U.S. patent application number 10/703981 was filed with the patent office on 2004-05-27 for irradiated, oxidized olefin polymer dispersing agents.
This patent application is currently assigned to Basell Poliolefine Italia S.p.A.. Invention is credited to Dang, Vu A., Fezza, Richard J., Song, Cheng Q..
Application Number | 20040102582 10/703981 |
Document ID | / |
Family ID | 29780423 |
Filed Date | 2004-05-27 |
United States Patent
Application |
20040102582 |
Kind Code |
A1 |
Dang, Vu A. ; et
al. |
May 27, 2004 |
Irradiated, oxidized olefin polymer dispersing agents
Abstract
Irradiated, oxidized olefin polymer dispersing aids for use in
the manufacture of additive concentrates and additive-containing
olefin polymer compositions.
Inventors: |
Dang, Vu A.; (Bear, DE)
; Fezza, Richard J.; (Wilmington, DE) ; Song,
Cheng Q.; (Wilmington, DE) |
Correspondence
Address: |
BASELL USA INC.
INTELLECTUAL PROPERTY
912 APPLETON ROAD
ELKTON
MD
21921
US
|
Assignee: |
Basell Poliolefine Italia
S.p.A.
Milan
IT
|
Family ID: |
29780423 |
Appl. No.: |
10/703981 |
Filed: |
November 6, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10703981 |
Nov 6, 2003 |
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10305844 |
Nov 27, 2002 |
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6677395 |
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Current U.S.
Class: |
525/333.8 |
Current CPC
Class: |
C08K 5/0066 20130101;
C08L 2205/03 20130101; C08J 2323/02 20130101; C08L 23/06 20130101;
C08L 2205/02 20130101; C08L 23/0815 20130101; C08L 23/08 20130101;
C08L 23/30 20130101; C08L 23/20 20130101; C08K 3/04 20130101; C08L
2201/02 20130101; C08L 23/10 20130101; C08K 5/0058 20130101; C08K
3/016 20180101; C08L 23/12 20130101; C08L 23/16 20130101; C08K
3/013 20180101; C08L 23/142 20130101; C08J 3/28 20130101; C08K
5/0008 20130101; C08L 2205/035 20130101; C08L 23/06 20130101; C08L
2666/02 20130101; C08L 23/08 20130101; C08L 2666/02 20130101; C08L
23/0815 20130101; C08L 2666/06 20130101; C08L 23/10 20130101; C08L
2666/06 20130101; C08L 23/12 20130101; C08L 2666/02 20130101; C08L
23/12 20130101; C08L 2666/06 20130101; C08L 23/142 20130101; C08L
2666/02 20130101; C08L 23/20 20130101; C08L 2666/02 20130101 |
Class at
Publication: |
525/333.8 |
International
Class: |
C08F 210/00 |
Claims
We claim:
1. An additive-containing olefin polymer composition comprising: A.
2.0 to 30.0 wt % of an irradiated, oxidized olefin polymer
material; B. 0.1 to 40.0 wt % of an additive selected from the
group consisting of colorants, halogenated flame retardants,
conductive carbon black, anti-microbial agents, anti-acids and
mixtures thereof; and C. 30.0 to 97.9 wt % of a non-irradiated,
non-oxidized olefin polymer material; wherein the sum of components
A+B+C is equal to 100 wt %.
2. The composition of claim 1 wherein component A and component C
are selected from the group consisting of: (a) a crystalline
homopolymer of propylene having an isotactic index greater than
80%; (b) a crystalline random copolymer of propylene and an olefin
selected from the group consisting of ethylene and C.sub.4-C.sub.10
.alpha.-olefins, provided that when the olefin is ethylene, the
maximum polymerized ethylene content is 10% by weight, and when the
olefin is a C.sub.4-C.sub.10 .alpha.-olefin, the maximum
polymerized content thereof is 20% by weight; (c) a crystalline
random terpolymer of propylene and two olefins selected from the
group consisting of ethylene and C.sub.4-C.sub.8 .alpha.-olefins,
provided that the maximum polymerized C.sub.4-C.sub.8
.alpha.-olefin content is 20% by weight, and when ethylene is one
of the olefins, the maximum polymerized ethylene content is 5% by
weight; (d) an olefin polymer composition comprising: (i) 10 parts
to 60 parts by weight of a crystalline propylene homopolymer having
an isotactic index at least 80%, or a crystalline copolymer
selected from the group consisting of (a) propylene and ethylene,
(b) propylene, ethylene and a C.sub.4-C.sub.8 .alpha.-olefin, and
(c) propylene and a C.sub.4-C.sub.8 .alpha.-olefin, the copolymer
having a propylene content of more than 85% by weight, and an
isotactic index greater than 60%; (ii) 3 parts to 25 parts by
weight of a copolymer of ethylene and propylene or a
C.sub.4-C.sub.8 .alpha.-olefin that is insoluble in xylene at
ambient temperature; and (iii) 10 parts to 80 parts by weight of an
elastomeric copolymer selected from the group consisting of (a)
ethylene and propylene, (b) ethylene, propylene, and a
C.sub.4-C.sub.8 .alpha.-olefin, and (c) ethylene and a
C.sub.4-C.sub.8 .alpha.-olefin, the copolymer optionally containing
0.5% to 10% by weight of a diene, and containing less than 70% by
weight, and being soluble in xylene at ambient temperature and
having an intrinsic viscosity of 1.5 to 4.0 dl/g; the total of (ii)
and (iii), based on the total olefin polymer composition being from
50% to 90%, and the weight ratio of (ii)/(iii) being less than 0.4,
wherein the composition is prepared by polymerization in at least
two stages; (e) a thermoplastic olefin comprising: (i) 10% to 60%
of a propylene homopolymer having an isotactic index at least 80%,
or a crystalline copolymer selected from the group consisting of
(a) ethylene and propylene, (b) ethylene, propylene and a
C.sub.4-C.sub.8 .alpha.-olefin, and (c) ethylene and a
C.sub.4-C.sub.8 .alpha.-olefin, the copolymer having a propylene
content greater than 85% and an isotactic index of greater than
60%; (ii) 20% to 60% of an amorphous copolymer selected from the
group consisting of (a) ethylene and propylene, (b) ethylene,
propylene, and a C.sub.4-C.sub.8 .alpha.-olefin, and (c) ethylene
and a .alpha.-olefin, the copolymer optionally containing 0.5% to
10% of a diene, and containing less than 70% ethylene and being
soluble in xylene at ambient temperature; and (iii) 3% to 40% of a
copolymer of ethylene and propylene or an .alpha.-olefin that is
insoluble in xylene at ambient temperature; (f) homopolymers of
ethylene; (g) random copolymers of ethylene and an alpha-olefin
selected from the group consisting of C.sub.3-10 alpha-olefins
having a maximum polymerized alpha-olefin content of 20 wt %; (h)
random terpolymers of ethylene and C.sub.3-10 alpha-olefins having
a maximum polymerized alpha-olefin content of 20 wt %; (i)
homopolymers of butene-1; (j) copolymers or terpolymers of butene-1
with a non-butene alpha-olefin comonomer content from 1 to 15 mole
%; and (k) mixtures thereof.
3. The composition of claim 2 wherein the non-irradiated,
non-oxidized olefin polymer is a crystalline homopolymer of
propylene having an isotactic index greater than 80%.
4. The composition of claim 2 wherein the irradiated, oxidized
olefin polymer starting material is a crystalline homopolymer of
propylene having an isotactic index greater than 80%.
5. The composition of claim 1 wherein the irradiated, oxidized
olefin polymer is produced by a process comprising: a. irradiating
a non-irradiated, non-oxidized olefin polymer starting material
under a blanket of an inert gas, thereby producing an irradiated
olefin polymer material; b. adding a controlled amount of oxygen to
expose the irradiated olefin polymer material to a first active
oxygen concentration greater than 0.004% but less than 15% by
volume, at a first temperature of from 25 C to a temperature below
the softening point of the irradiated olefin polymer material; and
c. heating the irradiated, oxidized olefin polymer material of step
(b) to a second temperature of from at least 25.degree. C. to a
temperature below the softening point of the irradiated, oxidized
olefin polymer material of step (b), while adding a controlled
amount of oxygen to expose the irradiated, oxidized olefin polymer
material of step (b) to a second controlled active oxygen
concentration greater than 0.004%, but less than 15% by volume.
6. The composition of claim 1 wherein the additive is a colorant
present in an amount from 0.1 to 5.0 wt %.
