U.S. patent application number 09/180414 was filed with the patent office on 2002-11-07 for polyolefin composition with molecular weight maximum occuring in that part of the composition that has the highest comonomer content.
Invention is credited to CADY, LARRY D., FRYE, CHRISTOPHER J., HOWARD, PHILIP, KARJALA, TERESA P., MADDOX, PETER J., MUNRO, IAN M., PARIKH, DEEPAK R., PARTINGTON, S. ROY, PEIL, KEVIN P., SPENCER, LEE, VOLKENBURGH, WILLIAM R. VAN, WILLIAMS, PETER S., WILSON, DAVID R., WINTER, J. MARK.
Application Number | 20020165330 09/180414 |
Document ID | / |
Family ID | 22660376 |
Filed Date | 2002-11-07 |
United States Patent
Application |
20020165330 |
Kind Code |
A1 |
CADY, LARRY D. ; et
al. |
November 7, 2002 |
POLYOLEFIN COMPOSITION WITH MOLECULAR WEIGHT MAXIMUM OCCURING IN
THAT PART OF THE COMPOSITION THAT HAS THE HIGHEST COMONOMER
CONTENT
Abstract
This invention relates to a polyolefin copolymer composition
produced with a catalyst having a metallocene complex in a single
reactor in a process for the polymerization of an &agr;olefin
monomer with one or more olefin comonomers, and a molecular weight
maximum which occurs in that 50 percent by weight of the
composition which has the highest weight percent comonomer content.
Preferably, the composition has a comonomer partitioning factor C
pf which is equal to or greater than 1.10 or molecular weight
partitioning factor M pf which is equal to or greater than 1.15.
Preferred composition also have at least 0.01 long chain branches
per 1000 carbon atoms along the polymer backbone. These
compositions with reverse molecular engineering have superior
properties and are easily processable due to the simultaneous
presence of the association of high molecular weight with high
comonomer content and of long chain branching.
Inventors: |
CADY, LARRY D.; (HOUSTON,
TX) ; FRYE, CHRISTOPHER J.; (BOUC BEL AIR, FR)
; HOWARD, PHILIP; (MIDDLESEX, GB) ; KARJALA,
TERESA P.; (LAKE JACKSON, TX) ; MADDOX, PETER J.;
(MARTIGUES, FR) ; MUNRO, IAN M.; (LAKE JACKSON,
TX) ; PARIKH, DEEPAK R.; (LAKE JACKSON, TX) ;
PARTINGTON, S. ROY; (WALTON-ON-THAMES SURREY, GB) ;
PEIL, KEVIN P.; (AUBURN, MI) ; SPENCER, LEE;
(PEARLAND, TX) ; VOLKENBURGH, WILLIAM R. VAN;
(LAKE JACKSON, TX) ; WILLIAMS, PETER S.; (ROUTE DE
GALICE, FR) ; WILSON, DAVID R.; (MIDLAND, MI)
; WINTER, J. MARK; (LAKE JACKSON, TX) |
Correspondence
Address: |
STEPHEN S GRACE
PO BOX 1967
MIDLAND
MI
486411967
|
Family ID: |
22660376 |
Appl. No.: |
09/180414 |
Filed: |
November 6, 1998 |
PCT Filed: |
May 16, 1997 |
PCT NO: |
PCT/US97/08206 |
Current U.S.
Class: |
526/160 ;
526/161; 526/347; 526/348.6; 526/916; 526/943 |
Current CPC
Class: |
C08L 23/0815 20130101;
C08L 2207/07 20130101; C08L 2666/04 20130101; C08L 2308/00
20130101; C08L 2314/06 20130101; C08L 2205/02 20130101; C08L
23/0815 20130101; C08L 2205/025 20130101 |
Class at
Publication: |
526/160 ;
526/161; 526/943; 526/348.6; 526/916; 526/347 |
International
Class: |
C08F 004/44 |
Claims
1. A polyolefin copolymer composition produced with a catalyst
having a metallocene complex in a single reactor in a process for
the polymerization of an .alpha.-olefin monomer with one or more
olefin comonomers, the composition having a molecular weight
maximum which occurs in that 50 percent by weight of the
composition which has the highest weight percent comonomer content,
as expressed by having a conomoner partitioning factor C.sub.pf
which is equal to or greater than 1.10 and/or a molecular weight
partitioning factor M.sub.pf which is equal to or greater than
1.15, where the comonomer partitioning factor C.sub.pf is
calculated from the equation: 5 C pf = ( i = 1 n w i c i i = 1 n w
i ) ( j = 1 m w j c j j = 1 m w j ) where c.sub.l is the mole
fraction comonomer content and w.sub.i is the normalized weight
fraction as determined by GPC/FTIR for the n FTIR data points above
the median molecular weight, c.sub.j is the mole fraction comonomer
content and w.sub.j is the normalized weight fraction as determined
by PGC/FTIR for the m FTIR data points below the median molecular
weight, wherein only those weight fractions w.sub.1 or w.sub.j
which have associated mole fraction comonomer content values are
used to calculate C.sub.pf and n and m are greater than or equal to
3; and where the molecular weight partitioning factor M.sub.pf is
calculated from the equation: 6 M pf = ( i = 1 n w i M i i = 1 n w
i ) ( j = 1 m w j M j j = 1 m w j ) where M.sub.i is the viscosity
average molecular weight and w.sub.l is the normalized weight
fraction as determined by ATREF-DV for the n data points in the
fractions below the median elution temperature. M.sub.j is the
viscosity average molecular weight and w.sub.j is the normalized
weight fraction as determined by ATREF-DV for the m data points in
the fractions above the median elution temperature, wherein only
those weight fractions, w.sub.i or w.sub.j which have associated
viscosity average molecular weights greater than zero are used to
calculated M.sub.pf and n and m are greater than or equal to 3.
2. The polyolefin composition of claim 1, having long chain
branches along the polymer backbone.
3. The polyolefin copolymer composition of claim 1 or 2, wherein
C.sub.pf is equal to or greater than 1.15.
4. The polyolefin copolymer composition of claim 3 wherein C.sub.pf
is equal to or greater than 1.20.
5. The polyolefin copolymer composition of claim 2 wherein M.sub.pf
is equal to or greater than 1.30.
6. The polyolefin copolymer composition of claim 5 wherein M.sub.pf
is equal to or greater than 1.50.
7. The polyolefin copolymer composition of claim 1 wherein the
density of the composition is from 0.87 to 0.96 g/cm.sup.3.
8. The polyolefin copolymer composition of claim 7 wherein the
density of the composition is from 0.90 to 0.94 g/cm.sup.3.
9. The polyolefin copolymer composition of claim 8 wherein the
density of the composition is from 0.910 to 0.925 g/cm.sup.3.
10. The polyolefin copolymer composition of claim 1 wherein the
composition has a melt index I.sub.2 of from 0.01 to 150.
11. The polyolefin copolymer composition of claim 1 wherein the
composition has an I.sub.21/I.sub.2 which is equal to or greater
than 24.
12. The polyolefin copolymer composition of claim 1 wherein the
composition has a Mw/Mn of from 2.0 to 10.
13. The polyolefin copolymer composition of claim 1 wherein the
composition has an I.sub.21/I.sub.2 which is equal to or greater
than 24 and a Mw/Mn of from 2.0 to3.5.
14. The polyolefin copolymer composition of claim 1 wherein the
composition has a flow activation energy of at least 8
kcal/mol.
15. The polyolefin copolymer composition of claim 14 wherein the
composition has a flow activation energy of at least 10
kcal/mol.
16. The polyolefin copolymer composition of claim 15 wherein the
composition has a flow activation energy of at least 12
kcal/mol.
17. The polyolefin copolymer composition of claim 2 wherein the
composition has at least 0.01 long chain branches per 1000 carbon
atoms along the polymer backbone.
18. The polyolefin copolymer composition of claim 17 wherein the
composition has from 0.01 to 8 long chain branches per 1000 carbon
atoms along the polymer backbone.
19. The polyolefin copolymer composition of claim 18 wherein the
composition has from 0.01 to 3 long chain branches per 1000 carbon
atoms along the polymer backbone.
20. The polyolefin copolymer composition of claim 1 wherein the
olefin comonomer is propene, 1-butene, 1-pentene,
4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1,7-octadiene, 1,5-hexadiene, 1,4-pentadiene,
1,9-decadiene, ethylidenenorbornene, styrene or a mixture
thereof.
21. The polyolefin copolymer composition of claim 1 wherein the
composition contains in polymerized form from 0.01 to 99.99 mole
percent ethylene as the monomer and from 99.99 to 0.01 mole percent
of one or more olefin comonomers.
22. The polyolefin copolymer composition of claim 21 wherein the
composition contains in polymerized form from 0.1 to 99.99 mole
percent ethylene as the monomer and from 99.99 to 0.1 mole percent
of one or more olefin comonomers.
23. The polyolefin copolymer composition of claim 22 wherein the
composition contains in polymerized form from 50 to 99.99 mole
percent ethylene as the monomer and from 50 to 0.1 mole percent of
one or more olefin comonomers.
24. The polyolefin copolymer composition of claim 23 wherein the
composition contains in polymerized form from 96 to 99.9 mole
percent ethylene as the monomer and from 4 to 0.1 mole percent of
one or more olefin comonomers.
25. The polyolefin copolymer composition of claim 1 wherein the
composition contains in polymerized form from 0.01 to 99.99 weight
percent propylene as the monomer and from 99.99 to 0.01 weight
percent of one or more olefin comonomers.
26. The polyolefin copolymer composition of claim 1 wherein the
composition has been produced with a mono-Cp catalyst.
27. The polyolefin copolymer composition of claim 26 wherein the
metallocene complex of the catalyst has a central metal Ti in which
the formal oxidation state is +2.
28. The polyolefin copolymer composition of claim 27 wherein the
composition has been produced with a catalyst having a metallocene
complex of the formula: 5wherein M is titanium or a zirconium in
the +2 formal oxidation state; L is a group containing a cyclic,
delocalized anionic, .pi.-system through which the group is bound
to M, and which group is also bound to 2; Z is a moiety bound to M
via .sigma.-bond, comprising boron, and the members of Group 14 of
the Periodic Table of the Elements, and also comprising an element
selected from the groups consisting of an element selected from the
groups consisting of nitrogen, phosphorus, sulfur and oxygen, said
moiety having up to 60 nonhydrogen atoms; and X is a neutral,
conjugated or nonconjugated diene, optionally substituted with one
or more groups selected from hydrocarbyl or trimethylsilyl groups,
said X having up to 40 carbon atoms and forming a .pi.-complex with
M.
29. The polyolefin copolymer composition of claim 26 wherein the
metallocene complex of the catalyst has a central metal Ti in which
the formal oxidation state is +3 or +4.
30. The polyolefin copolymer composition of claim 1 wherein the
composition has been produced with a bis-Cp metallocene
catalyst.
31. The polyolefin copolymer composition of claim 30 wherein the
composition has been produced with a bridged bis-Cp metallocene
catalyst.
32. The polyolefin copolymer composition of claim 31 wherein the
composition has been produced with a catalyst having a metallocene
complex of the formula: 6wherein Cp.sup.1, Cp.sup.2 are
independently a substituted or unsubstituted indenyl or
hydrogenated indenyl group; Y is a univalent anionic ligand, or
Y.sub.2 is a diene; M is zirconium, titanium or hafnium; and Z is a
bridging group comprising an alkylene group having 1 to 20 carbon
atoms or a dialkyl silyl- or germyl-group, or alkyl phosphine or
amine radical.
33. The polyolefin copolymer composition of claim 1 wherein the
catalyst has a single metallocene complex.
34. The polyolefin copolymer composition of claim 1 wherein the
catalyst is supported on a support material.
35. The polyolefin copolymer composition of claim 34 wherein the
support material is an inorganic oxide or magnesium halide.
36. The polyolefin copolymer composition of claim 35 wherein the
support material is silica, alumina, silica-alumina, or a mixture
thereof.
37. The polyolefin copolymer composition of claim 36 wherein the
support material is silica.
38. The polyolefin copolymer composition of claim 34 wherein the
support material is a polymer.
39. The polyolefin copolymer composition of claim 1 wherein the
process is a continuous process conducted in a single gas phase
reactor.
40. The polyolefin copolymer composition of claim 1 wherein the
composition is produced in a reactor with a reaction zone having a
temperature of 60.degree. C. or higher.
41. The polyolefin copolymer composition of claim 40 wherein the
composition is produced in a reactor with a reactor zone having a
temperature of 70.degree. C. or higher.
42. The polyolefin copolymer composition of claim 1 wherein the
comonomer to monomer molar ratio is less than 0.02.
43. The polyolefin copolymer composition of claim 1 wherein the
hydrogen to monomer molar ratio is less than 0.02.
44. The polyolefin copolymer composition of claim 1 wherein the
composition has a short chain branching distribution that is
multimodal, or wherein the composition has a molecular weight
distribution that is multimodal.
45. The polyolefin copolymer composition of claim 1 wherein the
density of the composition is from 0.910 to 0.925, the comonomer to
monomer molar ratio is less than 0.02, the hydrogen to monomer
ratio is less than 0.02, and the composition is produced in a
reactor with a reaction zone having a temperature of 70.degree. C.
or higher.
46. A polyolefin copolymer composition according to claim 1
produced in a continuous gas phase process.
47. A polyolefin copolymer composition according to claim 1
produced with a catalyst having a bis-Cp metallocene complex.
48. A polyolefin copolymer composition according to claim 1
produced with a catalyst having an organometallic compound.
49. A process for the polymerization of an .alpha.-olefin monomer
with one or more olefin comonomers using a metallocene catalyst in
a single reactor, the composition having long chain branches along
the polymer backbone and a molecular weight maximum which occurs in
that 50 percent by weight of the composition which has the highest
weight percent comonomer content, as expressed by having a
comonomer partitioning factor C.sub.pf which is equal to or greater
than 1.10, and/or a molecular weight partitioning factor M.sub.pf
which is equal to or greater than 1.15, where the comonomer
partitioning factor C.sub.pf and the molecular weight partitioning
factor M.sub.pf are as defined in claim 1.
50. A continuous gas phase process for the polymerization of an
.alpha.-olefin monomer with one or more olefin comonomers using a
catalyst having a metallocene complex in a single reactor, the
process producing a composition having a comonomer partitioning
factor C.sub.pf which is equal to or greater than 1.10, and/or a
molecular weight partitioning factor M.sub.pf which is equal to or
greater than 1.15, where the comonomer partitioning factor C.sub.pf
and the molecular weight partitioning factor M.sub.pf are as
defined in claim 1.
51. A process for the polymerization of an .alpha.-olefin monomer
with one or more olefin comonomers using a catalyst having a bis-Cp
metallocene complex in a single reactor, the process producing a
composition having a comonomer partitioning factor C.sub.pf which
is equal to or greater than 1.10, and/or a molecular weight
partitioning factor M.sub.pf which is equal to or greater than
1.15, where the comonomer partitioning factor C.sub.pf and the
molecular weight partitioning factor M.sub.pf are as defined in
claim 1.
52. An organometallic polymerization catalyst suitable for a
continuous gas phase polymerization process for the
copolymerization of 1-hexene and ethylene in a molar ratio of 0.02
or less at a temperature of 70.degree. C. and an ethylene pressure
of 8 bar which produces a polyolefin copolymer composition having a
density of 0.918, wherein the composition has long chain branches
along the polymer backbone, or a molecular weight maximum which
occurs in that 50 percent by weight of the composition which has
the highest weight percent comonomer content, or wherein the
composition has long chain branches along the polymer backbone and
a molecular weight maximum which occurs in that 50 percent by
weight of the composition which has the highest weight percent
comonomer content.
53. A film or other article of manufacture produced with the
polyolefin copolymer composition of claim 1 which has a melt
strength of greater than 4 cN, or which has a seal strength of
greater than 1.9 kg (4.2 lb.), or which has a hot tack greater than
0.23 kg (0.5 lb.), or which has a dart impact strength greater than
100 g.
