. C.) MFR (g/10 minutes) 0.52 3.0 2.0 0.48 2.8 2.1 initial
final (g/10 minutes) 0.51 3.1 1.9 0.48 2.9 2.0 .DELTA.MFR (g/10
minutes) -0.01 0.1 -0.01 0.00 0.1 -0.1 Note 1 Generated amount (g)
per 1 g of transitional metal compound catalyst component Note 2
Composition ratio (wt %) in the propylene (co-) polymer
composition
Example 9
[0287] (1) Preparation of catalyst composition including transition
metal component
[0288] Using the same conditions as example 1, a supported titanium
catalyst component was obtained.
[0289] (2) Preparation of preactivated catalyst
[0290] Using the same conditions as example 1, a preactivated
catalyst slurry was obtained.
[0291] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0292] After providing a nitrogen gas atmosphere in a 500 liter
capacity stainless steel polymerization container with an agitator,
240 liters of n-hexane, 780 millimole of triethyl aluminum (organic
metal compound (AL2)), 78 millimole of diisopropyldimethoxy silane
(electron donor (E2)) and 1/2amount of the preactivated catalyst
slurry obtained as mentioned above were added at 20.degree. C. Then
after supplying so as to have the hydrogen/propylene ratio and the
propylene/ethylene ratio at 0.04 and 0.03 respectively and the
temperature was raised to 60.degree. C., polypropylene, hydrogen
and ethylene were supplied continuously for two hours while
maintaining the gas phase pressure inside the polymerization
reactor at 0.79 MPa to implement the copolymerization of
propylene'.alpha.-olefin.
[0293] After the polymerization period, 1 liter of methanol was
introduced into the polymerization reactor and the deactivation of
catalyst was conducted at 60.degree. C. for 15 minutes. Then after
discharging unreacted gas, solvent was separated and the polymer
was dried to obtain 41.0 kg of a polymer having an intrinsic
viscosity [.eta..sub.T] of 1.91 dl/g.
[0294] The obtained polymer was a polypropylene'.alpha.-olefin
random copolymer composition containing 0.24 weight % of
polyethylene (A) according to the preliminary activating
polymerization as the (a) component and the intrinsic viscosity
[.eta..sub.P] of the propylene'.alpha.-olefin copolymer as the (b)
component was 1.83 dl/g.
[0295] Subsequently, using the same conditions as example 1,
polymer pellets were prepared with an extruder. Various physical
properties of the pellets were measured and evaluated to find the
MFR, the crystallization temperature, and the melt tension (MS) to
be 3.7 g/10 minutes, 115.2.degree. C. and 1.8 cN, respectively.
Example 10
[0296] (1) Preparation of catalyst composition including transition
metal compound
[0297] Using the same conditions as example 3, a supported titanium
catalyst component was obtained.
[0298] (2) Preparation of preactivated catalyst
[0299] Using the same conditions as example 3, a preactivated
catalyst slurry was obtained.
[0300] (3) Production of polypropylene composition (main
(co-)polymerization of propylene)
[0301] 25 kg of polypropylene powders were introduced to a 110
liter capacity continuous type horizontal gas phase reactor
(length/diameter=3.7) with an agitator, and further, a preactivated
catalyst slurry as the supported titanium catalyst component at the
rate of 0.81 g/h, and 15 weight % n-hexane solution of triethyl
aluminum (organic metal compound (AL2)) and diisopropyldimethoxy
silane (electron donor (E2)) were supplied continuously so as to
have the molar ratios with respect to titanium atoms in the
supported titanium catalyst component of 90 and 15,
respectively.
[0302] Under the condition of the polymerization temperature of
60.degree. C., hydrogen and ethylene were supplied so as to have
the hydrogen/propylene ratio and the ethylene/propylene ratio in
the polymerization reactor of 0.02. Further, by supplying propylene
so as to maintain the pressure inside the polymerization reactor at
1.77 MPa to conduct the gas phase polymerization of propylene
continuously for 150 hours.
[0303] During the polymerization period, polymer was taken out from
the polymerization reactor at the rate of 12 kg/h so as to keep the
polymer level inside the polymerization reactor at 60 volume The
taken-out polymer was treated by contacting with a nitrogen gas
containing 5 volume % of water vapor at 100.degree. C. for 30
minutes to obtain a polymer having an intrinsic viscosity
[.eta..sub.T] of 1.95 dl/g.
[0304] The ratio of polyethylene (A) generated by the preliminary
activating treatment in the polymer was 0.22 weight % and the
intrinsic viscosity [.eta..sub.P] of the propylene'.alpha.-olefin
block copolymer composition (b) was 1.89 dl/g.
[0305] Subsequently, using the same conditions as example 1,
polymer pellets were prepared with an extruder. Various physical
properties of the pellets were measured and evaluated to find the
MFR, the crystallization temperature, and the melt tension (MS) to
be 3.2 g/10 minutes, 110.0.degree. C. and 1.9 cN, respectively.
Example 11
[0306] (1) Preparation of catalyst composition including transition
metal compound
[0307] Using the same conditions as example 1, a supported titanium
catalyst component was obtained.
[0308] (2) Preparation of preactivated catalyst
[0309] Using the same conditions as example 1, a preactivated
catalyst slurry was obtained.
[0310] (3) Production of polypropylene composition (main
(co)polymerization of propylene)
[0311] After providing a nitrogen gas atmosphere in a 500 liter
capacity stainless steel polymerization reactor with an agitator,
240 liters of n-hexane, 780 millimole of triethyl aluminum (organic
metal compound (AL2)), 78 millimole of diisopropyldimethoxy silane
(electron donor (E2)) and 1/2amount of the preactivated catalyst
slurry obtained as mentioned above were added at 20.degree. C. Then
after supplying so as to have the hydrogen/propylene ratio, the
hydrogen/ethylene ratio and the propylene/butene-1 ratio of 0.08,
0.025 and 0.038, respectively and the temperature was raised to
60.degree. C., propylene, hydrogen, ethylene and butene-1 were
supplied continuously for two hours while maintaining the gas phase
pressure inside the polymerization reactor at 0.79 MPa to implement
the copolymerization of propylene'.alpha.-olefin.
[0312] After the polymerization period, 1 liter of methanol was
introduced into the polymerization reactor and the deactivation of
catalyst was conducted at 60.degree. C. for 15 minutes. Then after
discharging unreacted gas, solvent was separated and the polymer
was dried to obtain 39.6 kg of a polymer having an intrinsic
viscosity [.eta..sub.T] of 1.67 dl/g.
[0313] The obtained polymer was a propylene'.alpha.-olefin
copolymer composition containing 0.25 weight % of polyethylene (A)
according to the preliminary activating polymerization as the (a)
component and the intrinsic viscosity [.eta..sub.P] of the
propylene'.alpha.-olefin copolymer composition as the (b) component
was 1.59 dl/g.