7. The composition of claim 1 wherein the additive is a halogenated
flame retardant composition comprising a halogenated compound first
component present in an amount from 2.0 to 30 wt %, and a second
component selected from the group consisting of antimony trioxide,
boron compounds, tin oxide, zinc oxide, zinc borate, aluminum
trioxide, aluminum trihydroxide and mixtures thereof, present in an
amount from 0.5 to 10 wt %.
8. An additive concentrate composition comprising: A. 9.0 to 85.0
wt % of an additive selected from the group consisting of
colorants, halogenated flame retardants, conductive carbon black,
anti-microbial agents, anti-acids and mixtures thereof; and B. 91.0
to 15.0 wt % of an irradiated, oxidized, olefin polymer material;
wherein the sum of components A+B is equal to 100 wt %.
9. The composition of claim 8 wherein the irradiated, oxidized
olefin polymer starting material is produced from a non-irradiated,
non-oxidized olefin polymer starting material comprising: (a) a
crystalline homopolymer of propylene having an isotactic index
greater than 80%; (b) a crystalline random copolymer of propylene
and an olefin selected from the group consisting of ethylene and
C.sub.4-C.sub.10 .alpha.-olefins, provided that when the olefin is
ethylene, the maximum polymerized ethylene content is 10% by
weight, and when the olefin is a C.sub.4-C.sub.10 .alpha.-olefin,
the maximum polymerized content thereof is 20% by weight; (c) a
crystalline random terpolymer of propylene and two olefins selected
from the group consisting of ethylene and C.sub.4-C.sub.8
.alpha.-olefins, provided that the maximum polymerized
C.sub.4-C.sub.8 .alpha.-olefin content is 20% by weight, and, when
ethylene is one of the olefins, the maximum polymerized ethylene
content is 5% by weight; (d) an olefin polymer composition
comprising: (i) 10 parts to 60 parts by weight of a crystalline
propylene homopolymer having an isotactic index at least 80%, or a
crystalline copolymer selected from the group consisting of (a)
propylene and ethylene, (b) propylene, ethylene and a
C.sub.4-C.sub.8 .alpha.-olefin, and (c) propylene and a
C.sub.4-C.sub.8 .alpha.-olefin, the copolymer having a propylene
content of more than 85% by weight, and an isotactic index greater
than 60%; (ii) 3 parts to 25 parts by weight of a copolymer of
ethylene and propylene or a C.sub.4-C.sub.8 .alpha.-olefin that is
insoluble in xylene at ambient temperature; and (iii) 10 parts to
80 parts by weight of an elastomeric copolymer selected from the
group consisting of (a) ethylene and propylene, (b) ethylene,
propylene, and a C.sub.4-C.sub.8 .alpha.-olefin, and (c) ethylene
and a C.sub.4-C.sub.8 .alpha.-olefin, the copolymer optionally
containing 0.5% to 10% by weight of a diene, and containing less
than 70% by weight, and being soluble in xylene at ambient
temperature and having an intrinsic viscosity of 1.5 to 4.0 dl/g;
the total of (ii) and (iii), based on the total olefin polymer
composition being from 50% to 90%, and the weight ratio of
(ii)/(iii) being less than 0.4, wherein the composition is prepared
by polymerization in at least two stages; and (e) a thermoplastic
olefin comprising: (i) 10% to 60% of a propylene homopolymer having
an isotactic index at least 80%, or a crystalline copolymer
selected from the group consisting of (a) ethylene and propylene,
(b) ethylene, propylene and a C.sub.4-C.sub.8 .alpha.-olefin, and
(c) ethylene and a C.sub.4-C.sub.8 .alpha.-olefin, the copolymer
having a propylene content greater than 85% and an isotactic index
of greater than 60%; (ii) 20% to 60% of an amorphous copolymer
selected from the group consisting of (a) ethylene and propylene,
(b) ethylene, propylene, and a C.sub.4-C.sub.8 .alpha.-olefin, and
(c) ethylene and an .alpha.-olefin, the copolymer optionally
containing about 0.5% to about 10% of a diene, and containing less
than 70% ethylene and being soluble in xylene at ambient
temperature; and (iii) about 3% to about 40% of a copolymer of
ethylene and propylene or an .alpha.-olefin that is insoluble in
xylene at ambient temperature. (f) homopolymers of ethylene; (g)
random copolymers of ethylene and an alpha-olefin selected from the
group consisting of C.sub.3-10 alpha olefins having a maximum
polymerized alpha-olefin content of 20 wt %; (h) random terpolymers
of ethylene and C.sub.3-10 alpha olefins having a maximum
polymerized alpha-olefin content of 20 wt %; (i) homopolymers of
butene-1; (j) copolymers or terpolymers of butene-1 with a
non-butene alpha-olefin comonomer content from 1 to 15 mole %; and
(k) mixtures thereof.
10. The composition of claim 9, wherein the olefin polymer starting
material is a crystalline homopolymer of polypropylene having an
isotactic index of greater than 80%.
11. The composition of claim 9, wherein the irradiated, oxidized
olefin polymer is produced by a process comprising: a. irradiating
the non-irradiated, non-oxidized olefin polymer starting material
under a blanket of an inert gas, thereby producing an irradiated
olefin polymer material; b. adding a controlled amount of oxygen to
expose the irradiated olefin polymer material to a first active
oxygen concentration greater than 0.004% but less than 15% by
volume, at a first temperature of from 25.degree. C. to a
temperature below the softening point of the irradiated olefin
polymer material; and c. heating the irradiated, oxidized olefin
polymer material of step (b) to a second temperature of from at
least 25.degree. C. to a temperature below the softening point of
the irradiated, oxidized olefin polymer material of step (b) while
adding a controlled amount of oxygen to expose the irradiated,
oxidized olefin polymer material of step (b) to a second active
oxygen concentration greater than 0.004%, but less than 15% by
volume.
12. The composition of claim 8 wherein the additive is a colorant
present in an amount from 10 to 70 wt %.
13. The composition of claim 8 wherein the additive is a
halogenated flame retardant composition comprising a halogenated
compound first component present in an amount from 7 to 65 wt %,
and a second component selected from the group consisting of
antimony trioxide, boron compounds, tin oxide, zinc oxide, zinc
borate, aluminum trioxide, aluminum trihydroxide, and mixtures
thereof present in an amount from 2.0 to 20 wt %.
14. An irradiated, oxidized ethylene or butene-1 polymer material
produced by a process comprising: (I) irradiating an olefin polymer
material selected from the group consisting of: (1) homopolymers of
ethylene; (2) random copolymers of ethylene and an alpha-olefin
selected from the group consisting of C.sub.3-10 alpha-olefins
having a maximum polymerized alpha-olefin content of 20 wt %; (3)
random terpolymers of ethylene and C.sub.3-10 alpha-olefins having
a maximum polymerized alpha-olefin content of 20 wt %; (4)
homopolymers of butene-1; (5) copolymers or terpolymers of butene-1
with a non-butene alpha-olefin comonomer content from 1 to 15 mole
%; and (6) mixtures thereof, thereby producing an irradiated
ethylene or butene-1 polymer material; (II) adding a controlled
amount of oxygen to expose the irradiated ethylene or butene-1
polymer material of (I) to a first active oxygen concentration
greater than 0.004% but less than 15% by volume, at a first
temperature of from 25.degree. C. to a temperature below the
softening point of the irradiated, ethylene or butene-1 polymer
material employed in (I); and (III) heating the irradiated ethylene
or butene-1 polymer material from (II) to a second temperature of
from at least 25.degree. C. to a temperature below the softening
point of the irradiated ethylene or butene-1 polymer material
employed in (I), while adding a controlled amount of oxygen to
expose the irradiated ethylene or butene-1 polymer material to a
second active oxygen concentration greater than 0.004%, but less
than 15% by volume.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to irradiated, oxidized olefin
polymer dispersing aids for use in the manufacture of additive
concentrates and additive-containing olefin polymer
compositions.
BACKGROUND
[0002] The effective use of olefin-based polymers often requires
the incorporation of additives into the polymer composition to
enhance the polymer's performance, aesthetic appeal and/or impart
desirable properties. For example, pigments are often added to meet
aesthetic requirements, or to improve heat resistance, heat
absorption, and fade resistance. Halogenated flame retardants may
be incorporated to improve flame-retardancy in the end-use product.
Other additives, such as anti-acids, anti-microbial agents, and
conductive carbon black are also often included in polymer
compositions.