54. A blend of two or more resin component comprising: (A) from 1
weight percent to 99 weight percent of a polyolefin copolymer
composition according to claim 1; and (B) from 99 weight percent to
1 weight percent of one or more resins that are different from the
(A) component.
55. The blend of claim 54 wherein the blend comprises from 1 weight
percent to 30 weight percent of component (A) and from about 99
weight percent to 70 weight percent of component (B).
56. The blend of claim 55 wherein the blend comprises from 1 weight
percent to 15 weight percent of component (A) and from 99 weight
percent to 85 weight percent of component (B).
57. The blend of claim 54 wherein the blend comprises from 1 weight
percent to 30 weight percent of component (B) and from 99 weight
percent to 70 weight percent of component (A).
58. The blend of claim 57 wherein the blend comprises from 1 weight
percent to 15 weight percent of component (B) and from 99 weight
percent to 85 weight percent of component (A).
Description
FIELD OF THE INVENTION
[0001] This invention relates to polyolefin copolymer compositions
with the molecular weight maximum occurring in that part of the
composition that has the highest comonomer content, and,
preferably, with long chain branching, which have been produced
from an .alpha.-olefin monomer and one or more .alpha.-olefin
comonomers in a single reactor with a single metallocene catalyst,
and to processes for the production of these materials and the
catalysts used therefor.
BACKGROUND OF THE INVENTION
[0002] Recently there have been many advances in the production of
polyolefin copolymers due to the introduction of metallocene
catalysts. Metallocene catalysts offer the advantage of generally
higher activity than traditional Ziegler catalysts and are usually
described as catalysts which are single-site in nature. Because of
their single-site nature the polyolefin copolymers produced by
metallocene catalysts often are quite uniform in their molecular
structure. For example, in comparison to traditional Ziegler
produced materials, they have relatively narrow molecular weight
distributions (MWD) and narrow Short Chain Branching Distribution
(SCBD). By narrow SCBD, it is meant that the frequency of short
chain branches, formed where comonomers incorporate into the
polyolefin chain, is relatively independent of molecular weight.
Although certain properties of metallocene products are enhanced by
narrow MWD, difficulties are often encountered in the processing of
these materials into useful articles and films relative to Ziegler
produced materials. In addition, the uniform nature of the SCBD of
metallocene produced materials does not readily permit certain
structures to be obtained.
[0003] An approach to improving processability has been the
inclusion of long chain branching (LCB), which is particularly
desirable from the viewpoint of improving processability without
damaging advantageous properties. U.S. Pat. Nos. 5,272,236;
5,278,272; 5,380,810; and EP 659,773, EP 676,421, WO 94/07930
relate to the production of polyolefins with long chain
branching.
[0004] Another approach is the addition of the polymer processing
aids to the polymer prior to fabrication into films or articles.
This requires extra processing and is expensive.
[0005] A different approach to the problem has been to make
compositions which are blends or mixtures of individual polymeric
materials with the goal being to maximize the beneficial properties
while minimizing the processing problems. This requires extra
processing which increases the cost of materials produced. U.S.
Pat. Nos. 4,598,128; 4,547,551; 5,408,004; 5,382,630; 5,382,631;
and 5,326,602; and WO 94/22948 and WO 95/25141 relate to
blends.
[0006] Another way to provide a solution for the processability
problems and to vary SCBD has been the development of various
cascade processes, where the material is produced by a series of
polymerizations under different reactor conditions, such as in a
series of reactors. Essentially, a material similar in some ways to
a blend is produced, with a modality greater than one for various
physical properties, such as the molecular weight distribution.
While polyolefin compositions with superior processability
characteristics can be produced this way, these methods are
expensive and complicated relative to the use of a single reactor.
Processes of interest are disclosed in U.S. Pat. No. 5,442,018, WO
95/26990, WO 95/07942 and WO 95/10548.
[0007] Another potentially feasible approach to improving
processability and varying SCBD has been to use a multicomponent
catalyst. In some cases, a catalyst which has a metallocene
catalyst and a conventional Ziegler-Natta catalyst on the same
support to produce a multimodal material, in other cases two
metallocene catalysts have been used in polyolefin polymerizations.
Components of different molecular weights and compositions are
produced in a single reactor operating under a single set of
polymerization conditions. This approach is difficult from the
point of view of process control and catalyst preparation. Catalyst
systems of interest are disclosed in WO 95/11264 and EP
676,418.
SUMMARY OF THE INVENTION
[0008] It would be desirable to be able to produce a polyolefin
copolymer composition which has the molecular weight maximum
occurring in that portion of the composition that has the highest
number of short chain branches and which is very easy to process.
Further, it would be desirable to be able to accomplish this using
a single metallocene catalyst, preferably supported in a
polymerization process using a single reactor, preferably gas
phase, operating semi-continuously or, preferably, continuously
under a single set of reactor conditions. It would be especially
desirable to be able to produce a polyolefin copolymer composition
which has the molecular weight maximum occurring in that portion of
the composition that has the highest number of short chain branches
and which has significant long chain branching.
[0009] The short chain branching distribution of a polyolefin
composition, which is due to the incorporation of an .alpha.-olefin
comonomer during the polymerization of an .alpha.-olefin monomer,
can be examined by several techniques, such as, for example,
ATREF-DV and GPC-FTIR. If the material of the composition is
divided into portions starting at one end of the distribution or
the other, the relationship between high short chain branching
content due to high comonomer content and molecular weight can be
determined.
[0010] In one embodiment this invention is a polyolefin copolymer
composition produced with a catalyst having a metallocene complex
in a single reactor in a process for the polymerization of an
.alpha.-olefin monomer with one or more olefin comonomers, the
composition having long chain branches along the polymer backbone
and a molecular weight maximum which occurs in that 50 percent by
weight of the composition which has the highest weight percent
comonomer content.
[0011] A preferred embodiment of this invention is a polyolefin
copolymer composition wherein the composition has a comonomer
partitioning factor C.sub.pf which is equal to or greater than 1.10
or a molecular weight partitioning factor M.sub.pf which is equal
to or greater than 1.15, or a comonomer partitioning factor
C.sub.pf which is equal to or greater than 1.10 and a molecular
weight partitioning factor M.sub.pf which is equal to or greater
than 1.15, where the comonomer partitioning factor C.sub.pf is
calculated from the equation: 1 C pf = i = 1 n w i c i i = 1 n w i
j = 1 m w j c j j = 1 m w j ,
[0012] where c.sub.i is the mole fraction comonomer content and
w.sub.i is the normalized weight fraction as determined by GPC/FTIR
for the n FTIR data points above the median molecular weight,
c.sub.j is the mole fraction comonomer content and w.sub.j is the
normalized weight fraction as determined by GPC/FTIR for the m FTIR
data points below the median molecular weight, wherein only those
weight fractions w.sub.i or w.sub.j which have associated mole
fraction comonomer content values are used to calculate C.sub.pf
and n and m are greater than or equal to 3; and where the molecular
weight partitioning factor M.sub.pf is calculated from the
equation: 2 M pf = i = 1 n w i M i i = 1 n w i j = 1 m w j M j j =
1 m w j ,
[0013] where M.sub.i is the viscosity average molecular weight and
w.sub.i is the normalized weight fraction as determined by ATREF-DV
for the n data points in the fractions below the median elution
temperature, M.sub.j is the viscosity average molecular weight and
w.sub.j is the normalized weight fraction as determined by ATREF-DV
for the m data points in the fractions above the median elution
temperature, wherein only those weight fractions, w.sub.i or
w.sub.j which have associated viscosity average molecular weights
greater than zero are used to calculate M.sub.pf and n and m are
greater than or equal to 3.
[0014] In another embodiment this invention is a polyolefin
copolymer composition produced with a catalyst having a metallocene
complex in a single reactor in a continuous gas phase process for
the polymerization of an .alpha.-olefin monomer with one or more
olefin comonomers, the composition having a comonomer partitioning
factor C.sub.pf which is equal to or greater than 1.10, or a
molecular weight partitioning factor M.sub.pf which is equal to or
greater than 1.15, or a comonomer partitioning factor C.sub.pf
which is equal to or greater than 1.10 and a molecular weight
partitioning factor M.sub.pf which is equal to or greater than
1.15, where the comonomer partitioning factor C.sub.pf and the
molecular weight partitioning factor M.sub.pf are as previously
defined.
[0015] In another embodiment the invention is a polyolefin
copolymer composition produced with a catalyst having a bis-Cp
metallocene complex in a single reactor in a process for the
polymerization of an .alpha.-olefin monomer with one or more olefin
comonomers, the composition having a comonomer partitioning factor
C.sub.pf which is equal to or greater than 1.10, or a molecular
weight partitioning factor M.sub.pf which is equal to or greater
than 1.15, or a comonomer partitioning factor C.sub.pf which is
equal to or greater than 1.10 and a molecular weight partitioning
factor M.sub.pf which is equal to or greater than 1.15, where the
comonomer partitioning factor C.sub.pf and the molecular weight
partitioning factor M.sub.pf are as previously defined.
[0016] In a further embodiment this invention is a polyolefin
copolymer composition produced with a catalyst having an
organometallic compound in a single reactor in a process for the
polymerization of an .alpha.-olefin monomer with one or more olefin
comonomers, the composition having long chain branches along the
polymer backbone and a molecular weight maximum which occurs in
that 50 percent by weight of the composition which has the highest
weight percent comonomer content.
[0017] Polymerization processes to provide the aforementioned
compositions are within the scope of this invention and one
embodiment is a process for the polymerization of an .alpha.-olefin
monomer with one or more olefin comonomers using a metallocene
catalyst in a single reactor, the composition having long chain
branches along the polymer backbone and a molecular weight maximum
which occurs in that 50 percent by weight of the composition which
has the highest weight percent comonomer content. A preferred
embodiment is that where the composition has a comonomer
partitioning factor C.sub.pf which is equal to or greater than
1.10, or a molecular weight partitioning factor M.sub.pf which is
equal to or greater than 1.15, or a comonomer partitioning factor
C.sub.pf which is equal to or greater than 1.10 and a molecular
weight partitioning factor M.sub.pf which is equal to or greater
than 1.15, where the comonomer partitioning factor C.sub.pf and the
molecular weight partitioning factor M.sub.pf are as previously
defined.
[0018] Another embodiment of this invention is a continuous gas
phase process for the polymerization of an .alpha.-olefin monomer
with one or more olefin comonomers using a catalyst having a
metallocene complex in a single reactor, the process producing a
composition having a comonomer partitioning factor C.sub.pf which
is equal to or greater than 1.10, or a molecular weight
partitioning factor M.sub.pf which is equal to or greater than
1.15, or a comonomer partitioning factor C.sub.pf which is equal to
or greater than 1.10 and a molecular weight partitioning factor
M.sub.pf which is equal to or greater than 1.15, where the
comonomer partitioning factor C.sub.pf and the molecular weight
partitioning factor M.sub.pf are as previously defined.
[0019] Another embodiment of this invention is a process for the
polymerization of an .alpha.-olefin monomer with one or more olefin
comonomers using a catalyst having a bis-Cp metallocene complex in
a single reactor, the process producing a composition having a
comonomer partitioning factor C.sub.pf which is equal to or greater
than 1.10, or a molecular weight partitioning factor M.sub.pf which
is equal to or greater than 1.15, or a comonomer partitioning
factor C.sub.pf which is equal to or greater than 1.10 and a
molecular weight partitioning factor M.sub.pf which is equal to or
greater than 1.15, where the comonomer partitioning factor C.sub.pf
and the molecular weight partitioning factor M.sub.pf are as
previously defined.
[0020] A further embodiment of this invention is a process for the
polymerization of an .alpha.-olefin monomer with one or more olefin
comonomers using a catalyst having an organometallic compound in a
single reactor, the composition having long chain branches along
the polymer backbone and a molecular weight maximum which occurs in
that 50 percent by weight of the composition which has the highest
weight percent comonomer content.
[0021] Another embodiment of this invention is a process for the
polymerization of an .alpha.-olefin monomer with one or more olefin
comonomers using a catalyst having an organometallic compound in a
single reactor, the composition having long chain branches along
the polymer backbone and a molecular weight maximum which occurs in
that 50 percent by weight of the composition which has the highest
weight percent comonomer content.
[0022] The compositions of this invention have desirable properties
and can be easily processed into a film or other article of
manufacture which has a melt strength of greater than 4 cN, or
which has a seal strength of greater than 1.9 kg (4.2 lb.), or
which has a hot tack greater than 0.23 kg (0.5 lb.), or which has a
dart impact strength greater than 100 g.
[0023] A further embodiment of this invention relate to a blend of
two or more resin components comprising:
[0024] (A) from about 1 weight percent to about 99 weight percent
of a polyolefin copolymer composition produced with a catalyst
having a metallocene complex in a single reactor in a process for
the polymerization of an .alpha.-olefin monomer with one or more
olefin comonomers, the composition having long chain branches along
the polymer backbone and a molecular weight maximum which occurs in
that 50 percent by weight of the composition which has the highest
weight percent comonomer content; and
[0025] (B) from about 99 weight percent to about 1 weight percent
of one or more resins that are different from the (A)
component.
[0026] Another embodiment of this invention is a blend of two or
more resin components comprising:
[0027] (A) from about 1 weight percent to about 99 weight percent
of a polyolefin copolymer composition produced with a catalyst
having a metallocene complex in a single reactor in a continuous
gas phase process for the polymerization of an .alpha.-olefin
monomer with one or more olefin comonomers, the composition having
a comonomer partitioning factor C.sub.pf which is equal to or
greater than 1.10, or a molecular weight partitioning factor
M.sub.pf which is equal to or greater than 1.15, or a comonomer
partitioning factor C.sub.pf which is equal to or greater than 1.10
and a molecular weight partitioning factor M.sub.pf which is equal
to or greater than 1.15, where the comonomer partitioning factor
C.sub.pf and the molecular weight partitioning factor M.sub.pf are
as previously defined; and
[0028] (B) from about 99 weight percent to about 1 weight percent
of one or more resins that are different from the (A)
component.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 is an ATREF-DV plot for the composition of Example
1.
[0030] FIG. 2 is an ATREF-DV plot for the composition of Example
2.
[0031] FIG. 3 is an ATREF-DV plot for the composition of Example
3.
[0032] FIG. 4 is an ATREF-DV plot for the composition of Example
4.
[0033] FIG. 5 is an ATREF-DV plot for the composition of Example
5.
[0034] FIG. 6 is an ATREF-DV plot for the composition of
Comparative Example D, DOWLEX.TM. 2056, a commercially available
Ziegler-Natta produced polyethylene.
[0035] FIG. 7 is an ATREF-DV plot for the composition of
Comparative Example A, BP Innovex.TM. 7209.
[0036] FIG. 8 is an ATREF-DV plot for the composition of
Comparative Example B, Exxon Exceed.TM. 401.
[0037] FIG. 9 is an ATREF-DV plot for the composition of
Comparative Example E, solution INSITE.TM. metallocene produced
AFFINITY.TM..
[0038] FIG. 10 is an ATREF-DV plot for the composition of
Comparative Example C, Novacore, a gas phase produced PE.
[0039] FIG. 11 is a plot of GPC-FTIR data for the composition of
Example 1.
[0040] FIG. 12 is a plot of GPC-FTIR data for the composition of
Example 2.
[0041] FIG. 13 is a plot of GPC-FTIR data for the composition of
Example 3.
[0042] FIG. 14 is a plot of GPC-FTIR data for the composition of
Example 5.
[0043] All references herein to elements or metals belonging to a
certain Group refer to the Periodic Table of the Elements published
and copyrighted by CRC Press, Inc., 1989. Also any reference to the
Group or Groups shall be to the Group or Groups as reflected in
this Periodic Table of the Elements using the IUPAC system for
numbering groups.
[0044] Suitable catalysts for use herein may be derivatives of any
transition metal including Lanthanides, but preferably of Group 3,
4, or Lanthanide metals which are in the +2, +3, or +4 formal
oxidation state. Preferred compounds include metal complexes
containing from one to three .pi.-bonded anionic or neutral ligand
groups, which may be cyclic or noncyclic delocalized .pi.-bonded
anionic ligand groups. Exemplary of such .pi.-bonded anionic ligand
groups are conjugated or nonconjugated, cyclic or non-cyclic dienyl
groups, allyl groups, and arene groups. By the term ".pi.-bonded"
is meant that the ligand group is bonded to the transition metal by
means of a .pi. bond.