[0314] Subsequently, using the same conditions as example 1,
polymer pellets were prepared with an extruder. Various physical
properties of the pellets were measured and evaluated to find the
MFR, the crystallization temperature, and the melt tension (MS) to
be 7.6 g/10 minutes, 110.3.degree. C. and 1.3 cN, respectively.
Comparative Example 11
[0315] Using the same conditions as comparative example 3, a
supported titanium catalyst slurry was obtained. Using the
supported titanium catalyst slurry, a propylene'.alpha.-olefin
block copolymer composition was produced using the same conditions
as example 9 (3) to prepare an evaluation specimen of comparative
example 11.
[0316] Various physical properties of the obtained
propylene'.alpha.-olefi- n block copolymer composition are shown in
Table 4.
Comparative Example 12
[0317] Using the same conditions as comparative example 5, a
supported titanium catalyst slurry was obtained. Using the
supported titanium catalyst slurry, a propylene'.alpha.-olefin
block copolymer composition was produced using the same conditions
as example 10 (3) to prepare an evaluation specimen of comparative
example 12.
[0318] Various physical properties of the obtained
propylene'.alpha.-olefi- n block copolymer composition are shown in
Table 4.
Comparative Example 13
[0319] Using the same conditions as comparative example 3, a
supported titanium catalyst slurry was obtained. Using the
supported titanium catalyst slurry, a propylene'.alpha.-olefin
block copolymer composition was produced using the same conditions
as example 11 (3) to prepare an evaluation specimen of comparative
example 13.
[0320] Various physical properties of the obtained
propylene'.alpha.-olefi- n block copolymer composition are shown in
Table 4.
4 TABLE 4 Comparative Examples Examples 9 10 11 11 12 13
Preliminary polymerization <polypropylene (B)> 2.8 2.7 2.8
2.8 2.7 2.8 Intrinsic viscosity [.eta..sub.B] (dl/g) Generated
amount .sup.1 (g/g) 2.0 1.2 2.0 2.0 1.2 2.0 Composition ratio
.sup.2 (wt %) 0.02 0.01 0.02 0.02 0.01 0.02 Preliminary activation
<polyethylene (A)> 34.0 30.2 34.0 -- -- -- Intrinsic
viscosity [.eta..sub.A] (dl/g) Generated amount .sup.1 (g/g) 22.0
32.0 22.0 -- -- -- Composition ratio .sup.2 (wt %) 0.24 0.22 0.25
-- -- -- Addition polymerization <polypropylene (C)> 2.8 2.8
2.8 2.8 2.8 2.8 Intrinsic viscosity [.eta..sub.C] (dl/g) Generated
amount .sup.1 (g/g) 2.0 2.2 2.0 2.0 2.2 2.0 Composition ratio
.sup.2 (wt %) 0.02 0.01 0.02 0.02 0.01 0.02 Polymerization process
2.7 4.6 2.4 2.5 4.9 2.4 Ethylene (wt %) Butene-1 (wt %) 0 0 3.9 0 0
3.8 Intrinsic viscosity [.eta..sub.D] 1.83 1.89 1.59 1.97 1.97 1.69
(dl/g) Composition ratio .sup.2 (wt %) 99.7 99.8 99.7 100 100 100
Propylene (co-) polymer Intrinsic viscosity [.eta..sub.P] 1.83 1.89
1.59 1.97 1.97 1.69 (dl/g) Propylene (co-) polymer 2.9 4.8 2.7 2.5
4.9 2.4 composition Ethylene (wt %) Butene-1 (wt %) 0 0 3.9 0 0 3.8
Intrinsic viscosity [.eta..sub.T] 1.91 1.95 1.67 1.97 1.97 1.69
(dl/g) Melt tension (MS) (cN) 1.8 1.9 1.3 0.7 0.7 0.3
Crystallization temperature 115.2 110.0 110.3 109.4 102.9 104.8
(.degree. C.) MFR (g/10 minutes) 3.7 3.2 7.6 3.5 3.1 8.1 initial
final (g/10 minutes) 3.6 3.0 7.6 3.4 2.9 7.9 .DELTA.MFR (g/10
minutes) -0.1 -0.2 0.0 -0.1 -0.2 -0.2 Note 1: Generated amount (g)
per 1 g of transitional metal compound catalyst component Note 2:
Composition ratio (wt %) in the propylene (co-) polymer
composition
Example 12
[0321] (1) Preparation of catalyst composition including transition
metal compound
[0322] Using the same conditions as example 1, a supported titanium
catalyst component was obtained.
[0323] (2) Preparation of preactivated catalyst
[0324] Using the same conditions as example 1, a preliminary
activating polymerization with ethylene and an addition
polymerization with propylene were conducted without a preliminary
polymerization with propylene.
[0325] A polymer obtained by the preliminary activating
polymerization process in the same conditions was analyzed and it
was found that 22.2 g of polyethylene (A) existed per 1 g of the
supported titanium catalyst component, and the intrinsic viscosity
[.eta..sub.A] of the polymer measured in tetralin at 135.degree. C.
was 32.5 dl/g.
[0326] A polymer generated by the preliminary activating
polymerization process using the same conditions and further
treated by an addition polymerization was analyzed and it was found
that 2.0 g of polymer existed per 1 g of the supported titanium
catalyst component only by the addition polymerization, and the
intrinsic viscosity [.eta.] of the polymer measured in tetralin at
135.degree. C. was 2.3 dl/g.
[0327] (3) Production of polypropylene composition (main
(co-)polymerization of propylene)
[0328] Using the prepared preactivated catalyst, the main
polymerization of propylene was conducted using the same conditions
as example 1 to produce polypropylene. The obtained polypropylene
was pelletized using the same conditions as example 1 to obtain an
evaluation specimen of comparative example 12.
[0329] Various physical properties of the obtained polypropylene
are shown in Table 5.
Comparative Example 14
[0330] A preactivated catalyst was prepared using the same
conditions as example 1 except that the preliminary activating
polymerization with propylene or the preliminary activating
polymerization with ethylene was not conducted and only the
addition polymerization with propylene was conducted. The obtained
preactivated catalyst was used for the main polymerization of
propylene using the same conditions as example 1 to produce
polypropylene. The obtained polypropylene was pelletized using the
same conditions as example 1 to obtain an evaluation specimen of
comparative example 14.
[0331] Various physical properties of comparative example 14 are
shown in Table 5.
[0332] Example 13 and Comparative Example 15 Polypropylene
compounds having different polyethylene (A) contents were produced
using the same conditions as example 1 except that the preliminary
activating polymerization with propylene was not conducted and the
conditions of the preliminary activating polymerization with
ethylene were changed. The polypropylene compounds were treated
using the same process as example 1 to obtain evaluation specimens
of example 13 and comparative example 15.