[0003] Improving the dispersion of additives in polymer
compositions enhances the performance of those additives. In U.S.
Pat. No. 6,384,148, oxidates of polyethylene produced using
metallocene catalysts have been disclosed for the dispersion of
pigments. In U.S. Pat. No. 5,079,283, organic peroxides and azo
compounds were used to promote propylene polymer scission in
polypropylene-based compositions containing flame retardants. The
resulting higher melt flow material possessed improved flame
retardancy. Still another approach to dispersion is to use
polyethylene waxes, however, these compounds can result in polymer
blooming, and an associated decrease in the useful life of products
made from the polymer. Thus, there continues to be a need for
improved dispersion of additives in olefin polymer
compositions.
[0004] The dispersion of additives in olefin polymer compositions
using the irradiated, oxidized olefin polymer dispersants of this
invention provides a more homogenous distribution of the additive,
and promotes desirable flexibility in the formulation of commercial
olefin polymer materials. For example, at the same additive
concentration, an olefin polymer composition containing an additive
dispersed therein using the irradiated, oxidized polymer
dispersants of this invention provides improved performance over
the same olefin polymer composition without the dispersants of this
invention. Alternately, a polymer manufacturer could take advantage
of the performance enhancement provided by the irradiated, oxidized
polymer dispersants of this invention, by reducing the additive
levels in the olefin polymer compositions containing the
dispersants, while maintaining equivalent additive performance of
the same olefin polymer composition containing higher additive
levels without the dispersants of this invention.
[0005] The irradiation of olefin polymers has been described in a
number of patents. For example, U.S. Pat. No. 5,688,839 discloses
irradiating colored olefin polymer resin particles and mixing the
irradiated, colored resin particles with a background component,
where the colored resin particles only partially disperse, so as to
impart a marbleized appearance. U.S. Pat. No. 5,508,319 discloses
the irradiation of polyethylene. U.S. Pat. Nos. 5,508,318,
5,554,668, 5,731,362, and 5,591,785 disclose irradiated propylene
polymer material having long chain branching, high melt strength,
and strain hardening elongational viscosity. U.S. Pat. Nos.
5,820,981 and 5,804,304 disclose a polymer that is subjected to
irradiation in the substantial absence of oxygen, followed by a
multistage treatment in the presence of a controlled amount of
oxygen. However, none of these references disclose irradiated,
oxidized olefin polymer dispersing aids for use in the manufacture
of additive concentrates and additive-containing olefin polymer
compositions. It has unexpectedly been found that the dispersants
of the present invention provide distinct advantages in the
dispersion of additives in olefin polymer compositions.
SUMMARY OF THE INVENTION
[0006] In one embodiment, the present invention relates to an
additive-containing olefin polymer composition comprising:
[0007] A. 2.0 to 30.0 wt % of an irradiated, oxidized olefin
polymer material;
[0008] B. 0.1 to 40.0 wt % of an additive selected from the group
consisting of colorants, halogenated flame retardants, conductive
carbon black, anti-microbial agents, anti-acids and mixtures
thereof; and
[0009] C. 30.0 to 97.9 wt % of a non-irradiated, non-oxidized
olefin polymer material;
[0010] wherein the sum of components A+B+C is equal to 100 wt
%.
[0011] In another embodiment, the present invention relates to an
additive concentrate composition, the composition comprising:
[0012] A. 9.0 to 85.0 wt % of an additive selected from the group
consisting of colorants, halogenated flame retardants, conductive
carbon black, anti-microbial agents, anti-acids and mixtures
thereof; and
[0013] B. 15 to 91 wt % of an irradiated, oxidized olefin polymer
material;
[0014] wherein the sum of components A+B is equal to 100 wt %.
DETAILED DESCRIPTION OF THE INVENTION
[0015] Suitable olefin polymers useful as the irradiated and
oxidized or non-irradiated and non-oxidized olefin polymers are
propylene polymer materials, ethylene polymer materials, butene-1
polymer materials, and mixtures thereof.
[0016] When a propylene polymer material is used as the
non-irradiated and non-oxidized olefin polymer material or as the
starting material for making the irradiated, oxidized olefin
polymer of the present invention, the propylene polymer material
can be:
[0017] (A) a crystalline homopolymer of propylene having an
isotactic index greater than 80%, preferably about 90% to about
99.5%;
[0018] (B) a crystalline random copolymer of propylene and an
olefin selected from the group consisting of ethylene and
C.sub.4-C.sub.10 .alpha.-olefins, provided that when the olefin is
ethylene, the maximum polymerized ethylene content is 10% by
weight, preferably about 4%, and when the olefin is a
C.sub.4-C.sub.10 .alpha.-olefin, the maximum polymerized content
thereof is 20% by weight, preferably about 16%, the copolymer
having an isotactic index greater than 60%, preferably at least
70%;
[0019] (C) a crystalline random terpolymer of propylene and two
olefins selected from the group consisting of ethylene and
C.sub.4-C.sub.8 .alpha.-olefins, provided that the maximum
polymerized C.sub.4-C.sub.8 .alpha.-olefin content is 20% by
weight, preferably about 16%, and when ethylene is one of the
olefins, the maximum polymerized ethylene content is 5% by weight,
preferably about 4%, the terpolymer having an isotactic index
greater than 85%;
[0020] (D) an olefin polymer composition comprising:
[0021] (i) about 10 parts to about 60 parts by weight, preferably
about 15 parts to about 55 parts, of a crystalline propylene
homopolymer having an isotactic index at least 80%, preferably
about 90 to about 99.5%, or a crystalline copolymer selected from
the group consisting of (a) propylene and ethylene, (b) propylene,
ethylene and a C.sub.4-C.sub.8 .alpha.-olefin, and (c) propylene
and a C.sub.4-C.sub.8 .alpha.-olefin, the copolymer having a
propylene content of more than 85% by weight, preferably about 90%
to about 99%, and an isotactic index greater than 60%;
[0022] (ii) about 3 parts to about 25 parts by weight, preferably
about 5 parts to about 20 parts, of a copolymer of ethylene and
propylene or a C.sub.4-C.sub.8 .alpha.-olefin that is insoluble in
xylene at ambient temperature; and
[0023] (iii) about 10 parts to about 80 parts by weight, preferably
about 15 parts to about 65 parts, of an elastomeric copolymer
selected from the group consisting of (a) ethylene and propylene,
(b) ethylene, propylene, and a C.sub.4-C.sub.8 .alpha.-olefin, and
(c) ethylene and a C.sub.4-C.sub.8 .alpha.-olefin, the copolymer
optionally containing about 0.5% to about 10% by weight of a diene,
and containing less than 70% by weight, preferably about 10% to
about 60%, most preferably about 12% to about 55%, of ethylene and
being soluble in xylene at ambient temperature and having an
intrinsic viscosity of about 1.5 to about 4.0 dl/g;
[0024] the total of (ii) and (iii), based on the total olefin
polymer composition being from about 50% to about 90%, and the
weight ratio of (ii)/(iii) being less than 0.4, preferably 0.1 to
0.3, wherein the composition is prepared by polymerization in at
least two stages;
[0025] (E) a thermoplastic olefin comprising:
[0026] (i) about 10% to about 60%, preferably about 20% to about
50%, of a propylene homopolymer having an isotactic index at least
80%, preferably 90-99.5% or a crystalline copolymer selected from
the group consisting of (a) ethylene and propylene, (b) ethylene,
propylene and a C.sub.4-C.sub.8 .alpha.-olefin, and (c) ethylene
and a C.sub.4-C.sub.8 .alpha.-olefin, the copolymer having a
propylene content greater than 85% and an isotactic index of
greater than 60%;
[0027] (ii) about 20% to about 60%, preferably about 30% to about
50%, of an amorphous copolymer selected from the group consisting
of (a) ethylene and propylene, (b) ethylene, propylene, and a
C.sub.4-C.sub.8 .alpha.-olefin, and (c) ethylene and a
.alpha.-olefin, the copolymer optionally containing about 0.5% to
about 10% of a diene, and containing less than 70% ethylene and
being soluble in xylene at ambient temperature; and
[0028] (iii) about 3% to about 40%, preferably about 10% to about
20%, of a copolymer of ethylene and propylene or an .alpha.-olefin
that is insoluble in xylene at ambient temperature; and
[0029] (F) mixtures thereof.