[0045] Each atom in the delocalized .pi.-bonded group may
independently be substituted with a radical selected from the group
consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl,
hydrocarbyl-substituted metalloid radicals wherein the metalloid is
selected from Group 14 of the Periodic Table of the Elements, and
such hydrocarbyl- or hydrocarbyl-substituted metalloid radicals
further substituted with a Group 15 or 16 hetero atom containing
moiety. Included within the term "hydrocarbyl" are C.sub.1-20
straight, branched and cyclic alkyl radicals, C.sub.6-20 aromatic
radicals, C.sub.7-20 alkyl-substituted aromatic radicals, and
C.sub.7-20 aryl-substituted alkyl radicals. In addition two or more
such radicals may together form a fused ring system, a hydrogenated
fused ring system, or a metallocycle with the metal. Suitable
hydrocarbyl-substituted organometalloid radicals include mono-, di-
and tri-substituted organometalloid radicals of Group 14 elements
wherein each of the hydrocarbyl groups contains from 1 to 20 carbon
atoms. Examples of suitable hydrocarbyl-substituted
organo-metalloid radicals include trimethylsilyl, triethylsilyl,
ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and
trimethylgermyl groups. Examples of Group 15 or 16 hetero atom
containing moieties include amine, phosphine, ether or thioether
moieties or divalent derivatives thereof, such as, for example,
amide, phosphide, ether or thioether groups bonded to the
transition metal or Lanthanide metal, and bonded to the hydrocarbyl
group or to the hydrocarbyl-substituted metalloid containing
group.
[0046] Examples of suitable anionic, delocalized .pi.-bonded groups
include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,
tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl,
cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, and
decahydroanthracenyl groups, as well as C.sub.1-10
hydrocarbyl-substituted or C.sub.1-10 hydrocarbyl-substituted silyl
substituted derivatives thereof. Preferred anionic delocalized
.pi.-bonded groups are cyclopentadienyl,
pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,
tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,
fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,
tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl.
[0047] A suitable class of catalysts are transition metal complexes
corresponding to the formula:
L.sub.lMX.sub.mX'.sub.nX".sub.p, or a dimer thereof
[0048] wherein:
[0049] L is an anionic, delocalized, .pi.-bonded group that is
bound to M, containing up to 50 nonhydrogen atoms, optionally two L
groups may be joined together forming a bridged structure, and
further optionally one L may be bound to X;
[0050] M is a metal of Group 4 of the Periodic Table of the
Elements in the +2, +3 or +4 formal oxidation state;
[0051] X is an optional, divalent substituent of up to 50
nonhydrogen atoms that together with L forms a metallocycle with
M;
[0052] X' is an optional neutral Lewis base having up to 20
non-hydrogen atoms;
[0053] X" each occurrence is a monovalent, anionic moiety having up
to 40 nonhydrogen atoms, optionally, two X" groups may be
covalently bound together forming a divalent dianionic moiety
having both valences bound to M, or, optionally two X" groups may
be covalently bound together to form a neutral, conjugated or
nonconjugated diene that is .pi.-bonded to M (whereupon M is in the
+2 oxidation state), or further optionally one or more X" and one
or more X' groups may be bonded together thereby forming a moiety
that is both covalently bound to M and coordinated thereto by means
of Lewis base functionality;
[0054] l is 0, 1 or 2;
[0055] m is 0 or 1;
[0056] n is a number from 0 to 3;
[0057] p is an integer from 0 to 3; and
[0058] the sum, l+m+p, is equal to the formal oxidation state of M,
except when two X" groups together form a neutral conjugated or
nonconjugated diene that is .pi.-bonded to M, in which case the sum
l+m is equal to the formal oxidation state of M.
[0059] Preferred complexes include those containing either one or
two L groups. The latter complexes include those containing a
bridging group linking the two L groups. Preferred bridging groups
are those corresponding to the formula (ER*.sub.2).sub.x wherein E
is silicon, germanium, tin, or carbon, R* independently each
occurrence is hydrogen or a group selected from silyl, hydrocarbyl,
hydrocarbyloxy and combinations thereof, said R* having up to 30
carbon or silicon atoms, and x is 1 to 8. Preferably, R*
independently each occurrence is methyl, ethyl, propyl, benzyl,
tert-butyl, phenyl, methoxy, ethoxy or phenoxy.
[0060] Examples of the complexes containing two L groups are
compounds corresponding to the formula: 1
[0061] wherein:
[0062] M is zirconium, zirconium or hafnium, preferably zirconium
or hafnium, in the +2 or +4 formal oxidation state;
[0063] R.sup.3 in each occurrence independently is selected from
the group consisting of hydrogen, hydrocarbyl, silyl, germyl,
cyano, halo and combinations thereof, said R.sup.3 having up to 20
nonhydrogen atoms, or adjacent R.sup.3 groups together form a
divalent derivative (that is, a hydrocarbadiyl, siladiyl or
germadiyl group) thereby forming a fused ring system; and
[0064] X" independently each occurrence is an anionic ligand group
of up to 40 nonhydrogen atoms, or two X" groups together form a
divalent anionic ligand group of up to 40 nonhydrogen atoms or
together are a conjugated diene having from 4 to 30 nonhydrogen
atoms forming a .pi.-complex with M, whereupon M is in the +2
formal oxidation state; and
[0065] R*, E and x are as previously defined.
[0066] The foregoing metal complexes are especially suited for the
preparation of polymers having stereoregular molecular structure.
In such capacity it is preferred that the complex possesses C.sub.s
symmetry or possesses a chiral, stereorigid structure. Examples of
the first type are compounds possessing different delocalized
.pi.-bonded systems, such as one cyclopentadienyl group and one
fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) were
disclosed for preparation of syndiotactic olefin polymers in Ewen,
et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral
structures include rac bis-indenyl complexes. Similar systems based
on Ti(IV) or Zr(IV) were disclosed for preparation of isotactic
olefin polymers in Wild et al., J. Organomet. Chem., 232, 233-47,
(1982).
[0067] Exemplary bridged ligands containing two .pi.-bonded groups
are: (dimethylsilyl-bis(cyclopentadienyl)),
(dimethylsilyl-bis(methylcyclopent- adienyl)),
(dimethylsilyl-bis(ethylcyclopentadienyl)),
(dimethylsilyl-bis(t-butylcyclopentadienyl)),
(dimethylsilyl-bis(tetramet- hylcyclopentadienyl)),
(dimethylsilyl-bis(indenyl)),
(dimethylsilyl-bis(tetrahydroindenyl)),
(dimethylsilyl-bis(fluorenyl)),
(dimethylsilyl-bis(tetrahydrofluorenyl)),
(dimethylsilyl-bis(2-methyl-4-p- henylindenyl)),
(dimethylsilyl-bis(2-methylindenyl)),
(dimethylsilyl-cyclopentadienyl-fluorenyl),
(dimethylsilyl-cyclopentadien- yl-octahydrofluorenyl),
(dimethylsilyl-cyclopentadienyl-tetrahydrofluoreny- l),
(1,1,2,2-tetramethyl-1, 2-disilyl-bis-cyclopentadienyl),
(1,2-bis(cyclopentadienyl)ethane, and
(isopropylidene-cyclopentadienyl-fl- uorenyl).
[0068] Preferred X" groups are selected from hydride, hydrocarbyl,
silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and
aminohydrocarbyl groups, or two X" groups together form a divalent
derivative of a conjugated diene or else together they form a
neutral, .pi.-bonded, conjugated diene. Most preferred X" groups
are C.sub.1-20 hydrocarbyl groups.
[0069] A further class of metal complexes utilized in the present
invention corresponds to the preceding formula
L.sub.lMX.sub.mX'.sub.nX".- sub.p, or a dimer thereof, wherein X is
a divalent substituent of up to 50 nonhydrogen atoms that together
with L forms a metallocycle with M.
[0070] Preferred divalent X substituents include groups containing
up to 30 nonhydrogen atoms comprising at least one atom that is
oxygen, sulfur, boron or a member of Group 14 of the Periodic Table
of the Elements directly attached to the delocalized .pi.-bonded
group, and a different atom, selected from the group consisting of
nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to
M.
[0071] A preferred class of such Group 4 metal coordination
complexes used according to the present invention corresponds to
the formula: 2
[0072] wherein:
[0073] M is titanium or zirconium in the +2 or +4 formal oxidation
state;
[0074] R.sup.3 in each occurrence independently is selected from
the group consisting of hydrogen, hydrocarbyl, silyl, germyl,
cyano, halo and combinations thereof, said R.sup.3 having up to 20
nonhydrogen atoms, or adjacent R.sup.3 groups together form a
divalent derivative (that is, a hydrocarbadiyl, siladiyl or
germadiyl group) thereby forming a fused ring system;
[0075] each X" is a halo, hydrocarbyl, hydrocarbyloxy or silyl
group, said group having up to 20 nonhydrogen atoms, or two X"
groups together form a neutral C.sub.5-30 conjugated diene or a
divalent derivative thereof;
[0076] Y is --O--, --S--, --NR*--, --PR*--; and
[0077] Z is SiR*.sub.2, CR*.sub.2, SiR*.sub.2SiR*.sub.2,
CR*.sub.2CR*.sub.2, CR*.dbd.CR*, CR*.sub.2SiR*.sub.2, or
GeR*.sub.2, wherein R* is as previously defined.
[0078] An especially preferred group of transition metal complexes
for use in the catalysts of this invention are those disclosed in
U.S. Pat. No. 5,470,993, incorporated herein by reference, which
correspond to the formula: 3
[0079] wherein:
[0080] M is titanium or zirconium in the +2 formal oxidation
state;
[0081] L is a group containing a cyclic, delocalized anionic,
.pi.-system through which the group is bound to M, and which group
is also bound to Z;
[0082] Z is a moiety bound to M via .sigma.-bond, comprising boron,
and the members of Group 14 of the Periodic Table of the Elements,
and also comprising an element selected from the groups consisting
of an element selected from the groups consisting of nitrogen,
phosphorus, sulfur and oxygen, said moiety having up to 60
nonhydrogen atoms; and
[0083] X is a neutral, conjugated or nonconjugated diene,
optionally substituted with one or more groups selected from
hydrocarbyl or trimethylsilyl groups, said X having up to 40 carbon
atoms and forming a .pi.-complex with M.
[0084] Illustrative Group 4 metal complexes that may be employed in
the practice of the present invention include:
[0085] cyclopentadienyltitaniumtrimethyl,
[0086] cyclopentadienyltitaniumtriethyl,
[0087] cyclopentadienyltitaniumtriisopropyl,
[0088] cyclopentadienyltitaniumtriphenyl,
[0089] cyclopentadienyltitaniumtribenzyl,
[0090] cyclopentadienyltitanium-2,4-dimethylpentadienyl,
[0091]
cyclopentadienyltitanium-2,4-dimethylpentadienyl.multidot.triethylp-
hosphine,
[0092]
cyclopentadienyltitanium-2,4-dimethylpentadienyl.multidot.trimethyl-
phosphine,
[0093] cyclopentadienyltitaniumdimethylmethoxide,
[0094] cyclopentadienyltitaniumdimethylchloride,
[0095] pentamethylcyclopentadienyltitaniumtrimethyl,
[0096] indenyltitaniumtrimethyl,
[0097] indenyltitaniumtriethyl,
[0098] indenyltitaniumtripropyl,
[0099] indenyltitaniumtriphenyl,
[0100] tetrahydroindenyltitaniumtribenzyl,
[0101] pentamethylcyclopentadienyltitaniumtriisopropyl,
[0102] pentamethylcyclopentadienyltitaniumtribenzyl,
[0103] pentamethylcyclopentadienyltitaniumdimethylmethoxide,
[0104] pentamethylcyclopentadienyltitaniumdimethylchloride,
[0105] bis(.eta..sup.5-2,4-dimethylpentadienyl)titanium,
[0106]
bis(.eta..sup.5-2,4-dimethylpentadienyl)titanium.multidot.trimethyl-
phosphine,
[0107]
bis(.eta..sup.5-2,4-dimethylpentadienyl)titanium.multidot.triethylp-
hosphine,
[0108] octahydrofluorenyltitaniumtrimethyl,
[0109] tetrahydroindenyltitaniumtrimethyl,
[0110] tetrahydrofluorenyltitaniumtrimethyl,
[0111]
(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8-hexahyd-
ronaphthalenyl)dimethylsilanetitaniumdimethyl,
[0112]
(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8--
hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,
[0113]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium dibenzyl,
[0114]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium dimethyl,
[0115]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)-1,2-eth-
anediyltitanium dimethyl,
[0116] (tert-butylamido)
(tetramethyl-.eta..sup.5-indenyl)dimethylsilaneti- tanium
dimethyl,
[0117] (tert-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethy- lsilane
[0118] titanium (III) 2-(dimethylamino)benzyl; (tert-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethylsilanetitanium
(III) allyl,
[0119]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium (III) 2,4-dimethylpentadienyl,
[0120] (tert-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethy- l-silanetitanium
(II) 1,4-diphenyl-1,3-butadiene,
[0121] (tert-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethy- l-silanetitanium
(II) 1,3-pentadiene,
[0122] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(II) 1,4-diphenyl-1,3-butadiene,
[0123] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(II) 2,4-hexadiene,
[0124] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) 2,3-dimethyl-1,3-butadiene,
[0125] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) isoprene,
[0126] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) 1,3-butadiene,
[0127] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) 2,3-dimethyl-1,3-butadiene,
[0128] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) isoprene
[0129] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) dimethyl
[0130] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) dibenzyl
[0131] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) 1,3-butadiene,
[0132] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(II) 1,3-pentadiene,
[0133] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(II) 1,4-diphenyl-1,3-butadiene,
[0134] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(II) 1,3-pentadiene,
[0135] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) dimethyl,
[0136] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) dibenzyl,
[0137]
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium
(II) 1,4-diphenyl-1,3-butadiene,
[0138]
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium
(II) 1,3-pentadiene,
[0139]
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium
(II) 2,4-hexadiene,
[0140] (tert-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethy- l-silanetitanium
(IV) 1,3-butadiene,
[0141] (tert-butylamido) (tetramethyl-.eta..sup.5-cyclopentadienyl)
dimethyl-silanetitanium (IV) 2,3-dimethyl-1,3-butadiene,
[0142]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
-silanetitanium (IV) isoprene,
[0143] (tert-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethy- l-silanetitanium
(II) 1,4-dibenzyl-1,3-butadiene,
[0144] (tert-butylamido) (tetramethyl-.eta..sup.5-cyclopentadienyl)
dimethyl-silanetitanium (II) 2,4-hexadiene,
[0145] (tert-butylamido) (tetramethyl-.eta..sup.5-cyclopentadienyl)
dimethyl-silanetitanium (II) 3-methyl-1,3-pentadiene,
[0146]
(tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethyl-silanetitaniu-
mdimethyl,
[0147]
(tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethyl-silanetitani-
umdimethyl,
[0148]
(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8-hexahyd-
ronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,
[0149]
(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8--
hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl
[0150] (tert-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)methylp-
henyl-silanetitanium (IV) dimethyl,
[0151] (tert-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)methylp-
henyl-silanetitanium (II) 1,4-diphenyl-1,3-butadiene,
[0152]
1-(tert-butylamido)-2-(tetramethyl-.eta..sup.5-cyclopentadienyl)
ethanediyl-titanium (IV) dimethyl, and
[0153]
1-(tert-butylamido)-2-(tetramethyl-.eta..sup.5-cyclopentadienyl)eth-
anediyl-titanium (II) 1,4-diphenyl-1,3-butadiene.