[0333] Various physical properties of example 13 and comparative
example 15 are shown in Table 5.
Example 14
[0334] (1) Preparation of catalyst composition including transition
metal compound
[0335] Using the same conditions as example 3, a supported titanium
catalyst component was obtained.
[0336] (2) Preparation of preactivated catalyst
[0337] Using the same conditions as example 3 except that the
preliminary polymerization with propylene was not conducted, the
preliminary activating polymerization with ethylene and the
addition polymerization with propylene were conducted.
[0338] A polymer obtained by the preliminary activating
polymerization in the same conditions was analyzed and it was found
that 32.0 g of polyethylene (A) existed per 1 g of the supported
titanium catalyst component, and the intrinsic viscosity
[.eta..sub.A] of the polymer measured in tetralin at 135.degree. C.
was 29.8 dl/g.
[0339] A polymer generated by the preliminary activating
polymerization using the same conditions and further an addition
polymerization was analyzed and it was found that 2.2 g of polymer
existed per 1 g of the supported titanium catalyst component only
by the addition polymerization, and the intrinsic viscosity
[.eta..sub.A] of polymer measured in tetralin at 135.degree. C. was
3.4 dl/g.
[0340] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0341] Using the prepared preactivated catalyst, the main
polymerization of propylene was conducted using the same conditions
as example 3 to produce polypropylene. The obtained polypropylene
was pelletized using the same conditions as example 3 to obtain an
evaluation specimen of comparative example 14.
[0342] Various physical properties of the obtained polypropylene
are shown in Table 5.
Comparative Example 16
[0343] A propylene (co-)polymer composition was produced using the
same conditions as example 3 except that the preliminary activating
treatment of (2) was not conducted and the polymerization of
propylene was conducted under the presence of the solid titanium
catalyst obtained in (1) under the conditions the same as (3) to
obtain an evaluation specimen of comparative example 16.
[0344] Various physical properties of the obtained polypropylene
are shown in Table 5.
5 TABLE 5 Comparative Examples Examples 12 13 14 14 15 16
Preliminary activation <polyethylene (A)> 32.5 32.5 29.8 --
32.5 -- Intrinsic viscosity [.eta..sub.A] (dl/g) Generated amount
.sup.1 (g/g) 22.2 4.5 32.0 -- 0.005 -- Composition ratio .sup.2 (wt
%) 0.25 0.05 0.18 -- 0.0001 -- Addition polymerization
<polypropylene (C)> 2.3 2.3 3.4 2.0 2.3 -- Intrinsic
viscosity [.eta..sub.C] (dl/g) Generated amount .sup.1 (g/g) 2.0
2.0 2.2 2.0 2.0 -- Composition ratio .sup.2 (wt %) 0.02 0.02 0.02
0.02 0.02 -- Polymerization process Intrinsic viscosity
[.eta..sub.D] 1.89 1.89 1.75 1.89 1.89 1.75 (dl/g) Composition
ratio .sup.2 (wt %) 99.7 99.9 99.8 100 100 100 Propylene (co-)
polymer Intrinsic viscosity [.eta..sub.P] 1.89 1.89 1.75 1.89 1.89
1.75 (dl/g) Propylene (co-) polymer composition Intrinsic viscosity
[.eta..sub.T] 1.97 1.91 1.80 1.89 1.89 1.75 (dl/g) Melt tension
(MS) (cN) 3.7 1.6 1.9 0.8 0.9 0.6 Crystallization temperature 121.5
120.8 121.0 116.1 116.2 116.0 (.degree. C.) MFR (g/10 minutes) 3.5
4.2 6.0 4.5 4.5 7.2 initial final (g/10 minutes) 3.6 4.3 6.1 4.6
4.6 7.4 .DELTA.MFR (g/10 minutes) 0.1 0.1 0.1 0.1 0.1 0.2 Note 1
Generated amount (g) per 1 g of transitional metal compound
catalyst component Note 2 Composition ratio (wt %) in the propylene
(co-) polymer composition
Example 15
[0345] (1) Preparation of catalyst composition including transition
metal compound
[0346] Using the same conditions as example 1, a supported titanium
catalyst component was obtained.
[0347] (2) Preparation of preactivated catalyst
[0348] Using the same conditions as example 5 except that the
preliminary polymerization with propylene or the addition
polymerization with propylene was not conducted, the preliminary
activating polymerization with a gas mixture of ethylene-propylene
was conducted.
[0349] An ethylene-propylene copolymer generated by the preliminary
activating polymerization using the same conditions was analyzed
and it was found that the propylene polymerization unit was 0.8
weight % (measured with .sup.13C-NMR), 25 g of ethylene-propylene
existed per 1 g of the supported titanium catalyst component, and
the intrinsic viscosity [.eta..sub.A] of the polymer measured in
tetralin at 135.degree. C. was 30.0 dl/g.
[0350] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0351] Using the prepared preactivated catalyst, the main
polymerization of propylene was conducted using the same conditions
as example 1 to produce polypropylene. The obtained polypropylene
was pelletized using the same conditions as example 1 to obtain an
evaluation specimen of comparative example 15.
[0352] Various physical properties of the obtained polypropylene
are shown in Table 6.
Comparative Example 17
[0353] A propylene (co-)polymer composition was produced using the
same conditions as example 1 except that the preliminary activating
treatment of (2) was not conducted and the polymerization of
propylene was conducted under the presence of the solid titanium
catalyst obtained in (1) under the conditions the same as (3) to
obtain an evaluation specimen of comparative example 17.
[0354] Various physical properties of the obtained polypropylene
are shown in Table 6.
Comparative Example 18
[0355] A propylene (co-)polymer composition was produced by the
polymerization of propylene using the same conditions as example 1
except that the preliminary activation with propylene or the
addition polymerization with propylene was not conducted, the
preliminary activating polymerization with ethylene was replaced by
the preliminary activating treatment with a gas mixture of
ethylene-propylene and 240 g of propylene was introduced into the
polymerization reactor to obtain an evaluation specimen of
comparative example 18.
[0356] Various physical properties of the obtained polypropylene
are shown in Table 6.
[0357] Example 16 and Comparative Example 19 Polypropylene
compounds having different polyethylene (A) contents were produced
using the same conditions as example 1 except that the preliminary
activating polymerization with propylene or the addition
polymerization with propylene was not conducted and the conditions
of the preliminary activating polymerization with ethylene were
changed. The polypropylene compounds were treated using the same
process as example 1 to obtain evaluation specimens of example 16
and comparative example 19.
[0358] Various physical properties of example 16 and comparative
example 19 are shown in Table 6.
Example 17
[0359] (1) Preparation of catalyst composition including transition
metal compound
[0360] Using the same conditions as example 3, a supported titanium
catalyst component was obtained.