[0030] When an ethylene polymer material is used as the
non-irradiated and non-oxidized olefin polymer material or as the
starting material for making the irradiated, oxidized olefin
polymer of the present invention, the ethylene polymer material is
selected from the group consisting of (a) homopolymers of ethylene,
(b) random copolymers of ethylene and an alpha-olefin selected from
the group consisting of C.sub.3-10 alpha-olefins having a maximum
polymerized alpha-olefin content of about 20 wt %, preferably a
maximum of about 16 wt %, by weight, (c) random terpolymers of
ethylene and said alpha-olefins, provided that the maximum
polymerized alpha-olefin content is about 20 wt %, preferably the
maximum is about 16 wt %, by weight, and (d) mixtures thereof. The
C.sub.3-10 alpha-olefins include the linear and branched
alpha-olefins such as, for example, propylene, 1-butene,
isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene,
3,4-dimethyl-1-butene, 1-heptene, 3-methyl-1-hexene, 1-octene and
the like.
[0031] When the ethylene polymer is an ethylene homopolymer, it
typically has a density of 0.89 g/cm.sup.3 or greater, and when the
ethylene polymer is an ethylene copolymer with a C.sub.3-10
alpha-olefin, it typically has a density of 0.91 g/cm.sup.3 or
greater but less than 0.94 g/cm.sup.3. Suitable ethylene copolymers
include ethylene/butene-1, ethylene/hexene-1, ethylene/octene-1 and
ethylene/4-methyl-1-pentene. The ethylene copolymer can be a high
density ethylene copolymer or a short chain branched linear low
density ethylene copolymer (LLDPE), and the ethylene homopolymer
can be a high density polyethylene (HDPE) or a low density
polyethylene (LDPE). Typically the LLDPE and LDPE have densities of
0.910 g/cm.sup.3 or greater to less than 0.940 g/cm.sup.3 and the
HDPE and high density ethylene copolymer have densities of greater
than 0.940 g/cm.sup.3, usually 0.95 g/cm.sup.3 or greater. In
general, ethylene polymer materials having a density from 0.89 to
0.97 g/cm.sup.3 are suitable for use in the practice of this
invention. Preferably the ethylene polymers are LLDPE and HDPE
having a density from 0.89 to 0.97 g/cm.sup.3.
[0032] When a butene-1 polymer material is used as the
non-irradiated and non-oxidized olefin polymer material or as the
starting material for making the irradiated, oxidized olefin
polymer of the present invention, the butene-1 polymer material is
selected from a normally solid, high molecular weight,
predominantly crystalline butene-1 polymer material selected from
the group consisting of:
[0033] (1) a homopolymer of butene-1;
[0034] (2) a copolymer or terpolymer of butene-1 with a non-butene
alpha-olefin comonomer content of 1-15 mole %, preferably 1-10 mole
%; and
[0035] (3) mixtures thereof.
[0036] Typically the non-butene alpha-olefin comonomer is ethylene,
propylene, a C.sub.5-8 alpha-olefin or mixtures thereof.
[0037] The useful polybutene-1 homo or copolymers can be isotactic
or syndiotactic and have a melt flow rate (MFR) from about 0.5 to
150, preferably from about 0.5 to 100, and most preferably from 0.5
to 75 g/10 min.
[0038] These poly-1-butene polymers, their methods of preparation,
and their properties are known in the art. An exemplary reference
containing additional information on polybutylene-1 is U.S. Pat.
No. 4,960,820, the disclosures of which are incorporated herein by
reference.
[0039] Suitable polybutene-1 polymers can be obtained, for example,
by Ziegler-Natta low-pressure polymerization of butene-1, e.g. by
polymerizing butene-1 with catalysts of TiCl.sub.3 or
TiCl.sub.3--AlCl.sub.3 and Al(C.sub.2H.sub.5).sub.2Cl at
temperatures of 10-100.degree. C., preferably 20-40.degree. C.,
e.g., according to the process described in DE-A-1,570,353. It can
also be obtained, for example, by using TiCl.sub.4--MgCl.sub.2
catalysts. High melt indices are obtainable by further processing
of the polymer by peroxide cracking or visbreaking, thermal
treatment or irradiation to induce chain scissions leading to a
higher MFR material.
[0040] Preferably, the polybutene-1 contains up to 15 mole % of
copolymerized ethylene or propylene, but more preferably it is a
homopolymer, for example, Polybutene PB0300 homopolymer marketed by
Basell USA Inc. This polymer is a homopolymer with a melt flow of
11 g/10 min. at 230.degree. C. and 2.16 kg and a weight average
molecular weight of 270,000 dalton.
[0041] Preferably, the polybutene-1 homopolymer has a crystallinity
of at least 55% by weight measured with wide-angle X-ray
diffraction after 7 days. Typically the crystallinity is less than
70%, preferably less than 60%.
[0042] The non-irradiated, non-oxidized olefin polymer material and
the starting material for the irradiated and oxidized olefin
polymer material can be the same or different from each other.
[0043] The olefin polymer starting material for the irradiated,
oxidized olefin polymer is exposed to high-energy ionizing
radiation under a blanket of inert gas, preferably nitrogen. The
ionizing radiation should have sufficient energy to penetrate the
mass of polymer material being irradiated to the extent desired.
The ionizing radiation can be of any kind, but preferably includes
electrons and gamma rays. More preferred are electrons beamed from
an electron generator having an accelerating potential of 500-4,000
kilovolts. Satisfactory results are obtained at a dose of ionizing
radiation of about 0.1 to about 15 megarads ("Mrad"), preferably
about 0.5 to about 9.0 Mrad.
[0044] The term "rad" is usually defined as that quantity of
ionizing radiation that results in the absorption of 100 ergs of
energy per gram of irradiated material regardless of the source of
the radiation using the process described in U.S. Pat. No.
5,047,446. Energy absorption from ionizing radiation is measured by
the well-known convention dosimeter, a measuring device in which a
strip of polymer film containing a radiation-sensitive dye is the
energy absorption sensing means. Therefore, as used in this
specification, the term "rad" means that quantity of ionizing
radiation resulting in the absorption of the equivalent of 100 ergs
of energy per gram of the polymer film of a dosimeter placed at the
surface of the olefin material being irradiated, whether in the
form of a bed or layer of particles, or a film, or a sheet.
[0045] The irradiated olefin polymer material is then oxidized in a
series of steps. The first treatment step consists of heating the
irradiated polymer in the presence of a first controlled amount of
active oxygen greater than 0.004% by volume but less than 15% by
volume, preferably less than 8% by volume, more preferably less
than 5% by volume, and most preferably from 1.3% to 3.0% by volume,
to a first temperature of at least 25.degree. C. but below the
softening point of the polymer, preferably about 25.degree. C. to
140.degree., more preferably about 25.degree. C. to 100.degree. C.,
and most preferably about 40.degree. C. to 80.degree. C. Heating to
the desired temperature is accomplished as quickly as possible,
preferably in less than 10 minutes. The polymer is then held at the
selected temperature, typically for about 5 to 90 minutes, to
increase the extent of reaction of the oxygen with the free
radicals in the polymer. The holding time, which can be determined
by one skilled in the art, depends upon the properties of the
starting material, the active oxygen concentration used, the
irradiation dose, and the temperature. The maximum time is
determined by the physical constraints of the fluid bed.
[0046] In the second treatment step, the irradiated polymer is
heated in the presence of a second controlled amount of oxygen
greater than 0.004% by volume but less than 15% by volume,
preferably less than 8% by volume, more preferably less than 5% by
volume, and most preferably from 1.3% to 3.0% by volume to a second
temperature of at least 25.degree. C. but below the softening point
of the polymer. Preferably, the second temperature is from
100.degree. C. to less than the softening point of the polymer, and
greater than the first temperature of the first step. The polymer
is then held at the selected temperature and oxygen concentration
conditions, typically for about 90 minutes, to increase the rate of
chain scission and to minimize the recombination of chain fragments
so as to form long chain branches, i.e., to minimize the formation
of long chain branches. The holding time is determined by the same
factors discussed in relation to the first treatment step.
[0047] In the optional third step, the oxidized olefin polymer
material is heated under a blanket of inert gas, preferably
nitrogen, to a third temperature of at least 80.degree. C. but
below the softening point of the polymer, and held at that
temperature for about 10 to about 120 minutes, preferably about 60
minutes. A more stable product is produced if this step is carried
out. It is preferred to use this step if the irradiated, oxidized
olefin polymer material is going to be stored rather than used
immediately, or if the radiation dose that is used is on the high
end of the range described above. The polymer is then cooled to a
fourth temperature of about 70.degree. C. over a period of about 10
minutes under a blanket of inert gas, preferably nitrogen, before
being discharged from the bed. In this manner, stable intermediates
are formed that can be stored at room temperature for long periods
of time without further degradation.