[0154] Complexes containing two L groups including bridged
complexes suitable for use in the present invention include:
[0155] bis(cyclopentadienyl)zirconiumdimethyl,
[0156] bis(cyclopentadienyl)zirconium dibenzyl,
[0157] bis(cyclopentadienyl)zirconium methyl benzyl,
[0158] bis(cyclopentadienyl)zirconium methyl phenyl,
[0159] bis(cyclopentadienyl)zirconiumdiphenyl,
[0160] bis(cyclopentadienyl)titanium-allyl,
[0161] bis(cyclopentadienyl)zirconiummethylmethoxide,
[0162] bis(cyclopentadienyl)zirconiummethylchloride,
[0163] bis (pentamethylcyclopentadienyl)zirconiumdimethyl,
[0164] bis(pentamethylcyclopentadienyl)titaniumdimethyl,
[0165] bis(indenyl)zirconiumdimethyl,
[0166] indenylfluorenylzirconiumdimethyl,
[0167] bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),
[0168] bis(indenyl)zirconium methyltrimethylsilyl,
[0169] bis(tetrahydroindenyl)zirconium methyltrimethylsilyl,
[0170] bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,
[0171] bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,
[0172]
bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,
[0173] bis(pentamethylcyclopentadienyl)zirconiummethylchloride,
[0174] bis(methylethylcyclopentadienyl)zirconiumdimethyl,
[0175] bis(butylcyclopentadienyl)zirconium dibenzyl,
[0176] bis(t-butylcyclopentadienyl)zirconiumdimethyl,
[0177] bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,
[0178] bis(methylpropylcyclopentadienyl)zirconium dibenzyl,
[0179] bis(trimethylsilylcyclopentadienyl)zirconium dibenzyl,
[0180] dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl,
[0181] dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium-(III)
allyl
[0182]
dimethylsilyl-bis(t-butylcyclopentadienyl)zirconiumdichloride,
[0183]
dimethylsilyl-bis(n-butylcyclopentadienyl)zirconiumdichloride,
[0184] methylene-bis(tetramethylcyclopentadienyl)titanium(III)
2-(dimethylamino)benzyl,
[0185] methylene-bis(n-butylcyclopentadienyl)titanium(III)
2-(dimethylamino)benzyl,
[0186] dimethylsilyl-bis(indenyl)zirconiumbenzylchloride,
[0187] dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl,
[0188]
dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl,
[0189]
dimethylsilyl-bis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadi-
ene,
[0190] dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium (II)
1,4-diphenyl-1,3-butadiene,
[0191] dimethylsilyl-bis(tetrahydroindenyl)zirconium(II)
1,4-diphenyl-1,3-butadiene,
[0192] dimethylsilyl-bis(fluorenyl)zirconiummethylchloride,
[0193] dimethylsilyl-bis(tetrahydrofluorenyl)zirconium
bis(trimethylsilyl),
[0194]
(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl,
and
[0195]
dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium
dimethyl.
[0196] An especially preferred bis-CP complex for use in the
catalysts useful in this invention are the bridged bis-Cp complexes
of EP 676,421 which correspond to the formula: 4
[0197] wherein
[0198] Cp.sup.1, Cp.sup.2 are independently a substituted or
unsubstituted indenyl or hydrogenated indenyl group;
[0199] Y is a univalent anionic ligand, or Y.sub.2 is a diene;
[0200] M is zirconium, titanium or hafnium; and
[0201] Z is a bridging group comprising an alkylene group having 1
to 20 carbon atoms or a dialkyl silyl- or germyl-group, or alkyl
phosphine or amine radical.
[0202] Other catalysts, especially catalysts containing other Group
4 metals, will, of course, be apparent to those skilled in the art.
A wide variety of organometallic compounds, including
nonmetallocenes, which are useful in this invention are also
apparent to those skilled in the art.
[0203] The complexes are rendered catalytically active by
combination with an activating cocatalyst or by use of an
activating technique. Suitable activating cocatalysts for use
herein include polymeric or oligomeric alumoxanes, especially
methylalumoxane, triisobutyl aluminum-modified methylalumoxane, or
diisobutylalumoxane; strong Lewis acids, such as C.sub.1-30
hydrocarbyl substituted Group 13 compounds, especially
tri(hydrocarbyl)aluminum--or tri(hydrocarbyl)boron--compounds and
halogenated derivatives thereof, having from 1 to 10 carbons in
each hydrocarbyl or halogenated hydrocarbyl group, especially
tris(pentafluorophenyl)borane; and nonpolymeric, inert, compatible,
noncoordinating, ion forming compounds (including the use of such
compounds under oxidizing conditions). A suitable activating
technique is bulk electrolysis (explained in more detail
hereinafter). Combinations of the foregoing activating cocatalysts
and techniques may also be employed if desired. The foregoing
activating cocatalysts and activating techniques have been
previously taught with respect to different metal complexes in the
following references: EP-A-277,003; U.S. Pat. No. 5,153,157; U.S.
Pat. No. 5,064,802; EP-A-468,651 (equivalent to U.S. Ser. No.
07/547,718); EP-A-520,732 (equivalent to U.S. Ser. No. 07/876,268);
and WO 93/23412 (equivalent to U.S. Ser. No. 07/884,966 filed May
1, 1992); the teachings of which are hereby incorporated by
reference.
[0204] Suitable nonpolymeric, inert, compatible, noncoordinating,
ion forming compounds useful as cocatalysts in one embodiment of
the present invention comprise a cation which is a Bronsted acid
capable of donating a proton, and a compatible, noncoordinating,
anion, A.sup.-. Preferred anions are those containing a single
coordination complex comprising a charge-bearing metal or metalloid
core which anion is capable of balancing the charge of the active
catalyst species (the metal cation) which is formed when the two
components are combined. Also, said anion can be displaced by
olefinic, diolefinic and acetylenically unsaturated compounds or
other neutral Lewis bases such as ethers or nitrites. Suitable
metals include, but are not limited to, aluminum, gold and
platinum. Suitable metalloids include, but are not limited to,
boron, phosphorus, and silicon. Compounds containing anions which
comprise coordination complexes containing a single metal or
metalloid atom are well known and many, particularly such compounds
containing a single boron atom in the anion portion, are available
commercially.
[0205] Preferably such cocatalysts may be represented by the
following general formula:
(L*-H).sup.+.sub.d A.sup.d-
[0206] wherein:
[0207] L* is a neutral Lewis base;
[0208] (L*-H).sup.+is a Bronsted acid;
[0209] A.sup.d- is a noncoordinating, compatible anion having a
charge of d-; and
[0210] d is an integer from 1 to 3.
[0211] More preferably d is one, that is, A.sup.d- is A.sup.-.
[0212] Highly preferably, A.sup.- corresponds to the formula:
[BQ.sub.4].sup.31
[0213] wherein:
[0214] B is boron in the +3 formal oxidation state; and
[0215] Q independently each occurrence is selected from hydride,
dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl,
and halosubstituted-hydrocarbyl radicals, said Q having up to 20
carbons with the proviso that in not more than one occurrence is Q
halide.
[0216] In a more highly preferred embodiment, Q is a fluorinated
C.sub.1-20 hydrocarbyl group, most preferably, a fluorinated aryl
group, especially, pentafluorophenyl.
[0217] Illustrative, but not limiting, examples of ion forming
compounds comprising proton donatable cations which may be used as
activating cocatalysts in the preparation of the catalysts of this
invention are tri-substituted ammonium salts such as:
[0218] trimethylammonium tetraphenylborate,
[0219] triethylammonium tetraphenylborate,
[0220] tripropylammonium tetraphenylborate,
[0221] tri(n-butyl)ammonium tetraphenylborate,
[0222] tri(t-butyl)ammonium tetraphenylborate,
[0223] N,N-dimethylanilinium tetraphenylborate,
[0224] N,N-diethylanilinium tetraphenylborate,
[0225] N,N-dimethyl(2,4,6-trimethylanilinium)
tetraphenylborate,
[0226] trimethylammonium tetrakis-(penta-fluorophenyl) borate,
[0227] triethylammonium tetrakis-(pentafluorophenyl) borate,
[0228] tripropylammonium tetrakis(pentafluorophenyl) borate,
[0229] tri(n-butyl)-ammonium tetrakis(pentafluorophenyl)
borate,
[0230] tri(sec-butyl)ammonium
tetrakis(pentafluorophenyl)borate,
[0231] N,N-dimethylanilinium tetrakis(pentafluorophenyl)
borate,
[0232] N,N-diethylanilinium tetrakis(pentafluoro-phenyl)
borate,
[0233] N,N-dimethyl(2,4,6-trimethyl-anilinium)
tetrakis-(pentafluorophenyl- ) borate,
[0234] trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)
borate,
[0235] triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)
borate,
[0236] tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)
borate,
[0237] tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)
borate,
[0238] dimethyl(t-butyl)ammonium
tetrakis(2,3,4,6-tetrafluorophenyl) borate,
[0239] N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)
borate,
[0240] N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)
borate, and
[0241] N,N-dimethyl-(2,4,6-trimethylanilinium)
tetrakis-(2,3,4,6-tetrafluo- rophenyl)borate.
[0242] Dialkyl ammonium salts such as:
[0243] di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,
and
[0244] dicyclohexylammonium tetrakis(pentafluorophenyl) borate.
[0245] Tri-substituted phosphonium salts such as:
triphenylphosphonium tetrakis(pentafluorophenyl) borate,
tri(o-tolyl)phosphonium tetrakis(penta-fluorophenyl) borate, and
tri(2,6-dimethylphenyl)-phosphon- ium tetrakis(penta-fluorophenyl)
borate.
[0246] Preferred are N,N-dimethylanilinium
tetrakis(pentafluorophenyl)bora- te and tributylammonium
tetrakis(pentafluorophenyl)borate.
[0247] Another suitable ion forming, activating cocatalyst
comprises a salt of a cationic oxidizing agent and a
noncoordinating, compatible anion represented by the formula:
(Ox.sup.e+).sub.d (A.sup.d-).sub.e
[0248] wherein:
[0249] Ox.sup.e+ is a cationic oxidizing agent having charge
e+;
[0250] e is an integer from 1 to 3; and
[0251] A.sup.d-, and d are as previously defined.
[0252] Examples of cationic oxidizing agents include: ferrocenium,
hydrocarbyl-substituted ferrocenium, Ag.sup.+, or Pb.sup.+2.
Preferred embodiments of A.sup.d- are those anions previously
defined with respect to the Bronsted acid containing activating
cocatalysts, especially tetrakis(pentafluorophenyl)borate.
[0253] Another suitable ion forming, activating cocatalyst
comprises a compound which is a salt of a carbenium ion or silylium
ion and a noncoordinating, compatible anion represented by the
formula:
{circle over (c)}.sup.+ A.sup.-
[0254] wherein:
[0255] {circle over (c)}.sup.+ is a C.sub.1-20 carbenium ion or
silylium ion; and
[0256] A.sup.- is as previously defined.
[0257] A preferred carbenium ion is the trityl cation, that is
triphenylcarbenium. A preferred silylium ion is
triphenylsilylium.
[0258] The foregoing activating technique and ion forming
cocatalysts are also preferably used in combination with a
tri(hydrocarbyl)aluminum compound having from 1 to 4 carbons in
each hydrocarbyl group, an oligomeric or polymeric alumoxane
compound, or a mixture of a tri(hydrocarbyl)aluminum compound
having from 1 to 4 carbons in each hydrocarbyl group and a
polymeric or oligomeric alumoxane.
[0259] An especially preferred activating cocatalyst comprises the
combination of a trialkyl aluminum compound having from 1 to 4
carbons in each alkyl group and an ammonium salt of
tetrakis(pentafluorophenyl)borat- e, in a molar ratio from 0.1:1 to
1:0.1, optionally up to 1000 mole percent of an alkylalumoxane with
respect to M, is also present.
[0260] The activating technique of bulk electrolysis involves the
electrochemical oxidation of the metal complex under electrolysis
conditions in the presence of a supporting electrolyte comprising a
noncoordinating, inert anion. In the technique, solvents,
supporting electrolytes and electrolytic potentials for the
electrolysis are used such that electrolysis byproducts that would
render the metal complex catalytically inactive are not
substantially formed during the reaction. More particularly,
suitable solvents are materials that are: liquids under the
conditions of the electrolysis (generally temperatures from
0.degree. C. to 100.degree. C.), capable of dissolving the
supporting electrolyte, and inert. "Inert solvents" are those that
are not reduced or oxidized under the reaction conditions employed
for the electrolysis. It is generally possible in view of the
desired electrolysis reaction to choose a solvent and a supporting
electrolyte that are unaffected by the electrical potential used
for the desired electrolysis. Preferred solvents include
difluorobenzene (all isomers), DME, and mixtures thereof.
[0261] The electrolysis may be conducted in a standard electrolytic
cell containing an anode and cathode (also referred to as the
working electrode and counter electrode respectively). Suitable
materials of construction for the cell are glass, plastic, ceramic
and glass coated metal. The electrodes are prepared from inert
conductive materials, by which are meant conductive materials that
are unaffected by the reaction mixture or reaction conditions.
Platinum or palladium are preferred inert conductive materials.
Normally, an ion permeable membrane such as a fine glass frit
separates the cell into separate compartments, the working
electrode compartment and counter electrode compartment. The
working electrode is immersed in a reaction medium comprising the
metal complex to be activated, solvent, supporting electrolyte, and
any other materials desired for moderating the electrolysis or
stabilizing the resulting complex. The counter electrode is
immersed in a mixture of the solvent and supporting electrolyte.
The desired voltage may be determined by theoretical calculations
or experimentally by sweeping the cell using a reference electrode
such as a silver electrode immersed in the cell electrolyte. The
background cell current, the current draw in the absence of the
desired electrolysis, is also determined. The electrolysis is
completed when the current drops from the desired level to the
background level. In this manner, complete conversion of the
initial metal complex can be easily detected.
[0262] Suitable supporting electrolytes are salts comprising a
cation and an inert, compatible, noncoordinating anion, A.sup.-.
Preferred supporting electrolytes are salts corresponding to the
formula:
G.sup.+A.sup.-;
[0263] wherein:
[0264] G.sup.+ is a cation which is nonreactive towards the
starting and resulting complex; and
[0265] A.sup.- is a noncoordinating, compatible anion.
[0266] Examples of cations, G.sup.+, include tetrahydrocarbyl
substituted ammonium or phosphonium cations having up to 40
nonhydrogen atoms. A preferred cation is the tetra-n-butylammonium
cation.
[0267] During activation of the complexes of the present invention
by bulk electrolysis the cation of the supporting electrolyte
passes to the counter electrode and A.sup.- migrates to the working
electrode to become the anion of the resulting oxidized product.
Either the solvent or the cation of the supporting electrolyte is
reduced at the counter electrode in equal molar quantity with the
amount of oxidized metal complex formed at the working
electrode.
[0268] Preferred supporting electrolytes are
tetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates
having from 1 to 10 carbons in each hydrocarbyl group, especially
tetra-n-butylammonium tetrakis(pentafluorophenyl) borate.
[0269] The molar ratio of catalyst/cocatalyst employed preferably
ranges from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1,
most preferably from 1:10 to 10:1.
[0270] In general, the catalysts can be prepared by combining the
two components (metal complex and activator) in a suitable solvent
at a temperature within the range from about .sup.-100.degree. C.
to about 300.degree. C. The catalyst may be separately prepared
prior to use by combining the respective components or prepared in
situ by combination in the presence of the monomers to be
polymerized.
[0271] It is understood with suitable functionality on the catalyst
or cocatalyst the catalyst system can be covalently or ionically
attached to the support material.
[0272] Preferred supports for use in the present invention include
highly porous silicas, aluminas, aluminosilicates, and mixtures
thereof. The most preferred support material is silica. The support
material may be in granular, agglomerated, pelletized, or any other
physical form. Suitable materials include, but are not limited to,
silicas available from Grace Davison (division of W.R. Grace &
Co.) under the designations SD 3216.30, Davison Syloid 245, Davison
948 and Davison 952, and from Crossfield under the designation
ES70, and from Degussa AG under the designation Aerosil 812; and
aluminas available from Akzo Chemicals Inc. under the designation
Ketzen Grade B.