[0361] (2) Preparation of preactivated catalyst
[0362] Using the same conditions as example 3 except that the
preliminary polymerization with propylene or the addition
polymerization with propylene was not conducted, the preliminary
activating polymerization with ethylene was conducted.
[0363] A polymer obtained by the preliminary activating
polymerization process using the same conditions was analyzed and
it was found that 29 g of polyethylene (A) existed per 1 g of the
supported titanium catalyst component, and the intrinsic viscosity
[.eta..sub.A] of the polymer measured in tetralin at 135.degree. C.
was 35.5 dl/g.
[0364] (3) Production of polypropylene composition (main (co-)
polymerization of propylene)
[0365] Using the prepared preactivated catalyst, the main
polymerization of propylene was conducted with the same conditions
as example 5 to produce polypropylene. The obtained polypropylene
was pelletized using the same conditions as example 1 to obtain an
evaluation specimen of example 17.
[0366] Various physical properties of the obtained polypropylene
are shown in Table 6.
6 TABLE 6 Comparative Examples Examples 15.sup.3 16 17 17 18.sup.4
19 Preliminary activation <polyethylene (A)> 30.0 30.0 35.5
-- 3.3 30.0 Intrinsic viscosity [.eta..sub.A] (dl/g) Generated
amount .sup.1 (g/g) 25.0 6.5 29.0 -- 16.6 0.005 Composition ratio
.sup.2 (wt %) 0.35 0.09 0.18 -- 0.23 0.0001 Polymerization process
Intrinsic viscosity [.eta..sub.D] 1.89 1.89 1.68 1.89 1.89 1.89
(dl/g) Composition ratio .sup.2 (wt %) 99.6 99.9 99.8 100 99.8 100
Propylene (co-) polymer Intrinsic viscosity [.eta..sub.P] 1.89 1.89
1.68 1.89 1.89 1.89 (dl/g) Propylene (co-) polymer composition
Intrinsic viscosity [.eta..sub.T] 1.99 1.92 1.81 1.89 1.89 1.89
(dl/g) Melt tension (MS) (cN) 2.7 1.4 1.4 0.8 0.8 0.8
Crystallization temperature 120.9 119.8 120.0 116.1 116.2 116.2
(.degree. C.) MFR (g/10 minutes) 3.3 4.1 5.9 4.5 4.5 4.5 initial
final (g/10 minutes) 3.3 4.2 6.0 4.6 4.5 4.6 .DELTA.MFR (g/10
minutes) 0.0 0.1 0.1 0.1 0.0 0.1 Note 1: Generated amount (g) per 1
g of transitional metal compound catalyst component Note 2:
Composition ratio (wt %) in the propylene (co-) polymer composition
Note 3 Comparative example 15; a gas mixture of ethylene and
propylene was used as the monomer for the preliminary activation
Note 4 Comparative example 18; propylene was used as the monomer
for the preliminary activation
Example 18
[0367] Using the same conditions as example 1 except that 0.1
weight part of a phosphorous type antioxydant tris(2,4-di-t-butyl
phenyl) phosphite was added to 100 weight parts of the obtained
polypropylene composition in place of 0.1 weight part of a phenol
type antioxydant 2,6-di-t-butyl-p-cresol in example 1 (3), pellets
were obtained by pelletizing with an extruder at 230.degree. C.
Various physical properties of the pellets were measured and
evaluated to find the MFR, the crystallization temperature, and the
melt tension (MS) to be 3.6 g/10 minutes, 119.5.degree. C. and 2.1
cN, respectively. Detailed physical properties are shown in Table
7.
Example 19
[0368] Using the same conditions as example 2 except that a
phosphorous type antioxydant tris(2,4-di-t-butyl phenyl) phosphite
was added to 100 weight parts of the obtained polypropylene
composition in place of a phenol type antioxydant
2,6-di-t-butyl-p-cresol in example 2 (3), a polypropylene
composition was produced to prepare an evaluation specimen of
example 19.
[0369] Various physical properties of the obtained polypropylene
are shown in Table 7.
Comparative Examples 20-23
[0370] Using the same conditions except that a phosphorous type
antioxydant tris(2,4-di-t-butyl phenyl) phosphate was added to 100
weight parts of the obtained polypropylene composition in place of
a phenol type antioxydant 2,6-di-t-butyl-p-cresol in comparative
examples 1 to 4, polypropylene compositions were produced to
prepare an evaluation specimens of comparative examples 20 to
23.
[0371] Various physical properties of the obtained polypropylene
are shown in Table 7.
7 TABLE 7 Comparative Examples Examples 18 19 20 21.sup.3 22 23
Preliminary polymerization <polypropylene (B)> 2.8 2.8 2.8
2.8 2.8 -- Intrinsic viscosity [.eta..sub.B] (dl/g) Generated
amount .sup.1 (g/g) 2.0 2.0 2.0 2.0 2.0 -- Composition ratio .sup.2
(wt %) 0.02 0.02 0.02 0.02 0.02 -- Preliminary activation
<polyethylene (A)> 34.0 34.0 34.0 2.8 -- -- Intrinsic
viscosity [.eta..sub.A] (dl/g) Generated amount .sup.1 (g/g) 22.0
4.5 0.005 22.0 -- -- Composition ratio .sup.2 (wt %) 0.25 0.05
0.0001 0.25 -- -- Addition polymerization <polypropylene (C)>
2.8 2.8 2.8 2.8 2.8 -- Intrinsic viscosity [.eta..sub.C] (dl/g)
Generated amount .sup.1 (g/g) 2.0 2.0 2.0 2.0 2.0 -- Composition
ratio .sup.2 (wt %) 0.02 0.02 0.02 0.02 0.02 -- Polymerization
process Intrinsic viscosity [.eta..sub.D] 1.89 1.90 1.89 1.89 1.89
1.67 (dl/g) Composition ratio .sup.2 (wt %) 99.7 99.9 100 99.7 100
100 Propylene (co-) polymer Intrinsic viscosity [.eta..sub.P] 1.89
1.90 1.89 1.89 1.89 1.67 (dl/g) Propylene (co-)polymer composition
Intrinsic viscosity [.eta..sub.T] 1.97 1.92 1.89 1.89 1.89 1.67
(dl/g) Melt tension (MS) (cN) 2.1 1.2 0.9 0.8 0.8 6.8
Crystallization temperature 119.5 118.3 116.8 116.1 116.0 129.4
(.degree. C.) MFR (g/10 minutes) 3.6 4.2 4.6 4.5 4.5 9.2 initial
final (g/10 minutes) 3.7 4.3 4.6 4.6 4.6 17.5 .DELTA.MFR (g/10
minutes) 0.1 0.1 0.0 0.1 0.1 8.3 YI initial -0.5 -0.4 0.5 -0.6 -0.4
1.0 final 1.5 1.5 1.4 1.5 1.6 3.5 .DELTA.YI 2.0 1.9 1.9 2.1 2.0 2.5
Note 1 Generated amount (g) per 1 g of transitional metal compound
catalyst component Note 2 Composition ratio (wt %) in the propylene
(co-) polymer composition Note 3 Comparative example 21; propylene
was used as the monomer for the preliminary activation
Examples 20-21
[0372] Using the same conditions as example 3 and example 5 except
that a phosphorous type antioxydant tris(2,4-di-t-butyl phenyl)
phosphite was added to 100 weight parts of the obtained
polypropylene composition in place of a phenol type antioxydant
2,6-di-t-butyl-p-cresol, polypropylene compositions were produced
to prepare evaluation specimens of examples 20 and 21.