[0048] The preferred method of carrying out the treatment is to
pass the irradiated polymer through a fluid bed assembly operating
at a first temperature in the presence of a first controlled amount
oxygen, passing the polymer through a second fluid bed assembly
operating at a second temperature in the presence of a second
controlled amount of oxygen, and then maintaining the polymer at a
third temperature under a blanket of nitrogen, in a third fluid bed
assembly. In commercial operation, a continuous process using
separate fluid beds for the first two steps, and a purged, mixed
bed for the third step is preferred. However, the process can also
be carried out in a batch mode in one fluid bed, using a fluidizing
gas stream heated to the desired temperature for each treatment
step. Unlike some techniques, such as melt extrusion methods, the
fluidized bed method does not require the conversion of the
irradiated polymer into the molten state and subsequent
re-solidification and comminution into the desired form. The
fluidizing medium can be, for example, nitrogen or any other gas
that is inert with respect to the free radicals present, e.g.,
argon, krypton, and helium.
[0049] As used in this specification, the expression "room
temperature" or "ambient" temperature means approximately
25.degree. C. The expression "active oxygen" means oxygen in a form
that will react with the irradiated olefin polymer material. It
includes molecular oxygen, which is the form of oxygen normally
found in air. The active oxygen content requirement of this
invention can be achieved by replacing part or all of the air in
the environment by an inert gas such as, for example, nitrogen.
[0050] The concentration of peroxide groups formed on the polymer
can be controlled easily by varying the radiation dose during the
preparation of the irradiated polymer and the amount of oxygen to
which such polymer is exposed after irradiation. The oxygen level
in the fluid bed gas stream is controlled by the addition of dried,
filtered air at the inlet to the fluid bed. Air must be constantly
added to compensate for the oxygen consumed by the formation of
peroxides in the polymer.
[0051] The irradiated, oxidized olefin polymer material of the
invention contains peroxide linkages that degrade during
compounding to form various oxygen-containing polar functional
groups, e.g., acids, ketones and esters. In addition, the number
average and weight average molecular weight of the irradiated,
oxidized olefin polymer is usually much lower than that of the
corresponding olefin polymer used to prepare same, due to the chain
scission reactions during irradiation and oxidation.
[0052] Preferably, the non-irradiated and non-oxidized olefin
polymer and the starting material for making the irradiated,
oxidized olefin polymer material is a propylene polymer material,
more preferably a propylene homopolymer having an isotactic index
greater than 80%.
[0053] Suitable additives include colorants, halogenated flame
retardants, anti-microbial agents, anti-acids, conductive carbon
black and mixtures thereof. Typically these additives have a
particle size of less than 5 micron.
[0054] In the additive-containing olefin polymer composition, the
additives can be present in an amount from 0.1 to 40 wt %,
preferably 0.1 to 30 wt %, more preferably 0.3 to 12%. The
irradiated, oxidized olefin polymer material can be present in an
amount from 2.0 to 30.0 wt %, preferably 2.0 to 25 wt %, more
preferably 2.0 to 20 wt %. The balance of the composition up to 100
wt % is the non-irradiated, non-oxidized olefin polymer
material.
[0055] When the additive is a colorant, the colorant is preferably
present in an amount from 0.1 to 5 wt %, more preferably 0.3 to 1.5
wt %. Typical examples include those organic or inorganic pigments
commonly used with polyolefins such as carbon black, titanium
oxide, graphite or color index (C.I.) pigment yellow series 62,
139, 151, 155, 169, 180, 181, 191, 194; C.I. pigment red series
122, 144, 149, 170, 175, 176, 185, 187, 209, 214, 242, 247, 262,
48:2, 48:3, 53:1, 57:1; C.I. pigment orange series 38, 43, 68, 72;
C.I. pigment violet series 19, 23; C.I. pigment blue series 15:1,
15:3, 15:4; C.I. pigment brown series 25 and 41, C.I. pigment green
series 7, and phthalocyanine blue. The irradiated, oxidized olefin
polymer material is preferably present in an amount from 2 to 30 wt
%, more preferably 2 to 20 wt %. The balance of the composition is
the non-irradiated, non-oxidized olefin polymer material.
[0056] When the additive is a halogenated flame retardant
composition, the flame retardant composition includes a halogenated
compound first component and a second component that interacts with
the halogenated compound to form an intermediate compound. The
halogenated compounds can include, for example, aliphatic,
cycloaliphatic and aromatic bromine or chlorine compounds, such as
tetrachlorobisphenol A, dibromopentaerythritol,
hexabromocyclododecane, octabromodiphenyl ether, decabromodiphenyl
ether (pentabromophenyl ether), hexabromobenzene,
poly(tribromostyrene), pentabromodiphenyl ether,
tribromophenyl-allyl ether, ethylene bis(tribromophenyl ether),
bis(dibromopropyl)ether of tetrabromobisphenol A,
tetrabromobisphenol A, tetrabromophthalic anhydride,
dibromoneopentylglycol, and poly(dibromophenylene oxide). The
second component can include compounds such as antimony trioxide,
boron compounds, tin oxide, zinc oxide, zinc borate, aluminum
trioxide, aluminum trihydroxide and mixtures thereof. The
halogenated compound first component is preferably present in an
amount from 2.0 to 30 wt %, more preferably from 2.0 to 20 wt %,
most preferably 2.0 to 10 wt %. The second component is preferably
present in an amount from 0.5 to 10 wt %, more preferably 0.5 to
7.0 wt %, most preferably 0.5 to 3 wt %. The irradiated, oxidized
olefin polymer material is preferably present in an amount from 2.0
to 30.0 wt %, more preferably 2 to 25 wt %, most preferably 2 to 20
wt %. The balance of the composition is the non-irradiated,
non-oxidized olefin polymer material.
[0057] Typical anti-acids include calcium stearate, hydrotalcite,
zinc stearate, calcium oxide, and sodium stearate. Typical
anti-microbial agents include compounds such as silver oxide.
[0058] The non-irradiated, non-oxidized olefin polymer material,
additives, and irradiated, oxidized olefin polymer material can be
combined at ambient temperature in conventional operations well
known in the art; including, for example, drum tumbling, or with
low or high speed mixers. The resulting composition is then
compounded in the molten state to disperse the additive in any
conventional manner well known in the art, in batch or continuous
mode; for example, by using a Banbury mixer, a kneading machine, or
a single or twin screw extruder. The material can then be
pelletized.
[0059] When producing an additive concentrate, the additive is
present in an amount from 9.0 to 85.0 wt %, preferably 9.0 to 40.0
wt %, more preferably 9 to 15 wt %. The balance of the composition
up to 100 wt % is the irradiated, oxidized olefin polymer
material.
[0060] When producing an additive concentrate where the additive is
a colorant, the colorant is preferably present in an amount from 10
to 70 wt %, more preferably 10 to 55 wt %. Suitable types of
colorants are as described above.
[0061] When producing an additive concentrate where the additive is
a halogenated flame retardant composition, the halogenated compound
first component is preferably present in an amount from 7.0 to 65
wt %, more preferably from 7.0 to 60 wt %. The second component is
preferably present in an amount from 2.0 to 20 wt %. The balance of
the concentrate is the irradiated, oxidized olefin polymer
material. Typical types of the first and second components of the
halogenated flame retardant composition are as described above.
[0062] The irradiated, oxidized olefin polymer material and
additives can be combined and compounded in the manner as described
above.
[0063] Unless otherwise specified, the properties of the olefin
polymer materials, compositions and concentrates that are set forth
in the following examples have been determined according to the
test methods set forth in Table I below.