[0273] Supports suitable for the present invention preferably have
a surface area as determined by nitrogen porosimetry using the
B.E.T. method from 10 to about 1000 m.sup.2/g, and preferably from
about 100 to 600 m.sup.2/g. The pore volume of the support, as
determined by nitrogen adsorption, advantageously is between 0.1
and 3 cm.sup.3/g, preferably from about 0.2 to 2 cm.sup.3/g. The
average particle size depends upon the process employed, but
typically is from 0.5 to 500 .mu.m, preferably from 1 to 100
.mu.m.
[0274] Both silica and alumina are known to inherently possess
small quantities of hydroxyl functionality. When used as a support
herein, these materials are preferably subjected to a heat
treatment and/or chemical treatment to reduce the hydroxyl content
thereof. Typical heat treatments are carried out at a temperature
from 30.degree. C. to 1000.degree. C. (preferably 250.degree. C. to
800.degree. C. for 5 hours or greater) for a duration of 10 minutes
to 50 hours in an inert atmosphere or under reduced pressure.
Typical chemical treatments include contacting with Lewis acid
alkylating agents such as trihydrocarbyl aluminum compounds,
trihydrocarbylchlorosilane compounds, trihydrocarbylalkoxysilane
compounds or similar agents. Residual hydroxyl groups are then
removed via chemical treatment.
[0275] The support may be functionalized with a silane or
chlorosilane functionalizing agent to attach thereto pendant silane
--(Si--R).dbd., or chlorosilane --(Si--Cl).dbd. functionality,
wherein R is a C.sub.1-10 hydrocarbyl group. Suitable
functionalizing agents are compounds that react with surface
hydroxyl groups of the support or react with the silicon or
aluminum of the matrix. Examples of suitable functionalizing agents
include phenylsilane, hexamethyldisilazane diphenylsilane,
methylphenylsilane, dimethylsilane, diethylsilane, dichlorosilane,
and dichlorodimethylsilane. Techniques for forming such
functionalized silica or alumina compounds were previously
disclosed in U.S. Pat. Nos. 3,687,920 and 3,879,368, the teachings
of which are herein incorporated by reference.
[0276] The support may also be treated with an aluminum component
selected from an alumoxane or an aluminum compound of the formula
AlR.sup.1.sub.x'R.sup.2.sub.y', wherein R.sup.1 independently each
occurrence is hydride or R, R.sup.2 is hydride, R or OR, x' is 2 or
3, y' is 0 or 1 and the sum of x' and y' is 3. Examples of suitable
R.sup.1 and R.sup.2 groups include methyl, methoxy, ethyl, ethoxy,
propyl (all isomers), propoxy (all isomers), butyl (all isomers),
butoxy (all isomers), phenyl, phenoxy, benzyl, and benzyloxy.
Preferably, the aluminum component is selected from the group
consisting of aluminoxanes and tri(C.sub.1-4 hydrocarbyl)aluminum
compounds. Most preferred aluminum components are aluminoxanes,
trimethylaluminum, triethyl luminum, tri-isobutyl luminum, and
mixtures thereof.
[0277] Alumoxanes (also referred to as aluminoxanes) are oligomeric
or polymeric aluminum oxy compounds containing chains of
alternating aluminum and oxygen atoms, whereby the aluminum carries
a substituent, preferably an alkyl group. The structure of
alumoxane is believed to be represented by the following general
formulae (--Al(R)--O).sub.m', for a cyclic alumoxane, and
R.sub.2Al--O(--Al(R)--O).sub.m'--AlR.sub.2, for a linear compound,
wherein R is as previously defined, and m' is an integer ranging
from 1 to about 50, preferably at least about 4. Alumoxanes are
typically the reaction products of water and an aluminum alkyl,
which in addition to an alkyl group may contain halide or alkoxide
groups. Reacting several different aluminum alkyl compounds, such
as for example trimethyl aluminum and tri-isobutyl aluminum, with
water yields so-called modified or mixed alumoxanes. Preferred
alumoxanes are methylalumoxane and methylalumoxane modified with
minor amounts of C.sub.2-4 alkyl groups, especially isobutyl.
Alumoxanes generally contain minor to substantial amounts of
starting aluminum alkyl compound.
[0278] Particular techniques for the preparation of alumoxane type
compounds by contacting an aluminum alkyl compound with an
inorganic salt containing water of crystallization are disclosed in
U.S. Pat. No. 4,542,119. In a particular preferred embodiment an
aluminum alkyl compound is contacted with a regeneratable
water-containing substance such as hydrated alumina, silica or
other substance. This is disclosed in EP-A-338,044. Thus the
alumoxane may be incorporated into the support by reaction of a
hydrated alumina or silica material, which has optionally been
functionalized with silane, siloxane, hydrocarbyloxysilane, or
chlorosilane groups, with a tri (C.sub.1-10 alkyl) aluminum
compound according to known techniques. For the teachings contained
therein the foregoing patents and publications, or there
corresponding equivalent United States applications, are hereby
incorporated by reference.
[0279] The treatment of the support material in order to also
include optional alumoxane or trialkylaluminum loadings involves
contacting the same before, after or simultaneously with addition
of the complex or activated catalyst hereunder with the alumoxane
or trialkylaluminum compound, especially triethylaluminum or
triisobutylaluminum. Optionally the mixture can also be heated
under an inert atmosphere for a period and at a temperature
sufficient to fix the alumoxane, trialkylaluminum compound, complex
or catalyst system to the support. Optionally, the treated support
component containing alumoxane or the trialkylaluminum compound may
be subjected to one or more wash steps to remove alumoxane or
trialkylaluminum not fixed to the support.
[0280] Besides contacting the support with alumoxane the alumoxane
may be generated in situ by contacting an unhydrolyzed silica or
alumina or a moistened silica or alumina with a trialkyl aluminum
compound optionally in the presence of an inert diluent. Such a
process is well known in the art, having been disclosed in
EP-A-250,600; U.S. Pat. No. 4,912,075; and U.S. Pat. No. 5,008,228;
the teachings of which, or of the corresponding U.S. application,
are hereby incorporated by reference. Suitable aliphatic
hydrocarbon diluents include pentane, isopentane, hexane, heptane,
octane, isooctane, nonane, isononane, decane, cyclohexane,
methylcyclohexane and combinations of two or more of such diluents.
Suitable aromatic hydrocarbon diluents are benzene, toluene,
xylene, and other alkyl or halogen substituted aromatic compounds.
Most preferably, the diluent is an aromatic hydrocarbon, especially
toluene. After preparation in the foregoing manner the residual
hydroxyl content thereof is desirably reduced to a level less than
1.0 meq of OH per gram of support by any of the previously
disclosed techniques.
[0281] The cocatalysts of the invention may also be used in
combination with a tri(hydrocarbyl)aluminum compound having from 1
to 10 carbons in each hydrocarbyl group, an oligomeric or polymeric
alumoxane compound, a di(hydrocarbyl)(hydrocarbyloxy)aluminum
compound having from 1 to 10 carbons in each hydrocarbyl or
hydrocarbyloxy group, or a mixture of the foregoing compounds, if
desired. These aluminum compounds are usefully employed for their
beneficial ability to scavenge impurities such as oxygen, water,
and aldehydes from the polymerization mixture. Preferred aluminum
compounds include C.sub.2-6 trialkyl aluminum compounds, especially
those wherein the alkyl groups are ethyl, propyl, isopropyl,
n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, and
methylalumoxane, modified methylalumoxane and diisobutylalumoxane.
The molar ratio of aluminum compound to metal complex is preferably
from 1:10,000 to 1000:1, more preferably from 1:5000 to 100:1, most
preferably from 1:100 to 100:1.
[0282] The molar ratio of catalyst/cocatalyst employed ranges from
1:1000 to 1:10, preferably ranges from 1:10 to 10:1, more
preferably from 1:5 to 1:1, most preferably from 1:1.2 to 1:1.
Mixtures of the activating cocatalysts of the present invention may
also be employed if desired. In most polymerization reactions the
molar ratio of catalyst:polymerizable compounds employed is from
10.sup.-12:1 to 10.sup.-1:1, more preferably from 10.sup.-12:1 to
10.sup.-5:1.
[0283] Molecular weight control agents can be used in combination
with the present cocatalysts. Examples of such molecular weight
control agents include hydrogen, trialkyl aluminum compounds or
other known chain transfer agents. It is understood that the
present invention is operable in the absence of any component which
has not been specifically disclosed. The following examples are
provided in order to further illustrate the invention and are not
to be construed as limiting. Unless stated to the contrary, all
parts and percentages are expressed on a weight basis.
[0284] The catalysts, whether or not supported, in any of the
processes of this invention, whether gas phase, solution, slurry,
or any other polymerization process, may be used to polymerize
addition polymerizable monomers include ethylenically unsaturated
monomers, acetylenic compounds, conjugated or nonconjugated dienes,
polyenes, and mixtures thereof. Preferred monomers include olefins,
for examples .alpha.-olefins having from 2 to 100,000, preferably
from 2 to 30, more preferably from 2 to 8 carbon atoms and
combinations of two or more of such .alpha.-olefins.
[0285] Particularly suitable .alpha.-olefins include, for example,
ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1,
1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,
1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, and
C.sub.16-C.sub.30 .alpha.-olefins or combinations thereof, as well
as long chain vinyl terminated oligomeric or polymeric reaction
products formed during the polymerization. Preferably, the
.alpha.-olefins are ethylene, propene, 1-butene,
4-methyl-pentene-1, 1-hexene, 1-octene, and combinations of
ethylene and/or propene with one or more of such other
.alpha.-olefins. Other preferred monomers include styrene, halo- or
alkyl substituted styrenes, tetrafluoroethylene, vinylcyclobutene,
1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and
1,7-octadiene. Mixtures of the above-mentioned monomers may also be
employed.
[0286] A preferred group of olefin comonomers for polymerizations
where ethylene is the monomer includes propene, 1-butene,
1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,
1-nonene, 1-decene, 1,7-octadiene, 1,5-hexadiene, 1,4-pentadiene,
1,9-decadiene, ethylidenenorbornene, styrene, or a mixture thereof.
For polymerizations wherein propene is the monomer, the preferred
comonomers are the same as that immediately previous, but with the
inclusion of ethylene instead of propene.
[0287] Long chain macromolecular .alpha.-olefins can be vinyl
terminated polymeric remnants formed in situ during continuous
solution polymerization reactions. Under suitable processing
conditions such long chain macromolecular units may be polymerized
into the polymer product along with ethylene and other short chain
olefin monomers to give small quantities of long chain branching in
the resulting polymer.
[0288] In general, the polymerization may be accomplished at
conditions well known in the prior art for Ziegler-Natta or
Kaminsky-Sinn type polymerization reactions. Suspension, solution,
slurry, gas phase or high pressure, whether employed in batch or
continuous form or other process conditions, may be employed if
desired. Examples of such well known polymerization processes are
depicted in WO 88/02009, U.S. Pat. Nos. 5,084,534; 5,405,922;
4,588,790; 5,032,652; 4,543,399; 4,564,647; 4,522,987, which are
incorporated herein by reference; and elsewhere. Preferred
polymerization temperatures are from 0-250.degree. C. Preferred
polymerization pressures are from atmospheric to 3000
atmospheres.
[0289] Preferably, the processes of this invention are performed in
a single reactor, which may have a single reaction vessel or two or
more vessels producing essentially the same polyolefin copolymer
composition. Thus, the polymerization processes of this invention
do not produce blends, or where more than one reaction vessel is
used do not require blending to produce essentially homogeneous
polyolefin copolymer compositions.
[0290] In most polymerization reactions the molar ratio of
catalyst:polymerizable compounds employed is from 10.sup.-12:1 to
10.sup.-1:1, more preferably from 10.sup.-12:1 to 10.sup.-5:1.
[0291] Suitable solvents for polymerization via a solution process
are noncoordinating, inert liquids. Examples include straight and
branched-chain hydrocarbons such as isobutane, butane, pentane,
hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic
hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane,
methylcycloheptane, and mixtures thereof; perfluorinated
hydrocarbons such as perfluorinated C.sub.4-10 alkanes, and
aromatic and alkyl-substituted aromatic compounds such as benzene,
toluene, and xylene. Suitable solvents also include liquid olefins
which may act as monomers or comonomers including ethylene,
propylene, 1-butene, butadiene, cyclopentene, 1-hexene, 1-heptene
3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene,
1,7-octadiene, 1,9-decadiene, 1-octene, 1-decene, styrene,
divinylbenzene, ethylidenenorbornene, allylbenzene, vinyltoluene
(including all isomers alone or in admixture), 4-vinylcyclohexene,
and vinylcyclohexane. Mixtures of the foregoing are also
suitable.
[0292] One such polymerization process comprises: contacting,
optionally in a solvent, one or more .alpha.-olefins with a
catalyst in one or more continuous stirred tank or tubular
reactors. U.S. Pat. Nos. 5,272,236 and 5,278,272 related to olefin
polymerizations in solution and are incorporated herein by
reference.
[0293] The process of the present invention can be employed to
advantage in the gas phase copolymerization of olefins. Gas phase
processes for the polymerization of olefins, especially the
homopolymerization and copolymerization of ethylene and propylene,
and the copolymerization of ethylene with higher .alpha.-olefins
such as, for example, 1-butene, 1-hexene, 4-methyl-1-pentene are
well known in the art. Such processes are used commercially on a
large scale for the manufacture of high density polyethylene
(HDPE), medium density polyethylene (MDPE), linear low density
polyethylene (LLDPE) and polypropylene.
[0294] The gas phase process employed can be, for example, of the
type which employs a mechanically stirred bed or a gas fluidized
bed as the polymerization reaction zone. Preferred is the process
wherein the polymerization reaction is carried out in a vertical
cylindrical polymerization reactor containing a fluidized bed of
polymer particles supported above a perforated plate, the
fluidisation grid, by a flow of fluidisation gas.
[0295] The gas employed to fluidize the bed comprises the monomer
or monomers to be polymerized, and also serves as a heat exchange
medium to remove the heat of reaction from the bed. The hot gases
emerge from the top of the reactor, normally via a tranquilization
zone, also known as a velocity reduction zone, having a wider
diameter than the fluidized bed and wherein fine particles
entrained in the gas stream have an opportunity to gravitate back
into the bed. It can also be advantageous to use a cyclone to
remove ultra-fine particles from the hot gas stream. The gas is
then normally recycled to the bed by means of a blower or
compressor and a one or more heat exchangers to strip the gas of
the heat of polymerization.
[0296] A preferred method of cooling of the bed, in addition to the
cooling provided by the cooled the recycle gas, is to feed a
volatile liquid to the bed to provide an evaporative cooling
effect. The volatile liquid employed in this case can be, for
example, a volatile inert liquid, for example, a saturated
hydrocarbon having about 3 to about 8, preferably 4 to 6, carbon
atoms. In the case that the monomer or comonomer itself is a
volatile liquid, or can be condensed to provide such a liquid, this
can be suitably be fed to the bed to provide an evaporative cooling
effect. Examples of olefin monomers which can be employed in this
manner are olefins containing about three to about eight,
preferably three to six carbon atoms. The volatile liquid
evaporates in the hot fluidized bed to form gas which mixes with
the fluidizing gas. If the volatile liquid is a monomer or
comonomer, it will undergo some polymerization in the bed. The
evaporated liquid then emerges from the reactor as part of the hot
recycle gas, and enters the compression/heat exchange part of the
recycle loop. The recycle gas is cooled in the heat exchanger and,
if the temperature to which the gas is cooled is below the dew
point, liquid will precipitate from the gas. This liquid is
desirably recycled continuously to the fluidized bed. It is
possible to recycle the precipitated liquid to the bed as liquid
droplets carried in the recycle gas stream. This type of process is
described, for example in EP 89691; U.S. Pat. No. 4,543,399; WO
94/25495 and U.S. Pat. No. 5,352,749, which are hereby incorporated
by reference. A particularly preferred method of recycling the
liquid to the bed is to separate the liquid from the recycle gas
stream and to reinject this liquid directly into the bed,
preferably using a method which generates fine droplets of the
liquid within the bed. This type of process is described in BP
Chemicals' WO 94/28032, which is hereby incorporated by
reference.