[0373] Various physical properties of the obtained polypropylene
are shown in Table 8.
Comparative Examples 24-26
[0374] Using the same conditions as comparative examples 5 to 7
except that a phosphorous type antioxydant tris(2,4-di-t-butyl
phenyl) phosphate was added to 100 weight parts of the obtained
polypropylene composition in place of a phenol type antioxydant
2,6-di-t-butyl-p-cresol, polypropylene compositions were produced
to prepare evaluation specimens of examples 24 to 26.
[0375] Various physical properties of the obtained polypropylene
are shown in Table 8.
8 TABLE 8 Comparative Examples Examples 20 21 24 25 26.sup.3
Preliminary polymerization <polypropylene (B)> 2.7 2.7 2.7
2.7 -- Intrinsic viscosity [.eta..sub.B] (dl/g) Generated amount
.sup.1 (g/g) 1.2 1.2 1.2 1.2 -- Composition ratio .sup.2 (wt %)
0.01 0.01 0.01 0.01 -- Preliminary activation <polyethylene
(A)> 30.2 22.5 -- -- 32.5 Intrinsic viscosity [.eta..sub.A]
(dl/g) Generated amount .sup.1 (g/g) 32.0 22.0 -- -- -- Composition
ratio .sup.2 (wt %) 0.18 0.12 -- -- 0.25 Addition polymerization
<polypropylene (C)> 2.8 2.2 2.8 2.2 -- Intrinsic viscosity
[.eta..sub.C] (dl/g) Generated amount .sup.1 (g/g) 2.2 2.1 2.2 2.1
-- Composition ratio .sup.2 (wt %) 0.01 0.01 0.01 0.01 --
Polymerization process Intrinsic viscosity [.eta..sub.D] 1.75 1.52
1.75 1.52 1.89 (dl/g) Composition ratio .sup.2 (wt %) 99.8 99.9 100
100 99.7 Propylene (co-) polymer Intrinsic viscosity [.eta..sub.P]
1.75 1.52 1.75 1.52 1.89 (dl/g) Propylene (co-)polymer composition
Intrinsic viscosity [.eta..sub.T] 1.80 1.54 1.75 1.52 1.97 (dl/g)
Melt tension (MS) (cN) 1.2 1.7 0.6 0.3 1.0 Crystallization
temperature 119.0 118.5 116.1 115.2 116.0 (.degree. C.) MFR initial
(g/10 minutes) 6.0 15.4 7.2 16.7 3.5 final (g/10 minutes) 6.1 15.6
7.3 16.5 3.6 .DELTA.MFR (g/10 minutes) 0.1 0.2 0.1 -0.2 0.1 YI
initial -0.8 -0.4 -0.8 -0.3 -0.5 final 1.4 1.5 1.3 1.8 1.5
.DELTA.YI 2.2 1.9 2.1 2.1 2.0 Note 1 Generated amount (g) per 1 g
of transitional metal compound catalyst component Note 2
Composition ratio (wt %) in the propylene .alpha.-olefin copolymer
composition Note 3 Comparative example 26; mechanical simple mixing
of polyethylene and main polymerization polypropylene
Example 22
[0376] Using the same conditions as example 1 except that 0.09
weight part of a phosphorous type antioxydant tris(2,4-di-t-butyl
phenyl) phosphite and 0.01 weight part of a phenol type antioxidant
2,6-di-t-butyl-p-cresol were added to 100 weight parts of the
obtained polypropylene composition in place of 0.1 weight part of a
phenol type antioxydant 2,6-di-t-butyl-p-cresol in example 1 (3),
polypropylene composition was produced with an extruder. Various
physical properties of the obtained polypropylene composition were
measured and evaluated to find the intrinsic viscosity
[.eta..sub.T], the MFR, the crystallization temperature, and the
melt tension (MS) to be 1.97 dl/g, 3.5 g/10 minutes, 120.7.degree.
C. and 2.8 cN, respectively. Detailed physical properties are shown
in Table 9.
Example 23
[0377] Using the same conditions as example 1 (3) except that 0.08
weight part of a phosphorous type antioxydant tris(2,4-di-t-butyl
phenyl) phosphite and 0.02 weight part of dimyristyl
thiodipropionate were added to 100 weight parts of the obtained
polypropylene composition in place of 0.1 weight part of a phenol
type antioxydant 2,6-di-t-butyl-p-cresol, a polypropylene
composition was produced with an extruder as in example 1. Various
physical properties of the obtained polypropylene composition were
measured and evaluated to find the intrinsic viscosity
[.eta..sub.T] the MFR, the crystallization temperature, and the
melt tension (MS) to be 1.97 dl/g, 3.5 g/10 minutes, 119.8.degree.
C. and 2.5 cN, respectively. Detailed physical properties are shown
in Table 9.
9 TABLE 9 Examples 22 23 Preliminary polymerization
<polypropylene (B)> 2.8 2.8 Intrinsic viscosity [.eta..sub.B]
(dl/g) Generated amount .sup.1 (g/g) 2.0 2.0 Composition ratio
.sup.2 (wt %) 0.02 0.02 Preliminary activation <polyethylene
(A)> 34.0 34.0 Intrinsic viscosity [.eta..sub.A] (dl/g)
Generated amount .sup.1 (g/g) 22.0 22.0 Composition ratio .sup.2
(wt %) 0.25 0.25 Addition polymerization <polypropylene (C)>
2.8 2.8 Intrinsic viscosity [.eta..sub.C] (dl/g) Generated amount
.sup.1 (g/g) 2.0 2.0 Composition ratio .sup.2 (wt %) 0.02 0.02
Polymerization process Intrinsic viscosity [.eta..sub.D] 1.89 1.89
(dl/g) Composition ratio .sup.2 (wt %) 99.7 99.7 Propylene (co-)
polymer Intrinsic viscosity [.eta..sub.P] 1.89 1.89 (dl/g)
Propylene (co-)polymer composition Intrinsic viscosity
[.eta..sub.T] 1.97 1.97 (dl/g) Melt tension (MS) (cN) 2.8 2.5
Crystallization temperature 120.7 119.8 (.degree. C.) MFR initial
(g/10 minutes) 3.5 3.5 final (g/10 minutes) 3.6 3.6 .DELTA.MFR
(g/10 minutes) 0.1 0.1 YI initial -0.5 -0.6 final 2.5 2.1 .DELTA.YI
3.0 2.7 Note 1 Generated amount (g) per 1 g of transitional metal
compound catalyst component Note 2 Composition ratio (wt %) in the
propylene (co-) polymer composition
Example 24
[0378] (1) Preparation of catalyst composition including transition
metal compound
[0379] Using the same conditions as example 1, a supported titanium
catalyst component was obtained.