1TABLE I Melt Flow ASTM D1238, units of dg/min Rate Propylene
polymer material: (230.degree. C.; 2.16 kg) ("MFR") Ethylene
polymer material: (190.degree. C.; 2.16 kg) Butene-1 polymer
material: (230.degree. C.; 2.16 kg) Colorant ASTM E1347 dispersion
testing Flammability Underwriters Laboratories Inc. UL-94 procedure
for testing vertical test burning Isotactic Defined as the percent
of olefin polymer insoluble Index, in xylene. The weight percent of
olefin polymer ("I.I.") soluble in xylene at room temperature is
determined by dissolving 2.5 g of polymer in 250 ml of xylene at
room temperature in a vessel equipped with a stirrer, and heating
at 135.degree. C. with agitation for 20 minutes. The solution is
cooled to 25.degree. C. while continuing the agitation, and then
left to stand without agitation for 30 minutes so that the solids
can settle. The solids are filtered with filter paper, the
remaining solution is evaporated by treating it with a nitrogen
stream, and the solid residue is vacuum dried at 80.degree. C.
until a constant weight is reached. These values correspond
substantially to the isotactic index determined by extracting with
boiling n-heptane, which by definition constitutes the isotactic
index of polypropylene. Peroxide Quantitative Organic Analysis via
Functional Groups, Concentration by S. Siggia et al., 4.sup.th Ed.,
NY, Wiley 1979, pp. 334-42
[0064] Unless otherwise specified, all references to parts,
percentages and ratios in this specification refer to percentages
by weight.
EXAMPLE 1
[0065] This example illustrates a general procedure for preparing
an irradiated, oxidized propylene polymer. A polypropylene
homopolymer having an MFR of 0.7 dg/min and I.I. of 95.6%
commercially available from Basell USA Inc. was irradiated at 0.5
Mrad under a blanket of nitrogen. The irradiated polymer was then
treated with 2.5% by volume of oxygen at 55.degree. C. for 60
minutes and then with 2.5% by volume of oxygen at 140.degree. C.
for an additional 60 minutes. The oxygen was then removed. The
polymer was then heated at 140.degree. C. under a blanket of
nitrogen for 90 minutes, cooled and collected. The MFR of the
resultant polymer material was 1300 dg/min. The peroxide
concentration was 28 mmol/kg of polymer.
EXAMPLE 2
[0066] An irradiated, oxidized propylene polymer was prepared from
a propylene homopolymer, commercially available from Basell USA
Inc., having an MFR of 0.12 and I.I. of 95.6% according to the
procedure of Example 1, except that the homopolymer was irradiated
at 1.0 Mrad. The irradiated polymer was then treated with 2.5% by
volume of oxygen at 60.degree. C. for 60 minutes and then with 2.5%
by volume of oxygen at 140.degree. C. for another 60 minutes. The
MFR of the resulting polymer material was 10000 dg/min.
EXAMPLE 3
[0067] An irradiated, oxidized propylene polymer was prepared from
a propylene homopolymer, commercially available from Basell USA
Inc., having an MFR of 0.12 and I.I. of 95.6% according to the
procedure of Example 2, except that the irradiated polymer was
treated with 1.8% by volume of oxygen at 60.degree. C. for 60
minutes and then with 1.8% by volume of oxygen at 140.degree. C.
for another 60 minutes. The MFR of the resulting material was 343
dg/min.
EXAMPLE 4
[0068] An irradiated, oxidized propylene polymer was prepared from
a propylene homopolymer, commercially available from Basell USA
Inc., having an MFR of 0.48 and I.I. index of 95.4%, according to
the procedure of Example 1, except that the irradiated polymer was
treated with 1.35% by volume of oxygen at 80.degree. C. for 5
minutes and then with 1.30% by volume of oxygen at 140.degree. C.
for another 60 min. The MFR of the resulting polymer material was
18 dg/min. The peroxide concentration was 8.2 mmole/kg of
polymer.
EXAMPLE 5
[0069] An irradiated, oxidized propylene polymer was prepared from
a propylene homopolymer, commercially available from Basell USA
Inc., having an MFR of 12.6 and I.I. of 95.0%, according to the
procedure of Example 1, except that the irradiated polymer was
treated with 1.60% by volume of oxygen at 80.degree. C. for 5
minutes and then with 1.60% by volume of oxygen at 140.degree. C.
for another 60 min. The MFR of the resulting polymer material was
310 dg/min. The peroxide concentration was 17.1 mmole/kg of
polymer.
EXAMPLE 6
[0070] An irradiated, oxidized propylene polymer was prepared from
a propylene homopolymer commercially available from Basell USA
Inc., having an MFR of 0.48 and I.I. of 95.4%, according to the
procedure of Example 1, except that the irradiated polymer was
treated with 3.0% by volume of oxygen at 80.degree. C. for 5
minutes and then with 3.0% by volume of oxygen at 140.degree. C.
for another 60 min. The MFR of the resulting polymer material was
2500 dg/min. The peroxide concentration was 61.0 mmole/kg of
polymer.
EXAMPLE 7
[0071] An irradiated, oxidized ethylene polymer was prepared from a
random copolymer of ethylene and butene, with a butene content of
9%, having an MFR of 2.1 dg/min and density of 0.916 g/cm.sup.3
commercially available from Haladia Petrochemicals LTD. The
copolymer was irradiated at 1.0 Mrad under a blanket of nitrogen.
The irradiated polymer was then treated with 5.0% by volume of
oxygen at ambient temperature for 60 minutes and then with 5.0% by
volume of oxygen at 110.degree. C. for an additional 60 minutes.
The oxygen was then removed. The polymer was then heated at
110.degree. C. under a blanket of nitrogen for 60 minutes, cooled
and collected. The MFR of the resultant polymer material was 7.9
dg/min.
EXAMPLE 8
[0072] An irradiated, oxidized propylene polymer was prepared from
a propylene homopolymer commercially available from Basell USA
Inc., having an MFR of 0.7 dg/min and I.I. of 95.6%, according to
the procedure of Example 1, except that the irradiated polymer was
then treated with 1.9% by volume of oxygen at 60.degree. C. for 60
minutes and then with 1.9% by volume of oxygen at 130.degree. C.
for an additional 60 minutes. The oxygen was then removed. The
polymer was then heated at 130.degree. C. under a blanket of
nitrogen for 90 minutes, cooled and collected. The MFR of the
resultant polymer material was 498 dg/min. The peroxide
concentration was 25 mmol/kg of polymer.
[0073] Unless otherwise indicated, all extrusion conditions were
conducted using a 1.5" Wayne single-screw extruder, commercially
available from Wayne Machine & Die Company, with a barrel
temperature of 232.2.degree. C. and a screw speed of 60 r.p.m.
[0074] Compositions were prepared using phthalocyanine green #7
(16-2024 PV Fast Green GNX), commercially available from Clariant
International Ltd., having a particle size of 50 nm, to evaluate
pigment dispersion efficiency in a propylene homopolymer using
various levels of irradiated, oxidized propylene polymer.
[0075] The compositions for Control Example 9 and Examples 10-16
are set forth in Table II.
2TABLE II Control Examples Ex. 9 10 11 12 13 14 15 16
Non-irradiated, non-oxidized 98.84 97.86 96.87 93.90 88.96 79.07
97.86 88.96 propylene homopolymer, wt % MFR = 12.6, I.I. = 95%
Irradiated, oxidized propylene 0.99 1.98 4.94 9.88 19.77 of Example
1, wt % Irradiated, oxidized propylene 0.99 9.88 of Example 3, wt %
Green#7, 16-2024 PV Fast 0.99 0.99 0.99 0.99 0.99 0.99 0.99 0.99
Green GNX, wt % Irganox B225 antioxidant.sup.1, 0.12 0.12 0.12 0.12
0.12 0.12 0.12 0.12 wt % Calcium stearate, wt % 0.05 0.05 0.05 0.05
0.05 0.05 0.05 0.05 .sup.1Irganox B225 is a blend of 1 part
Irganox-1010 stabilizer and 1 part Irgafos phosphite, commercially
available from Ciba Specialty Chemicals Corporation.
[0076] The color dispersion test results for Control Example 9 and
for Examples 10-16 are set forth in Table III.
3TABLE III Ex. L a b Delta L Delta a Delta b Control 26.503 -4.486
-3.558 Ex. 9 10 26.494 -4.456 -3.572 -0.009 0.03 -0.014 11 26.53
-4.545 -3.605 0.027 -0.059 -0.047 12 26.606 -4.736 -3.651 0.103
-0.25 -0.093 13 26.612 -4.849 -3.593 0.109 -0.363 -0.035 14 26.635
-5.038 -3.591 0.132 -0.552 -0.033 15 26.563 -4.536 -3.671 0.06
-0.05 -0.113 16 26.65 -4.85 -3.633 0.147 -0.364 -0.075
[0077] The degree of pigment dispersion was evaluated by comparing
the "Delta a" value of each sample relative to the Control, where a
more negative "Delta a" value indicates greener color. As is
evident from the data in Table III, the addition of the irradiated,
oxidized propylene polymer dispersants of this invention improved
the pigment dispersion over a range of concentrations.