[0297] The polymerization reaction occurring in the gas fluidized
bed is catalyzed by the continuous or semi-continuous addition of
catalyst. Such catalyst can be supported on an inorganic or organic
support material as described above. The catalyst can also be
subjected to a prepolymerization step, for example, by polymerizing
a small quantity of olefin monomer in a liquid inert diluent, to
provide a catalyst composite comprising catalyst particles embedded
in olefin polymer particles.
[0298] The polymer is produced directly in the fluidized bed by
catalyzed copolymerization of the monomer and one or more
comonomers on the fluidized particles of catalyst, supported
catalyst or prepolymer within the bed. Start-up of the
polymerization reaction is achieved using a bed of preformed
polymer particles, which are preferably similar to the target
polyolefin, and conditioning the bed by drying with inert gas or
nitrogen prior to introducing the catalyst, the monomers and any
other gases which it is desired to have in the recycle gas stream,
such as a diluent gas, hydrogen chain transfer agent, or an inert
condensable gas when operating in gas phase condensing mode. The
produced polymer is discharged continuously or discontinuously from
the fluidized bed as desired.
[0299] The gas phase processes suitable for the practice of this
invention are preferably continuous processes which provide for the
continuous supply of reactants to the reaction zone of the reactor
and the removal of products from the reaction zone of the reactor,
thereby providing a steady-state environment on the macro scale in
the reaction zone of the reactor.
[0300] Typically, the fluidized bed of the gas phase process is
operated at temperatures greater than 50.degree. C., preferably
from about 60.degree. C. to about 110.degree. C., more preferably
from about 70.degree. C. to about 110.degree. C.
[0301] Typically the molar ratio of comonomer to monomer used in
the polymerization depends upon the desired density for the
composition being produced and is about 0.5 or less. Desirably,
when producing materials with a density range of from about 0.91 to
about 0.93 the comonomer to monomer ratio is less than 0.2,
preferably less than 0.05, even more preferably less than 0.02, and
may even be less than 0.01. Typically, the ratio of hydrogen to
monomer is less than about 0.5, preferably less than 0.2, more
preferably less than 0.05, even more preferably less than 0.02 and
may even be less than 0.01.
[0302] The above-described ranges of process variables are
appropriate for the gas phase process of this invention and may be
suitable for other processes adaptable to the practice of this
invention.
[0303] A number of patents and patent applications describe gas
phase processes which are adaptable for use in the process of this
invention, particularly, U.S. Pat. Nos. 4,588,790; 4,543,399;
5,352,749; 5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453,471;
5,032,562; 5,028,670; 5,473,028; 5,106,804; and EP applications
659,773; 692,500; and PCT Applications WO 94/29032, WO 94/25497, WO
94/25495, WO 94/28032; WO 95/13305; WO 94/26793; and WO 95/07942
all of which are hereby incorporated herein by reference.
[0304] Desirably, the polyolefin copolymer composition of this
invention contains in polymerized form from 0.01 to 99.99 mole
percent ethylene as the monomer and from 99.99 to 0.01 mole percent
of one or more olefin comonomers. More desirably, the composition
contains in polymerized form from 0.1 to 99.9 mole percent ethylene
as the monomer and from 99.9 to 0.1 mole percent of one or more
olefin comonomers. Preferably, the composition contains in
polymerized form from 50 to 99.9 mole percent ethylene as the
monomer and from 50 to 0.1 mole percent of one or more olefin
comonomers. A highly preferred embodiment is that where the
composition contains in polymerized form from 96 to 99.9 mole
percent ethylene as the monomer and from 4 to 0.1 mole percent of
one or more olefin comonomers.
[0305] Generally, it is desirable that the density of the
composition be from about 0.87 to about 0.96, although it may be
higher or lower than this range. More highly desirably, the density
is from about 0.90 to about 0.94, and preferably from 0.910 to
about 0.925. The composition desirably has a melt index I.sub.2 of
from about 0.01 to about 150, and an I.sub.21/I.sub.2 which is
equal to or greater than 24, and a Mw/Mn of from about 2.0 to about
10.
[0306] A preferred polyolefin copolymer composition is that wherein
the composition has an I.sub.21/I.sub.2 which is equal to or
greater than 24 and a Mw/Mn of from about 2.0 to about 3.5.
[0307] A preferred polyolefin copolymer composition is that wherein
the composition has a short chain branching distribution that is
multimodal, or wherein the composition has a molecular weight
distribution that is multimodal.
[0308] Another preferred polyolefin copolymer composition of is
that wherein the density of the composition is from about 0.910 to
about 0.925, the comonomer to monomer molar ratio is less than
0.02, the hydrogen to monomer ratio is less than 0.02, and the
composition is produced in a reactor with a reaction zone having a
temperature of 70.degree. C. or higher.
[0309] The homogeneity of the polymers is typically described by
the SCBDI (Short Chain Branch Distribution Index) or CDBI
(Composition Distribution Branch Index) and is defined as the
weight percent of the polymer molecules having a comonomer content
within 50 percent of the median total molar comonomer content. The
SCBDI of a polymer is readily calculated from data obtained from
techniques known in the art, such as, for example, temperature
rising elution fractionation (abbreviated herein as "TREF") as
described, for example, in Wild et al, Journal of Polymer Science,
Poly. Phys. Ed., Vol. 20, p. 441 (1982), in U.S. Pat. No. 4,798,081
(Hazlitt et al.), or in U.S. Pat. No. 5,089,321 (Chum et al.) the
disclosures of all of which are incorporated herein by reference.
The SCBDI or CDBI for the homogeneous linear and for the
substantially linear ethylene/.alpha.-olefin polymers used in the
present invention is preferably greater than 50 percent.
[0310] For the polyolefin polymer compositions of this invention,
the long chain branch is longer than the short chain branch that
results from the incorporation of one or more .alpha.-olefin
comonomers into the polymer backbone. The empirical effect of the
presence of long chain branching in the copolymers of this
invention is manifested as enhanced rheological properties which
are indicated by higher flow activation energies, and greater
I.sub.21/I.sub.2 than expected from the other structural properties
of the compositions.
[0311] Measurement of comonomer content vs log molecular weight by
GPC/FTIR
[0312] The comonomer content as a function of molecular weight was
measured by coupling a Fourier transform infrared spectrometer
(FTIR) to a Waters 150.degree. C. Gel Permeation Chromatograph
(GPC). The setting up, calibration and operation of this system
together with the method for data treatment has been described
previously (L. J. Rose et al, "Characterisation of Polyethylene
Copolymers by Coupled GPC/FTIR" in "Characterisation of
Copolymers", Rapra Technology, Shawbury UK, 1995, ISBN
1-85957-048-86.) In order to characterize the degree to which the
comonomer is concentrated in the high molecular weight part of the
polymer, the GPC/FTIR was used to calculate a parameter named
comonomer partition factor, Cpf. M.sub.n and M.sub.w were also
determined using standard techniques from the GPC data.
[0313] Comonomer Partitioning Factor (GPC-FTIR)
[0314] The comonomer partitioning factor C.sub.pf is calculated
from GPC/FTIR data. It characterizes the ratio of the average
comonomer content of the higher molecular weight fractions to the
average comonomer content of the lower molecular weight fractions.
Higher and lower molecular weight are defined as being above or
below the median molecular weight respectively, that is, the
molecular weight distribution is divided into two parts of equal
weight. C.sub.pf is calculated from the following equation: 3 C pf
= i = 1 n w i c i i = 1 n w i j = 1 m w j c j j = 1 m w j ,
[0315] where: c.sub.i is the mole fraction comonomer content and
w.sub.i is the normalized weight fraction as determined by GPC/FTIR
for the n FTIR data points above the median molecular weight.
c.sub.j is the mole fraction comonomer content and w.sub.i is the
normalized weight fraction as determined by GPC/FTIR for the m FTIR
data points below the median molecular weight. Only those weight
fractions, w.sub.i or w.sub.j which have associated mole fraction
comonomer content values are used to calculate C.sub.pf. For a
valid calculation, it is required that n and m are greater than or
equal to 3. FTIR data corresponding to molecular weight fractions
below 5,000 are not included in the calculation due to the
uncertainties present in such data.
[0316] For the polyolefin copolymer compositions of this invention,
C.sub.pf desirably is equal to or greater than 1.10, more desirably
is equal to or greater than 1.15, even more desirably is equal to
or greater than 1.20, preferably is equal to or greater than 1.30,
more preferably is equal to or greater than 1.40, even more
preferably is equal to or greater than 1.50, and still more
preferably is equal to or greater than 1.60.
[0317] ATREF-DV
[0318] ATREF-DV has been described in U.S. Pat. No. 4,798,081,
which is hereby incorporated by reference, and in "Determination of
Short-Chain Branching Distributions of Ethylene copolymers by
Automated Analytical Temperature Rising Elution Fractionation"
(Auto-ATREF), J. of Appl Pol Sci: Applied Polymer Symposium 45,
25-37 (1990). ATREF-DV is a dual detector analytical system that is
capable of fractionating semi-crystalline polymers like Linear Low
Density Polyethylene (LLDPE) as a function of crystallization
temperature while simultaneously estimating the molecular weight of
the fractions. With regard to the fractionation, ATREF-DV is
analogous to Temperature Rising Elution Fractionation (TREF)
analysis that have been published in the open literature over the
past 15 years. The primary difference is that this Analytical-TREF
(ATREF) technique is done on a small scale and fractions are not
actually isolated. Instead, a typical liquid chromatographic (LC)
mass detector, such as an infrared single frequency detector, is
used to quantify the crystallinity distribution as a function of
elution temperature. This distribution can then be transformed to
any number of alternative domains such as short branching
frequency, comonomer distribution, or possibly density. Thus, this
transformed distribution can then be interpreted according to some
structural variable like comonomer content, although routine use of
ATREF for comparisons of various LLDPE's is often done directly in
the elution temperature domain.
[0319] To obtain ATREF-DV data, a commercially available viscometer
especially adapted for LC analysis, such as a Viskotek.TM. is
coupled with the IR mass detector. Together these two LC detectors
can be used to calculate the intrinsic viscosity of the ATREF-DV
eluant. The viscosity average molecular weight of a given fraction
can then be estimated using appropriate Mark Houwink constants, the
corresponding intrinsic viscosity, and suitable coefficients to
estimate the fractions concentration (dl/g) as it passes through
the detectors. Thus, a typical ATREF-DV report will provide the
weight fraction polymer and viscosity average molecular weight as a
function of elution temperature. Mpf is then calculated using the
equation given.
[0320] Molecular Weight Partitioning Factor
[0321] The molecular weight partitioning factor M.sub.pf is
calculated from TREF/DV data. It characterizes the ratio of the
average molecular weight of the fractions with high comonomer
content to the average molecular weight of the fractions with low
comonomer content. Higher and lower comonomer content are defined
as being below or above the median elution temperature of the TREF
concentration plot respectively, that is, the TREF data is divided
into two parts of equal weight. M.sub.pf is calculated from the
following equation: 4 M pf = i = 1 n w i M i i = 1 n w i j = 1 m w
j M j j = 1 m w j ,
[0322] where: M.sub.i is the viscosity average molecular weight and
w.sub.i is the normalized weight fraction as determined by ATREF-DV
for the n data points in the fractions below the median elution
temperature. M.sub.j is the viscosity average molecular weight and
w.sub.j is the normalized weight fraction as determined by ATREF-DV
for the m data points in the fractions above the median elution
temperature. Only those weight fractions, w.sub.i or w.sub.j which
have associated viscosity average molecular weights greater than
zero are used to calculate M.sub.pf. For a valid calculation, it is
required that n and m are greater than or equal to 3.
[0323] For the polyolefin copolymer compositions of this invention,
M.sub.pf desirably is equal to or greater than 1.15, more desirably
is equal to or greater than 1.30, even more desirably is equal to
or greater than 1.40, preferably is equal to or greater than 1.50,
more preferably is equal to or greater than 1.60, even more
preferably is equal to or greater than 1.70.
[0324] Activation Energy as an Indicator of Long Chain
Branching
[0325] The significance and determination of the activation energy
of flow, which represents the temperature dependence of the
viscosity, has been described extensively (J. M. Dealy and K. F.
Wissbrun, "Melt Rheology and its Role in Plastics Processing", Van
Nostrand Reinhold, New York (1990)). For polyolefins, the Arrhenius
equation is generally used to describe the temperature dependence
of viscosity since T>Tg+100 (that is, the melt temperature (T)
is greater than the glass transition temperature (Tg)+100; if this
inequality is not true the Williams-Landel-Ferry or WLF equation is
used to describe the temperature dependence of the viscosity). It
has also been well established that long chain branched polymers
have higher activation energies than comparable linear polymers.
These comparisons have been shown for homopolymer polyethylene, in
which the activation energy for the linear homopolymer is about 6.5
kcal/mol as compared to about 12 to 14 kcal/mol for long chain
branched polymers produced by the high pressure, free radical
process. When using an activation energy technique as an indicator
of long chain branching, one must be careful to take into account
sources of extraneous effects such as crosslinking, comonomer
content effects, or impurities such as cocatalyst residue.
[0326] For polyolefin copolymers, taking into account the effects
described in the preceding paragraph, a value for the activation
energy of about 8 kcal/mol or more in combination with greater
I.sub.21/I.sub.2 than expected from the other structural properties
of the compositions can be indicative of the presence of long chain
branching, and especially a value for the activation energy of
about 10 kcal/mol or more, in combination with greater
I.sub.21/I.sub.2 than expected from the other structural properties
of the compositions, definitely indicates the presence of long
chain branching. The preferred polyolefin copolymer compositions of
one embodiment of this invention desirably have at least about 0.01
long chain branches per 1000 carbon atoms along the polymer
backbone, more desirably from about 0.01 to about 8 long chain
branches per 1000 carbon atoms along the polymer backbone,
preferably from about 0.01 to about 3 long chain branches per 1000
carbon atoms along the polymer backbone, more preferably from about
0.01 to about 1 long chain branches per 1000 carbon atoms along the
polymer backbone, and still more preferably from about 0.02 to
about 0.5 long chain branches per 1000 carbon atoms along the
polymer backbone. It should be understood that, when long chain
branching is measured by some experimental techniques, such as NMR,
the units for the aforementioned ranges of values for the number of
long chain branches are per 1000 total carbon atoms.
[0327] The temperature dependence of the viscosity for
polyethylenes can be expressed in terms of an Arrhenius equation,
in which the activation energy can be related to a shift factor,
a.sub.T, used to determine a mastercurve for the material by
time-temperature superposition. The values of the shift factor
a.sub.T are independent of molecular weight and molecular weight
distribution (W. W. Graessley, "Viscoelasticity and Flow in Polymer
Melts and Concentrated Solutions", in J. E. Mark et al., Ed.,
"Physical Properties of Polymers", 2.sup.nd Ed., ACS, New York
(1993); J. Wang and R. S. Porter, "On The Viscosity-Temperature
Behavior of Polymer Melts", Rheol. Acta, 34, 496 (1995); R. S.
Porter, J. P. Knox, and J. F. Johnson, "On the Flow and Activation
Energy of Branched Polyethylene Melts", Trans. Soc. Rheol., 12, 409
(1968).), and thus the activation energy is independent of
molecular weight and molecular weight distribution for polymers
that obey an Arrhenius relationship between shift factors and
inverse temperature. Others (V. R. Raju et al., "Properties of
Amorphous and Crystallizable Hydrocarbon Polymers. IV. Melt
Rheology of Linear and Star-Branched Hydrogenated Polybutadiene",
J. Polym. Sci., Polym. Phys. Ed., 17, 1223 (1979).) have shown that
the high activation energies (10-18 kcal/mol) of long chain
branched polybutadienes as compared to that of linear polyethylene
(6.4 kcal/mol) are related to long-chain branching. Variation of
the activation energy among long chain branched samples was
concluded to be due to variations in average branch lengths.
[0328] Determination of Activation Energy
[0329] Stabilization of Samples
[0330] If samples were received unstabilized, the samples were
stabilized with the following stabilization package: 1250 ppm
calcium stearate, 500 ppm Irganox 1076, and 800 ppm PEPQ. This
stabilization package was dissolved in acetone, which was then
gently poured over the sample. The sample was then placed in a
vacuum oven and dried at a temperature of 50-60.degree. C. until
the sample was dry (approximately one day).