[0380] (2) Preparation of preactivated catalyst
[0381] Using the same conditions as example 1, a preactivated
catalyst slurry was obtained.
[0382] (3) Production of polypropylene composition (main
(co)polymerization of propylene)
[0383] After providing a nitrogen gas atmosphere in a 500 liter
capacity stainless steel polymerization reactor with an agitator,
240 liters of n-hexane, 780 millimole of triethyl aluminum (organic
metal compound (AL2)), 78 millimole of diisopropyldimethoxy silane
(electron donor (E2)) and 1/2amount of the preactivated catalyst
slurry obtained as mentioned above were added at 20.degree.C. Then
after introducing 95 liters of hydrogen into the polymerization
reactor and the temperature was raised to 70.degree. C., propylene
was supplied continuously for 45 minutes while maintaining the gas
phase pressure inside the polymerization reactor at 0.79 MPa to
implement the polymerization process (I). After the polymerization
process (I), the propylene supply was terminated and the
temperature inside the polymerization reactor was cooled to
30.degree. C. Hydrogen and unreacted gas were discharged. A part of
the polymerization slurry was taken out and analyzed to find the
MFR and the intrinsic viscosity [.eta..sub.T] measured in tetralin
at 135.degree. C. to be 6.5 g/10 minutes and 1.78 dl/g,
respectively. The intrinsic viscosity [.eta..sub.P1] obtained in
the polymerization process (I) was 1.59 dl/g.
[0384] Then 45 liters of hydrogen was introduced into the
polymerization reactor and the temperature inside the
polymerization reactor was raised to 70.degree. C., propylene was
supplied continuously for 60 minutes while maintaining the
polymerization temperature at 70.degree. C. and the gas phase
pressure inside the polymerization reactor at 0.98 MPa to implement
the polymerization process (II). After the polymerization process
(II), the propylene supply was terminated and the temperature
inside the polymerization reactor was cooled to 30.degree. C.
Hydrogen and unreacted propylene were discharged. A part of the
polymerization slurry was taken out and analyzed to find the MFR
and the intrinsic viscosity [.eta..sub.T2] measured in tetralin at
135.degree. C. to be 3.1 g/10 minutes, 2.01 dl/g, respectively. The
intrinsic viscosity [.eta..sub.P2] obtained in the polymerization
process (II) was 2.29 dl/g.
[0385] Then 30 liters of hydrogen was introduced into the
polymerization reactor and the temperature inside the
polymerization reactor was raised to 70.degree. C., propylene was
supplied continuously for 90 minutes while maintaining the
polymerization temperature at 70.degree. C. and the gas phase
pressure inside the polymerization reactor at 0.98 MPa to implement
the polymerization process (III). After the polymerization process
(III), the propylene supply was terminated and the temperature
inside the polymerization reactor was cooled to 30.degree. C.
Hydrogen and unreacted propylene were discharged.
[0386] After the polymerization period, 1 liter of methanol was
introduced into the polymerization reactor and the deactivation of
catalyst was conducted at 70.degree. C. for 15 minutes. Then after
discharging unreacted gas, solvent was separated and the polymer
was dried to obtain 39.1 kg of a polymer having an intrinsic
viscosity [.eta..sub.T3] of 2.33 dl/g. The intrinsic viscosity
[.eta..sub.P3] of the polymer obtained in the polymerization
process (III) was 3.86 dl/g.
[0387] The obtained polymer was a polypropylene polymer composition
containing 0.25 weight % of polyethylene (A) according to the
preliminary activating polymerization as the (a) component and the
intrinsic viscosity [.eta..sub.P] of the (b) component was 2.25
dl/g.
[0388] The weight ratios of the polymerization process (I), the
polymerization process (II) and the polymerization process (III)
are calculated from the magnesium content in the powders in each
stage and shown in Table 10.
[0389] Subsequently, using the same conditions as example 1,
polymer pellets were prepared with an extruder. Various physical
properties of the pellets were measured and evaluated to find the
MFR, the crystallization temperature, and the melt tension (MS) to
be 1.3 g/10 minutes, 122.3.degree. C. and 9.9 cN, respectively.
[0390] Various physical properties of the obtained propylene
polymer composition are shown in Table 10.
Comparative Example 27
[0391] Using the same conditions as comparative example 3, a
supported titanium catalyst slurry was obtained. Using the
supported titanium catalyst slurry, a propylene polymer composition
was produced using the same conditions as example 24 (3) to prepare
an evaluation specimen of the comparative example 27.
[0392] Various physical properties of the obtained propylene
polymer composition are shown in Table 10.
10 TABLE 10 Ex Com Ex 24 27 Preliminary polymerization
<polypropylene (B)> 2.8 2.8 Intrinsic viscosity [.eta..sub.B]
(dl/g) Generated amount .sup.1 (g/g) 2.0 2.0 Composition ratio
.sup.2 (wt %) 0.02 0.02 Preliminary activation <polyethylene
(A)> 34.0 -- Intrinsic viscosity [.eta..sub.A] (dl/g) Generated
amount .sup.1 (g/g) 22.0 -- Composition ratio .sup.2 (wt %) 0.25 --
Addition polymerization <polypropylene (C)> 2.8 2.8 Intrinsic
viscosity [.eta..sub.C] (dl/g) Generated amount .sup.1 (g/g) 2.0
2.0 Composition ratio .sup.2 (wt %) 0.02 0.02 Polymerization
process (I) Intrinsic viscosity [.eta..sub.P1] 1.59 1.77 (dl/g)
Composition ratio .sup.2 (wt %) 43.9 40.9 Polymerization process
(II) Intrinsic viscosity [.eta..sub.P2] 2.29 2.21 (dl/g)
Composition ratio .sup.2 (wt %) 38.9 37.0 Polymerization process
(III) Intrinsic viscosity [.eta..sub.P3] 3.86 3.84 (dl/g)
Composition ratio .sup.2 (wt %) 16.9 22.1 Propylene (co-) polymer
Intrinsic viscosity [.eta..sub.P] 2.25 2.39 (dl/g) Propylene (co-)
polymer composition Intrinsic viscosity [.eta..sub.T] 2.33 2.39
(dl/g) Melt tension (MS) (cN) 9.9 3.4 Crystallization temperature
122.3 116.3 (.degree. C.) MFR initial (g/10 minutes) 1.3 1.1 final
(g/10 minutes) 1.4 1.1 .DELTA.MFR (g/10 minutes) 0.1 0.0 Note 1:
Generated amount (g) per 1 g of transitional metal compound
catalyst component Note 2 Composition ratio (wt %) in the propylene
(co-) polymer composition
Example 25
[0393] 50 weight % of the propylene polymer composition of example
1 and 50 weight % of the propylene polymer composition of
comparative example 3 were mixed, and 0.1 weight % of
2,6-di-t-butyl-p-cresol and 0.1 weight % of calcium stearate were
mixed. The mixture was pelletized with an extruder having a screw
diameter of 40 mm at 230.degree. C. Various physical properties of
the obtained pellets are shown in Table 11.