[0078] Examples 17 to 38 demonstrate the use of the irradiated,
oxidized propylene polymer dispersants of this invention for
reducing pigment levels in a propylene polymer composition. In
these examples, a yellow shade red pigment (13-3415 Graphtol Red),
having a particle size of 125 nm, commercially available from
Clariant International Ltd. was used.
[0079] The compositions for Control Example 17 and Examples 18-23
are set forth in Table IV.
4TABLE IV Control Examples Ex. 17 18 19 20 21 22 23 Non-irradiated,
non-oxidized propylene 98.84 88.96 89.05 89.14 89.22 89.31 89.40
homopolymer, wt % MFR = 12.6, I.I. = 95%, wt % Irradiated, oxidized
propylene of 9.88 9.89 9.90 9.91 9.92 9.93 Example 1, wt % Yellow
shade red (13-3415 Graphtol 0.99 0.99 0.89 0.79 0.69 0.60 0.50 Red
LG), wt % Irganox B225 antioxidant.sup.1, wt % 0.12 0.12 0.12 0.12
0.12 0.12 0.12 Calcium stearate, wt % 0.05 0.05 0.05 0.05 0.05 0.05
0.05 .sup.1Irganox B225 is a blend of 1 part Irganox-1010
stabilizer and 1 part Irgafos phosphite, commercially available
from Ciba Specialty Chemicals Corporation.
[0080] The compositions for Examples 24-26 are set forth in Table
V.
5TABLE V Examples 24 25 26 Non-irradiated, non-oxidized propylene
88.96 89.14 89.40 homopolymer, wt %; MFR = 12.6, I.I. = 95%
Irradiated, oxidized propylene of Example 3, wt % 9.88 9.90 9.93
Yellow shade red (13-3415 Graphtol Red LG), wt % 0.99 0.79 0.50
Irganox B225 antioxidant.sup.1, wt % 0.12 0.12 0.12 Calcium
stearate, wt % 0.05 0.05 0.50 .sup.1Irganox B225 is a blend of 1
part Irganox-1010 stabilizer and 1 part Irgafos phosphite,
commercially available from Ciba Specialty Chemicals
Corporation.
[0081] The compositions for Examples 27-32 are set forth in Table
VI.
6TABLE VI Examples 27 28 29 30 31 32 Non-irradiated, non-oxidized
propylene 88.96 88.96 89.14 89.40 89.49 89.58 homopolymer, wt %;
MFR = 12.6, I.I. = 95% Irradiated, oxidized propylene of Example 1,
9.88 wt % Irradiated, oxidized propylene of Example 2, 9.88 9.90
9.93 9.94 9.95 wt % Yellow shade red (13-3415 Graphtol Red LG),
0.99 0.99 0.79 0.50 0.40 0.30 25%, wt % Irganox B225
antioxidant.sup.1, wt % 0.12 0.12 0.12 0.12 0.12 0.12 Calcium
stearate, wt % 0.05 0.05 0.05 0.05 0.05 0.05 .sup.1Irganox B225 is
a blend of 1 part Irganox-1010 stabilizer and 1 part Irgafos
phosphite, commercially available from Ciba Specialty Chemicals
Corporation.
[0082] The compositions for Control Example 33 and Examples 34-38
are set forth in Table VII.
7TABLE VII Con- trol Ex. Examples 33 34 35 36 37 38 Non-irradiated,
non- 98.84 93.90 94.09 94.37 94.46 94.56 oxidized propylene
homopolymer, wt % MFR = 12.6, I.I. = 95% Irradiated, oxidized 4.94
4.95 4.97 4.97 4.98 propylene of Example 1, wt % Yellow shade red
(13-3415 0.99 0.99 0.79 0.50 0.40 0.3 Graphtol Red LG), wt %
Irganox B225 antioxidant.sup.1, 0.12 0.12 0.12 0.12 0.12 0.12 wt %
Calcium stearate, wt % 0.05 0.05 0.05 0.05 0.05 0.05 .sup.1Irganox
B225 is a blend of 1 part Irganox-1010 stabilizer and 1 part
Irgafos phosphite, commercially available from Ciba Specialty
Chemicals Corporation.
[0083] The color dispersion test results for Control Example 17 and
Examples 18-26 are set forth in Table VIII.
8TABLE VIII Ex. L a b Delta L Delta a Delta b Control Ex. 17 42.738
43.649 28.255 18 43.443 45.057 29.429 0.705 1.408 1.174 19 43.368
44.854 29.321 0.63 1.205 1.066 20 43.222 44.821 29.255 0.484 1.172
1 21 43.212 44.629 29.24 0.474 0.98 0.985 22 43.158 44.463 29.133
0.42 0.814 0.878 23 42.847 43.945 28.779 0.109 0.296 0.524 24 43.38
44.975 29.38 0.642 1.326 1.125 25 43.406 45.064 29.492 0.668 1.415
1.237 26 43.119 44.229 29.112 0.381 0.58 0.857
[0084] The color dispersion test results for Control Example 33 and
Examples 27-32 and 34-38 are set forth in Table IX.
9TABLE IX Ex. L A b Delta L Delta a Delta b Control Ex. 33 44.55
47.42 30.96 27 44.72 47.58 31.25 0.17 0.16 0.29 28 45.07 48.68
32.00 0.52 1.26 1.04 29 44.54 47.55 31.04 -0.01 0.13 0.08 30 44.71
47.47 31.35 0.16 0.05 0.39 31 44.27 47.29 30.94 -0.28 -0.13 -0.02
32 43.89 46.34 30.27 -0.66 -1.08 -0.69 34 44.66 47.49 31.17 0.11
0.07 0.21 35 44.59 47.36 31.08 0.04 -0.06 0.12 36 44.29 46.86 30.75
-0.26 -0.56 -0.21 37 44.01 46.64 30.51 -0.54 -0.78 -0.45 38 43.92
46.17 30.30 -0.63 -1.25 -0.66
[0085] In the color measurements, higher "Delta a" values reflect a
richer red color relative to a propylene homopolymer control. As
shown by the data in Tables VIII and IX, the use of the irradiated,
oxidized propylene polymer dispersants of this invention permit a
reduction in the pigment level required to maintain a base color
intensity.
[0086] Compositions were prepared using Cabot 800 carbon black,
commercially available from Cabot Corporation, to evaluate
dispersion in a propylene homopolymer commercially available from
Basell USA Inc. A 25 mm Berstoff twin screw extruder commercially
available from Berstorff Ltd was used for compounding the
compositions.
[0087] The composition and extrusion conditions for Control Example
39 and Examples 40-43 are set forth in Table X.
10TABLE X Con- trol Ex. Examples 39 40 41 42 43 Non-irradiated,
non- 98.84 96.87 93.90 88.96 79.07 oxidized propylene homopolymer,
wt % MFR = 12.6, I.I. = 95% Irradiated, oxidized 1.98 4.94 9.88
19.77 propylene of Example 8, wt % Carbon Black, Cabot 0.99 0.99
0.99 0.99 0.99 800, wt % Irganox B225 antioxi- 0.12 0.12 0.12 0.12
0.12 dant.sup.1, wt % Calcium stearate, wt % 0.05 0.05 0.05 0.05
0.05 25 mm Berstorff extruder conditions: Barrel 232.2 232.2 232.2
232.2 232.2 temperature, .degree. C. Screw speed, r.p.m. 120 120
120 120 120 .sup.1Irganox B225 is a blend of 1 part Irganox-1010
stabilizer and 1 part Irgafos phosphite, commercially available
from Ciba Specialty Chemicals Corporation.
[0088] The color dispersion test results for Control Example 39 and
Examples 40-43 are set forth in Table XI.
11TABLE XI Ex. L a b Delta L Delta a Delta b Control Ex. 39 26.20
0.00 0.22 40 26.10 -0.02 0.09 -0.10 -0.02 -0.13 41 26.14 -0.04 0.02
-0.06 -0.04 -0.20 42 26.07 -0.07 -0.11 -0.13 -0.07 -0.33 43 25.94
-0.10 -0.28 -0.26 -0.10 -0.5
[0089] In the color measurements, a higher negative value for
"Delta L" reflects a richer black color relative to a propylene
homopolymer control. As shown by the data in Table XI, the use of
the irradiated, oxidized propylene polymer dispersants of this
invention provide improved color intensity for carbon black.