[0331] Molding of Samples
[0332] All samples were compression molded with a Tetrahedron MTP-8
Hot Press before Theological testing. A tray was used to contain
the samples and to transfer the sample in and out of the press. A
metal plate was placed on the tray, and a Mylar sheet was placed on
top of the brass plate. The sample shims used were of approximately
2-3 mil thickness and slightly greater than 1 inch diameter in the
form of a circle/disk. These shims were filled with sample, with up
to 8 shims being used per molding. If many disks were required for
a given sample, a 3 inch diameter shim was used. Another piece of
Mylar was then placed over the top of the sample and over this was
placed a metal plate. The tray with samples was then placed between
the tetrahedron plates, which were at 350.degree. F. The
Tetrahedron plates are then brought together for 5 minutes with a
force of 1500 pounds. The tray was then removed from the press and
allowed to cool. An arc punch of 25 mm diameter was then used to
cut the samples for rheological testing.
[0333] Rheological Testing
[0334] Rheological testing was performed on a Rheometrics RMS-800
with 25 mm diameter parallel plates in the dynamic mode. Before
performing the flow activation energy experiments, two strain sweep
experiments were performed to determine the percent strain to
perform the activation energy experiments so that the testing would
be performed in the linear viscoelastic region and the torque
signals would be significant. One strain sweep experiment was
performed at the highest test temperature (210.degree. C.) at a low
frequency (0.1 rad/s) to determine the minimum percent strain
necessary to generate a significant torque signal. The second
strain sweep was performed at the lowest temperature (170.degree.
C.) at the highest frequency (100 rad/s) to determine the maximum
percent strain allowable to remain within the linear viscoelastic
region. In general, the percent strain ranged from 10-30 percent
depending upon the molecular weight/stiffness of the sample.
[0335] The activation energies were determined by performing a
frequency sweep from 100 to 0.01 rad/s with five points per decade
at 210, 190, and 170.degree. C. with a percent strain as determined
above. A separate 25 mm disk or plaque of material was used for
each experiment. The Theological data were analyzed with the
Rheometrics RHIOS 4.4 software. The following conditions were
selected for the time-temperature superposition (t-T) and the
determination of the flow activation energies (Ea) according to an
Arrhenius equation, a.sub.T=exp(Ea/RT), which relates the shift
factor (a.sub.T) to E (R is the gas constant, and T is the absolute
temperature):
[0336] Shift method: 2D
[0337] Shift accuracy: high
[0338] Interpolation: spline
[0339] all at 190.degree. C. reference temperature.
[0340] The polyolefin copolymer compositions of a preferred
embodiment of this invention desirably have a flow activation
energy of at least about 8 kcal/mol, more desirably of at least
about 10 kcal/mol, preferably of at least about 12 kcal/mol and
more preferably of at least about 15 kcal/mol.
[0341] The polyolefin copolymer compositions of this invention may
be blended with a wide variety of other resins to achieve a
desirable balance of physical properties, or for economic reasons.
Generally, the physical properties of the blends are what would be
expected from a weighted interpolation of the physical properties
of the individual components, with the greatest deviations from
linearity being seen when one of the blend components is small
relative to the other.
[0342] Desirably, the blends of this invention comprise two or more
resin components, (A) and (B), where the blend comprises from about
1 weight percent to about 99 weight percent of (A) and from about
99 weight percent to about 1 weight percent of one or more resins
that are different from the (A) component. The (A) component may be
any of the polyolefin copolymer compositions of this invention,
while the (B) component may be any other resin which is not
incompatible with component (A). Preferred (B) components are
various polyolefins.
[0343] In one embodiment, where it is desirable that the (B)
component predominate, the blend comprises from about 1 weight
percent to about 30 weight percent of (A), and from about 99 weight
percent to about 70 weight percent of (B) one or more resins that
are different from the (A) component. If a greater disparity in the
amounts of the components is desired, the blend comprises from
about 1 weight percent to about 15 weight percent of (A) and from
about 99 weight percent to about 85 weight percent of (B) one or
more resins that are different from the (A) component.
[0344] In an alternative embodiment, where it is desirable that the
(A) component predominate, the blend comprises from about 99 weight
percent to about 70 weight percent of (A), and from about 1 weight
percent to about 30 weight percent of (B) one or more resins that
are different from the (A) component. If a greater disparity in the
amounts of the components is desired, the blend comprises from
about 99 weight percent to about 85 weight percent of (A), and from
about 1 weight percent to about 15 weight percent of (B) one or
more resins that are different from the (A) component.
EXAMPLES
[0345] Examples 1-3 are three samples taken on three successive
days during a single polymerization run. The same catalyst was used
throughout the run and basically the same polymerization conditions
were maintained throughout the run.
[0346] Catalyst preparation for Examples 1-3
[0347] (i) Treatment of silica
[0348] 110 liters of hexane was placed in a 240 liter vessel under
nitrogen and 0.75 g of Stadis.TM. 425 (diluted at 1 weight percent
in hexane) was added. Stadis.TM. 425 is a hydrocarbon based
antistatic agent available from DuPont Chemicals. 5 Kg of
Sylopol.TM. 948 silica (previously dried at 200.degree. C. for 5
hours) was then added. 150 ml of water was then added at ambient
temperature during a period of 1 hour. 16.67 moles of TEA was then
added at 30.degree. C. during a period of 1 hour. After a holding
period of 30 minutes, the silica was washed 6 times with 130 liters
of hexane.
[0349] (ii) Catalyst fabrication
[0350] The silica treated as above was dried and then 25 liters of
toluene added. 59.59 liters of tris(pentafluorophenyl)boron
solution in hexane (3.1 wt percent) was then added at ambient
temperature during a period of 30 minutes. 3.38 liters of
C.sub.5Me.sub.4SiMe.sub.2NCMe.sub.3TiMe.sub.2
((t-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethylsilaneti-
tanium dimethyl) solution in hexane (12.25 wt percent) was then
added at ambient temperature during a period of 15 minutes. The
catalyst was then held at 25.degree. C. for 1 hour, and a further
0.125 g of Stadis.TM. 425 added (diluted at 1 wt. percent in
hexane). The catalyst was then dried at 40.degree. C. under vacuum
(20 mmHg) to give a free flowing powder with a brown/ochre
color.
[0351] (iii) Polymerization using continuous fluidized bed reactor
for Examples 1-3
[0352] Ethylene, n-hexene, hydrogen and nitrogen were fed into a
continuous fluidized bed reactor of diameter 45 cm. Polymer product
was continuously removed from the reactor. Operating conditions and
properties of the composition are reported in Table 1.
1TABLE 1 Resin Name Example 1 Example 2 Example 3 Example 4 Example
5 Example 6 .vertline.(2.16), dg/min 1.36 0.85 0.91 0.86 1.20 0.77
.vertline.(21.6), dg/min 43.8 26.7 29.1 20.9 -- -- Density, g/cc
.9230 .9158 .9120 .9178 .9200 .9153 Mw 86000 95400 95100 -- 120000
94592 Mw/Mn 2.68 2.63 2.19 3.4 6 3.43 Ea,kcal/mol 13.15 11.07 10.31
7.39 19.2 -- Cpf 1.34 1.24 1.26 1.22 1.12 1.67 Mpf 1.52 1.52 1.63
1.8 1.23 -- DSC PEAK,C 119.86 117.99 117.9 -- Temperature,C 80 80
80 70 80 65 Comonomer 1-Hexene 1-Hexene 1-Hexene 1-Hexene 1-Hexene
1-Hexene Catalyst Type mono-Cp mono-Cp mono-Cp mono-Cp bridged bis
bridged bis Cp Cp Activator Borane Borane Borane Borane MAO MAO Gas
Phase Operating Conditions Total Press., Bar 16 16 16 9 20.2 20
Temp., C 80.5 80 80.3 70 80 65 C2 Press., Bar 6.7 7.2 7.2 8 11 12
H2/C2 Press. 0.003 0.0032 0.0033 0.0018 0.0011 0.005 C6/C2 Press
0.0034 0.0045 0.0048 0.0033 0.012 0.009 Production, kg/hr 10 10 15
11 --
Example 4
[0353] (i) Treatment of silica
[0354] A suspension of ES70 silica (7 kg, previously calcined at
500.degree. C. for 5 hours) in 110 liters of hexane was made up in
a 240 liter vessel under nitrogen. A solution of TEA in hexane (9.1
moles, 0.976M solution) was added slowly to the stirred suspension
over 30 minutes, while maintaining the temperature of the
suspension at 30.degree. C. The suspension was stirred for a
further 2 hours. The hexane was filtered, and the silica washed 4
times with hexane, so that the aluminum content in the final
washing was less than 1 mmol Al/liter. Finally the suspension was
dried in vacuo at 40.degree. C. to give a free flowing treated
silica powder.
[0355] (ii) Catalyst fabrication
[0356] Na-dried, distilled toluene (55 ml) was added to 13 g of the
treated silica powder in a 250 ml round bottomed flask in a dry
nitrogen glove box. To the suspension was added a solution of
tris(pentafluorophenyl)boron in toluene (7.6 ml, 7.85 wt percent,
d=0.88 g/ml) by syringe. Then a solution of
(t-butylamido)(tetramethyl-.eta..sup-
.5-cyclopentadienyl)dimethylsilanetitanium
.eta..sup.4-1,3-pentadiene in toluene (2.6 ml, 10.7 wt percent,
d=0.88 g/ml) was added by syringe. The suspension was shaken well
for 5 minutes, then dried in vacuo at 20.degree. C. to give a
free-flowing pale green powder.
[0357] (iii) Polymerization using a semi-continuous fluidized bed
reactor
[0358] Ethylene, n-hexene, hydrogen and nitrogen were fed into a
batch fluidized bed reactor of diameter 15 cm. Starting with a seed
bed of LLDPE powder (.about.1 Kg), catalyst was injected and
polymerization carried out to increase the mass of the bed to
approximately 3.5 Kg. Product was then withdrawn to leave
approximately 1 Kg of the powder in the reactor. The steps of
polymerization and product withdrawal were carried out 5 times in
total to yield a product containing in the region of only 0.3
percent by weight of the starting bed. The product was a white free
flowing powder of bulk density 0.36 g/cm.sup.3. The average
productivity of the catalyst was about 1000 g polymer/g catalyst.
Operating conditions and properties of the composition are given in
Table 1.
2 Total pressure 9 bar Temperature 70.degree. C. Pressure C2 8 bar
Pressure H2/C2 0.0018 Pressure C6/C2 0.0033
Example 4A
[0359] (i) Treatment of silica
[0360] A suspension of ES70 silica (7 kg, previously calcined at
500.degree. C. for 5 hours) in 110 liters of hexane was made up in
a 240 liter vessel under nitrogen. A solution of TEA in hexane (9.1
moles, 0.976M solution) was added slowly to the stirred suspension
over 30 minutes, while maintaining the temperature of the
suspension at 30.degree. C. The suspension was stirred for a
further 2 hours. The hexane was filtered, and the silica washed 4
times with hexane, so that the aluminum content in the final
washing was less than 1 mmol Al/liter. Finally the suspension was
dried in vacuo at 40.degree. C. to give a free flowing treated
silica powder.
[0361] (ii) Catalyst fabrication
[0362] Na-dried, distilled toluene (55 ml) was added to 13 g of the
treated silica powder in a 250 ml round bottomed flask in a dry
nitrogen glove box. To the suspension was added a solution of
tris(pentafluorophenyl)boron in toluene (7.6 ml, 7.85 wt percent,
d=0.88 g/ml) by syringe. Then a solution of
(t-butylamido)(tetramethyl-.eta..sup-
.5-cyclopentadienyl)dimethylsilanetitanium
.eta..sup.4-3-methyl-1,3-pentad- iene in toluene (2.6 ml, 10.7 wt
percent, d=0.88 g/ml) was added by syringe. The suspension was
shaken well for 5 minutes, then dried in vacuo at 20.degree. C. to
give a free-flowing pale green powder.
[0363] (iii) Polymerization using a semi-continuous fluidized bed
reactor
[0364] Ethylene, n-hexene, hydrogen and nitrogen were fed into a
batch fluidized bed reactor of diameter 15 cm. Starting with a seed
bed of LLDPE powder (.about.1 Kg), catalyst was injected and
polymerization carried out to increase the mass of the bed to
approximately 3.5 Kg. Product was then withdrawn to leave
approximately 1 Kg of the powder in the reactor. The steps of
polymerization and product withdrawal were carried out 5 times in
total to yield a product containing in the region of only 0.3
percent by weight of the starting bed. The product was a white free
flowing powder of bulk density 0.36 g/cm.sup.3. The average
productivity of the catalyst was about 1000 g polymer/g catalyst.
Operating conditions and properties of the composition are given in
Table 1.
3 Total pressure 9 bar Temperature 70.degree. C. Pressure C2 8 bar
Pressure H2/C2 0.0018 Pressure C6/C2 0.0033
Example 5
[0365] Catalyst preparation
[0366] The catalyst was prepared in an inert atmosphere vessel of
volume 110 liters maintained under an inert atmosphere. Mixing was
applied throughout using a paddle stirrer operated at 20 rev/min.
7.5 moles of MAO (1.6 mole/liter in toluene) were added at ambient
temperature. A further 3.88 liters of toluene was added to rinse
the addition system. 100 mM of ethylene-bridged bis(indenyl)
zirconium dichloride diluted in 2.3 liters of toluene was then
added and a further 1 liter of toluene for rinsing. The temperature
was raised to 80.degree. C. and maintained at this value for 1
hour, and then cooled to 50.degree. C. and 2 Kg of ES70 silica
(dried for 5 hours at 800.degree. C.) was added. The temperature
was raised to 80.degree. C. and maintained for 2 hours 0.5 g of
Stadis.TM. 425 antistatic agent in 0.51 of toluene was then added
and the catalyst dried at 70.degree. C. under vacuum (700
torr).
[0367] Polymerization using continuous fluidized bed reactor for
Example 5
[0368] Ethylene, n-hexene, hydrogen and nitrogen were fed into a
continuous fluidized bed reactor of diameter 45 cm. Polymer product
was continuously removed from the reactor through a valve.
Operating conditions are as follows:
4 Total pressure 20.2 bar Temperature 80.degree. C. Pressure C2 11
bar Pressure H2/C2 0.0011 Pressure C6/C2 0.012
[0369] The properties of the composition are given in Table 1. The
value of activation energy found by flow activation analysis was
19.2 kcal/mol, which indicates significant long chain
branching.
Example 6
[0370] Catalyst preparation
[0371] The catalyst was prepared in an inert atmosphere vessel of
volume 110 liters maintained under an inert atmosphere. Mixing was
applied throughout using a paddle stirrer operated at 20 rev/min.
48.8 moles of MAO (1.85 mole/liter in toluene) were added at
ambient temperature. A further 3.88 liters of toluene was added to
rinse the addition system. 650 mM of ethylene-bridged bis(indenyl)
zirconium dichloride diluted in 5 liters of toluene was then added
and a further 1.2 liter of toluene for rinsing. The temperature was
raised to 80.degree. C. and maintained at this value for 1 hour,
and then cooled to 50.degree. C. and 13 kg of ES70 silica (dried
for 5 hours at 800.degree. C.) was added.
[0372] The temperature was raised to 80.degree. C. and maintained
for 2 hours 0.5 g of Stadis.TM. 425 antistatic agent in 0.11 of
toluene was then added and the catalyst dried at 70.degree. C.
under vacuum (700 mmHg).
[0373] Polymerization using continuous fluidized bed reactor for
Example 5
[0374] Ethylene, n-hexene, hydrogen and nitrogen were fed into a
continuous fluidized bed reactor of diameter 74 cm. Polymer product
was continuously removed from the reactor through a valve.
Operating conditions are as follows:
5 Total pressure 20.2 bar Temperature 65.degree. C. Pressure C2 12
bar Pressure H2/C2 0.005 Pressure C6/C2 0.009
[0375] The properties of the composition are given in Table 1.