11 TABLE 11 Ex 25 Preliminary polymerization 2.8 <polypropylene
(B) > Intrinsic viscosity [.eta. .sub.B] (dl/g) Composition
ratio.sup.1 (wt %) 0.02 Preliminary activation 34.0
<polyethylene (A) > Intrinsic viscosity [.eta. .sub.A] (dl/g)
Composition ratio.sup.1 (wt %) 0.12 Addition polymerization 2.8
<polypropylene (C) > Intrinsic viscosity [.eta. .sub.C]
(dl/g) Composition ratio.sup.1 (wt %) 0.02 Propylene (co-)polymer
1.89 Intrinsic viscosity [p] (dl/g) Propylene (co-)polymer 1.93
composition Intrinsic viscosity [.eta. .sub.T] (dl/g) Melt tension
(MS) (cN) 2.4 Crystallization temperature 119.8 (.degree. C.) MFR
initial (g/10 minutes) 4.0 final (g/10 minutes) 4.1 .DELTA. MFR
(g/10 minutes) 0.1
Example 26
[0394] Using the same conditions as example 1 except that the
amount of the preactivated catalyst containing a high molecular
weight polyethylene was altered to 0.24 weight % and 0.46 weight %,
polypropylene compositions were obtained. The obtained
polypropylene compositions were analyzed as mentioned below.
[0395] (1) Transmission electron microscope (TEM) observation
[0396] The transmission electron microscope (TEM) observation was
conducted as follows. Pellet specimens were preheated for three
minutes with a heat-press set at 200.degree. C., press-molded for 5
minutes under the pressure of 50 kg/cm , and solidified with a
cooling press of 50.degree. C. for three minutes to obtain a
plate-like testing piece of 1 mm thickness. After trimming, the
test piece was treated with electron staining of a vapor of an
aqueous solution of RuO.sub.4 to apply contrast for the TEM
observation. The aqueous solution of RuO.sub.4 was produced by
dissolving 0.6 g of NaIO.sub.4 (made by Wako Pure Chemical
Industries, Ltd., guaranteed reagent) and 0.1 g of
RuCl.sub.3'nH.sub.2O (made by Wako Pure Chemical Industries, Ltd.)
in 10 ml of pure water. The test piece was put in a sealed
container with the aqueous solution of RuO.sub.4 and left for 48
hours in a room temperature for staining. Although staining was
conducted by a vapor from an aqueous solution in this invention,
other methods can be used as well to obtain the same effect, such
as staining by soaking in an aqueous solution of RuO.sub.4 or by
sublimated gas from an RuO.sub.4 crystal. The stained specimen was
cut to form ultra-thin slices of approximately 80 nm thickness with
the Ultramicrotome made by JEOL, Ltd. using a knife angle of
45.degree.. The ultra-thin slices were observed with the
JEM-100CX.multidot.TEM made by JEOL, Ltd. with an acceleration
voltage of 100 kV.
[0397] A photograph observed with the above mentioned TEM with
75000 magnification is shown as FIG. 1. As apparently seen from
FIG. 1, a high molecular weight polyethylene having a numerical
average particle size of approximately 70 nm was dispersed in the
polymer of this embodiment. It was also observed that the high
molecular weight polyethylene has a lamella structure.
[0398] FIG. 2 is a traced diagram of FIG. 1 with explanation to
facilitate understanding. The globule and the lamella structure of
the high molecular weight polyethylene are added for
explanation.
[0399] On the other hand, particles are not dispersed in
conventional well-known polypropylenes as described in the TEM
photograph (FIG. 3) and its traced diagram (FIG. 4).
[0400] (2) Rheological analysis
[0401] {circle over (1)} Sample production for Rheometrics
Mechanical Spectrometer (RMS-800) measurement
[0402] Pellets for RMS-800 measurement (mixture of 0.1 weight % of
a thermal stabilizer: 2,6-di-t-butyl-p-cresol (BHT) and 0.1 weight
% of a lubricant: calcium stearate) were pressed with a plate
having a 25 mm diameter of 200.degree. C. The plate was set in the
RMS-800 for measurement.
[0403] {circumflex over (2)} Elongational viscosity measurement
[0404] (i) A thermal stabilizer (BHT: 0.1 weight %, lubricant
calcium stearate: 0.1 weight %) was added to powders and blended
with a Henschel mixer for three minutes.
[0405] (ii) The above mentioned blend was pelletized with an
extruder having a diameter of 40 mm with the temperature of
230.degree. C.
[0406] (iii) Strands having a uniform diameter were produced from
the above mentioned pellets with a Melt Tension Tester having a 3
mm orifice diameter from Toyo Seiki Seisaku-sho, Ltd. at a
temperature of 210.degree. C. and the extruding rate of 5 mm/minute
after the preheating time of 5 minutes before extruding.
[0407] Hereinafter the rheological behavior will be explained
[0408] 1. About G'
[0409] With respect to a molten product, a storage elastic modulus
G' at 230.degree.C. was measured with a strain in a linear range of
frequencies of 10.sup.-2 to 10.sup.2 [rad/sec] with a Rheometrics
Mechanical Spectrometer RMS-800 made by Rheometrics Incorporated
having a parallel plate with a 25 mm diameter attached thereto. the
results are shown in FIGS. 5 to 7.
[0410] As illustrated in FIGS. 5 and 6 (vertical axis: storage
elastic modulus G', horizontal axis : frequency .omega.), G' of a
polymer of the present invention (hereinafter abbreviated as
"HMS-PP") has a second plateau in a lower frequency region, which
is not seen in a conventional example, Conv. PP. The height of the
second plateau increases according to the amount of the pretreated
PE. The second plateau is known to be found in copolymers or
polymers filled with inorganic compounds having a configuration in
which rubber particles are dispersed in a plastic phase as islands.