[0090] Compositions were prepared using pentabromophenyl ether and
antimony oxide, or Fryebloc flame retardant concentrate as flame
retardant additives. Fryebloc flame retardant concentrate,
commercially available from Great Lake Chemical Corporation, is a
flame retardant concentrate containing 60 weight % pentabromophenyl
ether, 20 weight % antimony oxide and 20 weight % of a carrier.
Irganox B225 antioxidant, a blend of 1 part Irganox-1010 stabilizer
and 1 part Irgafos phosphite, commercially available from Ciba
Chemical Specialties Company, was used as a processing stabilizer,
and calcium stearate was used as an acid scavenger.
[0091] All ingredients were dry-blended and compounded in a
co-rotating intermeshing Leistritz LSM 34 GL twin-screw extruder,
commercially available from American Leistritz Extruder Corp., USA.
Extrusion temperatures were at 230.degree. C. for all zones, with a
throughput of 11.34 kg/hr., and screw speed of 250 rpm. All
materials were injection-molded on a Battenfeld injection-molding
machine into flex bars with dimensions of 127 mm.+-.5 mm, by 13
mm.+-.0.5 mm, by 3.13 mm.+-.0.05 mm. Flammability tests were
conducted on the injection-molded material using Underwriters
Laboratories Inc. UL-94 procedure for vertical test burning. The
total burn time set forth in Tables XII-XVI represents the sum of
time that five individually tested flex bars burned.
[0092] The composition and flammability test results for Control
Example 44 and Examples 45-46 are set forth in Table XII.
12TABLE XII Control Examples Ex. 44 45 46 Non-irradiated,
non-oxidized propylene 96.5 86.9 91.7 homopolymer, wt %; MFR = 4.6,
I.I. = 95% Irradiated, oxidized propylene of 9.6 4.8 Example 6, wt
% Pentabromophenyl ether, wt % 2.4 2.4 2.4 Antimony (III) oxide, wt
% 0.8 0.8 0.8 Irganox B225 antioxidant, wt % 0.2 0.2 0.2 Calcium
stearate, wt % 0.1 0.1 0.1 Flammability Results: UL-94 flammability
test Fail V-2 V-2 Total burn time after 1.sup.st and 2.sup.nd -- 52
73 ignition (seconds)
[0093] The composition and flammability test results for Examples
47-49 are set forth in Table XIII.
13TABLE XIII Examples 47 48 49 Non-irradiated, non-oxidized
propylene 85.7 85.7 85.7 homopolymer, wt %; MFR = 4.6, I.I. = 95%
Fyrebloc 5DB-380Y9 concentrate, wt % 9 9 9 Irradiated, oxidized
propylene of Example 4, wt % 5 Irradiated, oxidized propylene of
Example 5, wt % 5 Irradiated, oxidized propylene of Example 6, wt %
5 Irganox B225 antioxidant, wt % 0.2 0.2 0.2 Calcium stearate, wt %
0.1 0.1 0.1 Flammability Results: UL-94 flammability test V-2 V-2
V-2 Total Burn time after 1.sup.st and 2.sup.nd ignition (seconds)
47 41 37 MFR, dg/min 6.4 7.3 25
[0094] As demonstrated by burn time data in the Tables XII and
XIII, increasing the oxygen-containing functionality and MFR of the
irradiated, oxidized propylene polymer dispersants of the
invention, or the concentration of same enhances the flame
retardancy of the compositions.
[0095] The composition and flammability test results for Control
Examples 50 and 53, and Examples 51-52 are set forth in Table
XIV.
14TABLE XIV Control Control Examples Ex. 50 51 52 Ex. 53
Non-irradiated non-oxidized 88.2 79.4 79.4 propylene homopolymer,
wt %; MFR = 12.6, I.I. = 95% Irradiated, oxidized 88.2 propylene of
Example 4, wt % Irradiated, oxidized 8.8 propylene of Example 5, wt
% Non-irradiated, non-oxidized, 8.8 propylene homopolymer, MFR =
400, I.I = 97.5%, wt % Pentabromophenyl ether, wt % 8.8 8.8 8.8 8.8
Antimony (III) oxide, wt % 2.7 2.7 2.7 2.7 Irganox B225
antioxidant, wt % 0.2 0.2 0.2 0.2 Calcium stearate, wt % 0.1 0.1
0.1 0.1 Flammability Results: UL-94 flammability test V-2 V-2 V-2
V-2 Total burn time after 63 16 33 49 1.sup.st and 2.sup.nd
ignition (seconds) MFR, dg/min 20 60 29 23
[0096] The burn time data in Table XIV shows that compositions
containing the irradiated, oxidized dispersants of the invention
enhanced the dispersion of the additives relative to the
controls.
[0097] The composition and flammability test results for Control
Examples 54-56 and Examples 57-59 are set forth in Table XV.
15TABLE XV Con- Con- Con- trol trol trol Ex. Ex. Ex. Examples 54 55
56 57 58 59 Non-irradiated, non- 96.5 92.3 89 86.8 83.1 80.1
oxidized, propylene homopolymer, wt % MFR = 12.6, I.I. = 95%
Irradiated, oxidized 9.7 9.2 8.9 propylene of Example 1, wt %
Pentabromophenyl ether, 2.4 5.5 8.0 2.4 5.5 8.0 wt % Antimony (III)
oxide, 0.8 1.9 2.7 0.8 1.9 2.7 wt % Irganox B225 0.2 0.2 0.2 0.2
0.2 0.2 antioxidant, wt % Calcium stearate, wt % 0.1 0.1 0.1 0.1
0.1 0.1 Flammability Results: UL-94 flammability test Fail V-2 V-2
V-2 V-2 V-2 Total burn time after 502 51 46 39 22 14 1.sup.st and
2.sup.nd ignition (seconds)
[0098] As is evident from the data in Table XV, Control Examples
54-56 and Examples 57-59 show that one can achieve a base flame
retardance performance level at a lower flame retardant
concentration using the irradiated, oxidized olefin polymer
dispersants of the invention.
[0099] Compositions were prepared using an NA960-000 low density
polyethylene, with a density of 0.919 and MFR of 0.9, commercially
available from Equistar Chemicals LP, pentabromophenyl ether and
antimony oxide. Irganox B225 antioxidant, a blend of 1 part
Irganox-1010 stabilizer and 1 part Irgafos phosphite, commercially
available from Ciba Chemical Specialties Company was used as a
processing stabilizer, and calcium stearate was used as an acid
scavenger. All ingredients were dry-blended and compounded in a
co-rotating intermeshing Leistritz LSM 34 GL twin-screw extrider,
commercially available from American Leistritz Extruder Corp., USA.
Extrusion temperatures were at 190.degree. C. for all zones, with a
throughput of 11.34 kg/hr., and screw speed of 250 rpm. All
materials were injection-molded on a Battenfeld injection-molding
machine into flex bars with dimensions of 127 mm.+-.5 mm, by 13
mm.+-.0.5 mm, by 3.13 mm.+-.0.05 mm. Flammability tests were
conducted on the injection-molded material using Underwriters
Laboratories Inc. UL-94 procedure for vertical test burning. The
total burn time set forth in Table XVI represents the sum of time
that five individually tested flex bars burned.
[0100] The compositions and flammability test results for Control
Example 60 and Example 61 are set forth in Table XVI.
16 TABLE XVI Control Examples Ex. 60 61 Non-irradiated,
non-oxidized 92.3 83.1 polyethylene.sup.1, wt % Irradiated,
oxidized ethylene of 9.2 Example 7, wt % Pentabromophenyl ether, wt
% 5.5 5.5 Antimony (III) oxide, wt % 1.9 1.9 Irganox B225
antioxidant, wt % 0.2 0.2 Calcium stearate, wt % 0.1 0.1
Flammability Results: UL-94 flammability test V-2 V-2 Total burn
time after 1.sup.st and 2.sup.nd 21 7 ignition (seconds)
.sup.1NA960-000.
[0101] As is evident from the burn time data of Table XVI, the
irradiated, oxidized ethylene polymer dispersant of the invention
improves the flame retardancy of the ethylene homopolymer
composition.
[0102] Other features, advantages and embodiments of the invention
disclosed herein will be readily apparent to those exercising
ordinary skill after reading the foregoing disclosures. In this
regard, while specific embodiments of the invention have been
described in considerable detail, variations and modifications of
these embodiments can be effected without departing from the spirit
and scope of the invention as described and claimed.
* * * * *