Examples 100-104
[0376] The same catalyst formula and preparation method as for
Examples 1-3 was used for preparation of the catalyst for these
examples. However, only 3.5 Kg of silica was used and the
quantities of all other components were scaled down accordingly.
Polymerization was carried out in the same continuous fluidized bed
reactor of diameter 45 cm. Operating conditions and properties of
the composition are reported in Table 1A.
[0377] In the Tables that follow I.sub.2 and I.sub.2 were
determined by ASTM D-1238 and density by ASTM D-1505.
6TABLE 1A Example Example Example Example Example Example Example
Example 100 101 102 103 104 105 106 107 .vertline.(2.16), dg/min
0.85 0.84 3.70 3.00 2.00 0.96 1.41 0.96 .vertline.(21.6), dg/min 27
25.6 94 78 57 21.7 .44 24.5 Density, g/cc .9170 .9160 .9202 .9200
.9178 .9161 .9190 .9195 Mw Mw/Mn Ea, kcal/mol 13.4 14.7 8.9 7.8
10.2 7.66 13.3 11.1 Cpf 1.4 1.27 144 1.4 1.31 1.38 1.32 1.3 Mpf
1.89 1.52 1.81 1.84 1 68 1.54 1.52 DSC PEAK, C 1.54 1.52
Temperature,C 75 80 75 75 75 71 75 74 Comonomer C6 C6 C6 C6 C6 C6
C6 C6 Catalyst Type mono-Cp mono-Cp mono-Cp mono-Cp mono-Cp mono-Cp
mono-Cp mono-Cp Activator Borane Borane Borane Borane Borane Borane
Borane Borane Gas Phase Operating Conditions Total Press., Bar 16
16 16 16 16 18 16 16 Temp.,C 75 80 75 75 75 71 75 74 C2 Press., Bar
7.4 7.4 9 9.7 9.7 8.7 6.3 7.6 H2/C2 Press. 0.0035 0.004 0.0048
0.0042 0.0039 0.0019 0.0025 0.0032 C6/C2 Press 0.0032 0.0032 0.0032
0.0034 0.0035 0.0039 0.0036 0.0038 Production, kg/hr 14 12 9 13 12
8 65 50
[0378] Catalyst Preparation for Example 105
[0379] (i) Treatment of silica
[0380] 110 liters of hexane was placed in a 240 liter vessel under
nitrogen and 0.75 g of Stadis 425, diluted at 1 wt % in hexane, was
added. 2.9 Kg of Crossfield ES70 silica, which had previously been
dried at 500.degree. C. for 5 hours, and which contained 1.1 mM
OH/g) was then added. 3.75 moles of TEA was then added at
30.degree. C. during a period of 1 hour. After a holding period of
30 minutes, the silica was washed with hexane to eliminate excess
TEA and to reach the targeted aluminum in the supernatent of 1 mM
per liter of hexane.
[0381] (ii) Catalyst fabrication
[0382] The silica treated as above was dried and then 10.4 liters
of toluene added. 0.2 moles of tris(pentafluorophenyl)boron
solution in toluene (7.85 wt %) was then added at ambient
temperature during a period of 30 minutes. 0.15 moles of
(t-butylamido)(tetramethyl-.eta..sup.5-cyclo-
pentadienyl)dimethylsilanetitanium-.eta..sup.4-1,3-pentadiene in
toluene (10.17 wt %) was then added at ambient temperature during a
period of 15 minutes. A further 0.125 g of Stadis 425 was added
(diluted at 1 wt % in hexane). The catalyst was then dried at
40.degree. C. under vacuum (20 mmHg) to give a free flowing powder
with a green color.
[0383] (iii) Polymerization using continuous fluidized bed reactor
for examples 105
[0384] Ethylene, n-hexene, hydrogen and nitrogen were fed into a
continuous fluidized bed reactor of diameter 45 cm. Polymer product
was continuously removed from the reactor. Operating conditions are
given in Table 1A.
Example 106
[0385] The same catalyst formula and preparation method as for
Examples 1-3 was used for preparation of the catalyst for example
106. However, 10 Kg of silica was used and the quantities of all
other components were scaled up accordingly. Polymerization was
carried out in a continuous fluidized bed reactor of diameter 74
cm. Operating conditions and properties of the composition are
reported in Table 1A.
Example 107
[0386] The same catalyst formula and preparation method as for
Example 105 was used for preparation of the catalyst for Example
107. However, 17 Kg of silica was used and the quantities of all
other components were scaled up accordingly. Polymerization was
carried out in a continuous fluidized bed reactor of diameter 74
cm. Operating conditions and properties of the composition are
reported in Table 1A.
Comparative Examples A-F
[0387] Comparative Examples A-F are commercially available
materials which were tested and compared under the same conditions
to the compositions of Examples 1-6. The data for the comparatives
are in Table 2.
7TABLE 2 Comparative A Comparative B Comparative C Comparative D
Comparative E Comparative F Resin Name INNOVEX 7209 EXCEED 401
Novapol TD9022 DOWLEX 2056A AFFINITY FM Enhanced PE AA 1570
.vertline.(2.16), dg/min 0.90 4.50 0.87 1.00 1.00 0.85
.vertline.(21.6), dg/min -- -- -- -- -- Density, g/cc .9200 .9170
.9170 .9200 0.915 .9200 Mw -- 124200 113100 74700 118700 Mw/Mn 2.3
2.9 4.03 2.24 3.363 Ea, kcal/mol 6.82 8.47 (see pg 49) -- 7.28 14.1
Cpf <1 -- <1 -- 1.06 -- Mpf 0.45 1.11 0.61 0.62 0.73 2.32 DSC
PEAK,C 116 124 122 Temperature,C -- -- -- 195 -- -- Comonomer
4-methyl-1- 1-Hexene 1-Hexene 1-Octene 1-Octene 1-Octene pentene
Catalyst Type Traditional bis-Cp Traditional Traditional mono-Cp
Ziegler-Natta Ziegler-Natta Ziegler-Natta Promoter Type Gas Phase
Operating Conditions -- -- -- -- Total Press., Bar -- -- -- --
Temp., C -- -- -- -- C2 Press., Bar -- -- -- -- H2/C2 Press, -- --
-- -- C6/C2 Press -- -- -- -- Production, kg/hr
[0388] Comparative A is Innovex.TM. 7209, a commercially available
gas phase produced polyethylene produced by BP Chemicals using a
traditional Ziegler-Natta catalyst.
[0389] Comparative B is Exxon Exceed.TM. 401, a commercially
available gas phase produced polyethylene produced by Exxon
Chemical using a metallocene catalyst. (Note: A second sample of
this material was evaluated, and a value for E.sub.a of 7.53
kcal/mol was determined, as well as a value for I.sub.21 of 77.92
and I.sub.10 of 27.02, and, thus, a value of I.sub.21/I.sub.2 of
17.3 and I.sub.10/I.sub.2 of 6.0. In addition, the critical shear
rate at the onset of surface melt fracture was 294 s.sup.-1 at a
shear stress of 2.15.times.10.sup.6 dyn/cm.sup.2 and the critical
shear rate at the onset of gross melt fracture was 795 s.sup.-1 at
a shear stress of 3.45.times.10.sup.6 dyn/cm.sup.2. This data
indicates the absence of long chain branching.)
[0390] Comparative C is Novapol.TM. TD902, a commercially available
gas phase produced polyethylene produced by Novascor.TM. using a
traditional Ziegler-Natta catalyst.
[0391] Comparative D is DOWLEX.TM. 2056A, a commercially available
solution process polyethylene produced by The Dow Chemical Company
using a traditional Ziegler-Natta catalyst.
[0392] Comparative E is AFFINITY.TM. FM 1570, a commercially
available solution process polyethylene produced by The Dow
Chemical Company using a constrained geometry metallocene
catalyst.
[0393] Comparative F is enhanced polyethylene XU-59900.00, a
commercially available solution process polyethylene produced by
The Dow Chemical Company.
[0394] The improved processability observed for the compositions of
Examples 2a (see note 5 below) and 3 are due to the presence of
long chain branching in the polymer. DOWLEX.TM. 2056A, produced by
the solution process using Ziegler-Natta catalyst, contains no long
chain branching. The presence of long chain branching results in
higher melt strength which was measured by a Goettfert Rheotens
apparatus. The data is reported in Table 3.
8 TABLE 3 DOWLEX .TM. 2056A EX 2a EX 3 Resin Properties Melt Index,
dg/min. 1.0 1.1 0.91 Density, g/cc 0.920 0.915 0.912
Processability.sup.1 Motor Current, amp. 65 53 56 Pressure, psig
2690 2610 2770 Screw Power, hp 15 13 12 Bubble Stability.sup.2 Melt
Strength, cN 4 9 7 Sealing Properties.sup.3 Seal Strength, lb. 4.2
4.6 4.7 Hot Tack, lb. 0.4 2.7 2.8 Film Toughness.sup.4 Dart Impact
Strength, g 86 850 850 Notes: .sup.1Gloucester Film Line, 2.5-inch
screw, 6-inch barrel, 70 mil die gap, 120 lb/hr polymer extrusion
rate .sup.2Melt Strength at 190.degree. C. and 120 mm/s velocity
.sup.32.0 mil film, seal strength at 120.degree. C., Hot tack at
110.degree. C. .sup.40.8 mil blown film; Dart "B" test ASTM D-1709
.sup.5Material of Example 2a was produced in the run which gave
Examples 1-3 on the same day as Example 2, but at a lower
density.
[0395] The polyolefin copolymer compositions of this invention have
mechanical properties, such as dart impact strength, optical
properties and heat sealing properties which are superior to
conventional Ziegler produced compositions of comparable density.
They also have processability characteristics, as measured, for
example, by melt strength and melt flow ratio, which are superior
to conventional metallocene products of comparable density and melt
index, and in especially preferred embodiments, to conventional
Ziegler materials as well. The polyolefin copolymer compositions
also offer the advantage that they can be manufactured using a
single catalyst in a single reactor process. In the preferred
embodiment, the materials of the invention can be extruded through
conventional polyethylene extruders with lower power requirements,
lower extruder pressures, and lower melt temperatures then
conventional Ziegler-Natta and conventional metallocene
products.
[0396] Films and other articles of manufacture produced with the
polyolefin copolymer compositions of this invention desirably have
a melt strength of greater than 4 CNN, preferably equal to or
greater than 7, more preferably equal to or greater than 9. The
seal strength desirably is greater than 4.2 lb., preferably equal
to or greater than 4.6 lb., more preferably equal to or greater
than 4.8 lb. The hot tack is desirably is greater than 0.5 lb.,
preferably equal to or greater than 1.0 lb., more preferably equal
to or greater than 2.0 lb. The dart impact strength desirably is
greater than 100 g, more desirably greater than 200 g, preferably
equal to or greater than 500 g, more preferably equal to or greater
than 700, and even more preferably equal to or greater than 850
g.
[0397] Blends of the polyolefin copolymer composition with ethylene
homopolymer
[0398] Blends of the polyolefin copolymer composition of this
invention with an ethylene homopolymer produced by a high pressure
tubular process have been prepared and studied. Polyolefin
copolymer compositions designated by L022, from Example 100, and
L023, from Example 101, were individually blended with an ethylene
homopolymer resin (LDPE 501I) at levels between 0 and 100 per cent.
None of these resins contained slip or antiblock additives, except
the LDPE 501I, which was stabilized with 500 ppm Irganox 1076, a
phenolic antioxidant. Characteristics of the resins used for the
blends is reported in Table 4.
9TABLE 4 Resin Properties Resin Melt Index Density Description L022
0.89 0.9161 Gas Phase-Substantially linear ethylene polymer, INSITE
.TM. Catalyst L023 0.85 0.9177 Gas Phase-Substantially linear
ethylene polymer, INSITE .TM. Catalyst 501I 1.90 0.9220 Ethylene
Homopolymer, High pressure Tubular process
[0399] Data related to the composition of these blends and the
unblended materials are presented for Samples A through G in Table
5.
10TABLE 5 Blend Composition Weight % Resin Sample L022 L023 LDPE A
100 0 0 B 90 0 10 C 20 0 80 D 0 0 100 E 0 100 0 F 0 95 5 G 0 20
80
[0400] Blending LDPE into the substantially linear low density
polymer of this invention gave improvements in processability
relative to the unblended polyolefin copolymer composition of this
invention due to the increase in amounts of long chain branching,
and as demonstrated by a reduction in extruder amps and pressure.
Data related to processability are shown in Table 6. The blends
also provide significant improvements in optical characteristics,
as shown by a reduction in haze and an increase in both clarity and
gloss relative to the unblended polyolefin copolymer composition of
this invention, which is evident from the data in Table 7.
11TABLE 6 Processability Extruder Conditions Sample rpm lb/hr Melt
Temp amp psi A 57.2 120 442 51 2260 B 57.6 120 442 55 2440 C 54 120
438 36 1310 D 58.6 120 434 34 990 E 58.9 117 442 54 2510 F 58.6 119
442 55 2570 G 53.8 120 438 37 1450
[0401]
12TABLE 7 Optical Characteristics Gloss Gloss Sample Clarity 20
deg. 45 deg. A 91.6 44.1 61.1 B 92.9 59.2 66.7 C 93.1 57.5 71.5 D
95.5 74.1 76.1 E 90.2 49.5 62.2 F 92.2 59.3 66 G 92.5 54.4 69.6
[0402] For films made with the blends there was a noted improvement
in heat seal initiation temperature, as indicated by a reduction in
temperature required to obtain a 2 pound Heat Seal, and in the
final Seal Strength in pounds, relative to the unblended polyolefin
copolymer composition of this invention. Data related to this
aspect of Heat Seal and Seal Strength are presented in Table 8.
13TABLE 8 Heat Seal/Seal Strength Heat Seal % LDPE Initiation Temp.
Seal Strength, lb. 0 109 C. 2.1 10 108 C. 2.2 80 104 C. 2.9 100 102
C. 2.7
[0403] As levels of the homopolymer LDPE resin were increased, an
accompanying decrease in film strength, or mechanical properties,
relative to the unblended polyolefin copolymer composition of this
invention, was observed as the linear nature of the blend was
decreased. Reductions in the mechanical properties are shown in
Table 10 below.
[0404] Blending the polyolefin copolymer composition of this
invention into a LDPE homopolymer gave improvements in the
resulting film physical properties such as Ultimate Tensile
Strength, Dart Impact Resistance, Elmendorf Tear, and Hot Tack
Strength, relative to the unblended LDPE.
[0405] Hot Tack Strength is the strength, in Newtons, required to
pull apart two films in a partially molten condition. This test is
used to simulate the ability of a package to hold its seal, and not
spill the contents, while the heat seal has not yet cooled. As the
polyolefin copolymer composition of this invention was blended into
the LDPE, the hot tack strength increased as did the temperature
range in which the hot tack was observed. The data are presented in
Table 9.
14TABLE 9 Hot Tack % LDPE Hot Tack Strength, N Temperature Range,
C. 0 3.4 35 10 3.4 25 80 1.8 15 100 1.6 10
[0406] MD Elmendorf tear, being relatively low for the polyolefin
copolymer compositions of this invention, was relatively unaffected
by the addition of LDPE. The orientation effect did vary the CD
tear. The dart impact for the polyolefin copolymer compositions of
this invention is quite high, and only slightly affected at
moderate levels of blending with LDPE. Data for these film physical
properties are given in Table 10.
15TABLE 10 Film Physical Properties Description Elmendorf Tear Dart
Impact Sample L022 L023 LDPE MD CD grams A 100 0 0 187 317 658 B 90
0 10 186 613 654 C 20 0 80 162 256 100 D 0 0 100 152 238 100 E 0
100 0 168 646 508 F 0 95 5 155 726 556 G 0 20 80 166 650 100
[0407] Thus, it is clear that, while the high strength of the
polyolefin copolymer compositions of this invention were
compromised to some degree by blending with an LDPE homopolymer,
other properties may be advantageously affected. Similarly, while
some properties of an unblended LDPE homopolymer may be adversely
affected by blending with the polyolefin copolymer composition of
this invention, the strength of the blend is superior to unblended
LDPE.
* * * * *