It is regarded as caused by a long-term alleviation mechanism
derived from the dispersion phase structure. It is considered that
the second plateau appears because HMS-PP has dispersed ultra-high
molecular amount PE particles on a submicron order. "HIMONT LCB-PP"
in FIG. 5 denotes an electron beam crosslinked polypropylene
produced with an electron beam radiation method of Himont
Incorporated. What is important is that the electron beam
crosslinked polypropylene does not have a second plateau
neither.
[0411] 2. About N.sub.1
[0412] The first normal stress differences N.sub.1 of a molten
product at 190.degree. C., 230.degree. C. and 250.degree. C. were
measured in a shear rate range of 10.sup.-2 to 10 [sec .sup.-1]
with a Rheometrics Mechanical Spectrometer RMS-800 made by
Rheometrics Incorporated having a cone plate with a diameter of 25
mm and a cone angle of 0.1 radian attached thereto.
[0413] The measurement was initiated after 30 minutes from setting
a sample and stabilizing the temperature. The time to achieve a
constant flow state was determined by a preliminary
measurement.
[0414] Preliminary measurement: A constant flow was applied to 150
[S] at 0.01 [s.sup.-1] and 100 [S] samples at 0.1 [s.sup.-1] and
the minimum time to reach a predetermined viscosity was found.
[0415] As can be seen in FIG. 8 (vertical axis: first normal stress
difference N.sub.1, horizontal axis: shear rate .gamma.), FIG. 9
(vertical axis: first normal stress difference N.sub.1, horizontal
axis: MFR), N.sub.1 of HMS-PP is higher than that of Conv. PP, and
increases according to the pretreated PE amount. One having an
N.sub.1 higher than that of Conv. PP is the PP made by an electron
radiation method of Himont Incorporated. But as illustrated in FIG.
9 (vertical axis first normal stress difference N. vertical axis
temperature), an N.sub.1 of a Conv. PP or an electron beam
radiation method PP lowers as the temperature rises, whereas the
temperature dependency of the HMS-PP is small.
[0416] 3. About G(t)
[0417] An alleviated elastic modulus G(t) of a molten product at
230.degree. C. was measured with a strain of 500% and a time scale
of 330 [s] with a Rheometrics Mechanical Spectrometer RMS-800 made
by Rheometrics Incorporated having a cone plate with a diameter of
25 mm and a cone angle of 0.1 radian attached thereto.
Specifically, samples were set between cone plates having a cone
angle of 0.1, and the lower plate was rotated 28.65.degree. in an
instant to cause a 500% strain. The angle of 28.65.degree. was
determined in the following manner. The 500% strain means that the
strain .gamma. is expressed by 5. According to the formula
.gamma.=K.alpha..times..theta. wherein K.alpha. is a strain
constant and .theta. is an angle displacement (rad), .theta. is
expressed by .gamma./K.alpha.. In this case, K.alpha. is 10
according to 1/0.1 provided that the cone angle is 0.1. Therefore,
.theta. comes to be 5/10, that is 0.5 (rad), equal to 28.650 .
[0418] As illustrated in FIGS. 10 and 11 (vertical axis alleviated
elastic modulus G(t), horizontal axis: time), the G(t) curve of
HMS-PP has a tilt almost the same as that of Conv. PP at a short
time end, but the tilt becomes moderate at a long time end to show
a long time side plateau. An end region was not observed within the
measurement time scale (330 [s] or less), and the starting point of
the long time plateau moves toward the short time side according to
the increase of the pretreated PE amount.
[0419] The tilt of the G(t) curve of PP by the electron beam
radiation production method of Himont Incorporated is moderate
compared with that of Conv. PP or HMS-PP, but does not show a long
time plateau and has an end region as in the case of Conv. PP.
[0420] A long time plateau of the G(t) curve is observed also in PP
having a two way molecular weight distribution.
[0421] 4. About elongational viscosity
[0422] Strands having a uniform diameter were preheated for 5
minutes in a silicone oil bath of 180.degree. C. and elongated at a
constant strain rate (0.05, 0.10, 0.30) with Melten Reometer made
by Toyo Seiki Seisaku-sho Ltd. to measure an elongational
viscosity. The above mentioned elongational viscosity meter
measured the tension and the strand diameter with the passage of
time (the strand diameter was measure with a CCD camera).
[0423] FIG. 12 (vertical axis: elongational viscosity, horizontal
axis: time) illustrates a case in which a polypropylene composition
was obtained using the same conditions as example 1 except that the
amount of the preactivated catalyst containing a high molecular
weight polyethylene was changed to 0.46 weight % and the amount of
hydrogen was changed. Elongational viscosities of the obtained
polypropylene composition were measured with different strain rates
(.gamma.). The measurement results are shown in Table 12.
12 TABLE 12 Sample No. MFR (g/10 minutes) strain rate (sec.sup.-1)
HMSPP-1 0.5 0.021 HMSPP-2 0.5 0.037 HMSPP-3 0.5 0.128
[0424] FIG. 13 (vertical axis: elongational viscosity, horizontal
axis: time) illustrates a case in which a polypropylene composition
was obtained using the same conditions as comparative example 3
except that the amount of hydrogen was changed. Elongational
viscosities of the obtained polypropylene composition were measured
with different strain rates (.gamma.). The measurement results are
shown in Table 13.
13 TABLE 13 Sample No. MFR (g/10 minutes) strain rate (Sec.sup.-1)
Conv. PP-1 0.5 0.021 Conv. PP-2 1 0.020 Conv. PP-3 2 0.017
[0425] As described above, the elongational viscosity value of a
Conv.PP converges to a constant value even when a large deformation
by elongation was applied (Table 13). Whereas an HMS-PP shows a
strain hardening property with a viscosity rise beyond a certain
amount of deformation (Table 12). The viscosity rise is
advantageous in a forming molding or a blow molding having a large
deformation. The strain hardening property is seen in an electron
beam radiation production method PP or an ionomer of Himont
Incorporated. However, the phenomenon cannot be seen in a bulk
polypropylene composition.
[0426] As heretofore mentioned, it was confirmed that the HMS-PP of
the present invention shows, or remarkably shows the above
mentioned advantageous features compared with a blank PP without
adding a preactivated catalyst containing a high molecular weight
ethylene regardless of homo PP, random PP or block PP. It is
presumably because of the interaction among dispersed high
molecular weight ethylene molecules and polypropylene
molecules.
[0427] It was also confirmed that even when the preactivated
catalyst powders containing a high molecular weight ethylene were
blended to a base PP, the above mentioned Theological behavior does
not appear.
[0428] As this invention may be embodied in several forms without
departing from the spirit of essential characteristics thereof, the
present embodiments are therefore illustrative and not restrictive,
since the scope of the invention is defined by the appended claims
rather than by the description preceding them, and al changes that
fall within metes and bounds of the claims, or equivalence of such
metes and bounds are therefore intended to embraced by the
claims.
* * * * *