POLYMER COMPOSITIONS COMPATIBILIZED WITH STYRENE BLOCK COPOLYMERS AND ARTICLES PRODUCED THEREFROM

COMPOSITIONS POLYMERIQUES RENDUES COMPATIBLES A L'AIDE DE COPOLYMERES A SEQUENCE DE STYRENE; ARTICLES OBTENUS A PARTIR DE CES COMPOSITIONS

English Abstract

FERO-971(CIP)

Title: POLYMER COMPOSITIONS COMPATIBILIZED WITH STY-
RENE BLOCK COPOLYMERS AND ARTICLES PRODUCED
THEREFROM

Abstract of the Disclosure
Blended polymer compositions are described
which comprise (A) an olefin polymer, (B) at least one
second polymer having a glass transition temperature
greater than the glass transition temperature of olefin
polymer (A) such as: copolymers and terpolymers of
styrene and maleic anhydride or a maleimide; polystyrene
blended with a polyarylene ether, and optionally an
elastomer; blends or reaction products of styrene-maleic
anhydride or maleimide copolymers or terpolymers with
elastomers; polycarbonates, etc., and (C) at least one
compatibilizing agent selected from the group consisting
of various block copolymers of vinyl aromatic compounds
and conjugated dienes, and their partially hydrogenated
derivatives.
The blended polymer compositions of the present
invention can be extruded, coextruded, thermoformed,
blow-molded, injection-molded, compression-molded, calen-
dered, laminated, foamed, stamped, pultruded, or extru-
sion die coated onto a continuous fiber to form shaped
articles useful in a variety of applications. The com-
patibilized and blended polymer compositions of the
present invention exhibit excellent heat distortion
properties as well as excellent strength, toughness,
stiffness, gloss, ease of processing and forming, improv-
ed filler interaction, hardness, adherability and shrink-
age characteristics and they are retortable and micro-
waveable.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:


1. A polymer composition comprising:
(a) from 1% by weight to 99% by weight polypropylene;
(b) from 1% by weight to 99% by weight of a copolymer of
styrene and maleic anhydride; and
(c) from 1% by weight to 15% by weight of a
compatibilizing agent comprising a multiblock styrene-
butadiene copolymer.

2. A polymer composition as set forth in Claim 1, wherein said
polypropylene comprises a homopolymer of polypropylene.



3. A polymer composition s set forth in Claim 1, wherein said
polypropylene comprises a copolymer of polypropylene.



4. A polymer composition as set forth in Claim 1, wherein said
multiblock copolymer comprises from 40% to 75% by weight styrene.



5. A copolymer composition as set forth in Claim 1, wherein
said composition further includes:
(a) at least one filler, fibre or mixture thereof.




6. A polymer composition as set forth in Claim 5, wherein said
filler is talc or calcium carbonate and said fibre is a glass
fibre.


7. A polymer composition as set forth in Claim 1, wherein said
composition comprises from 49% by weight to 90% by eight of said
polypropylene, from 10% by weight to 30% by weight of said
copolymer of styrene and maleic anhydride, and from 2% by weight
to 10% by weight of said multiblock styrene-butadiene copolymer.

Description

POLYMER COMPOSITIONS COMPATIBILIZED WITH STYRENE
BLOCK COPOLYMERS AND ARTICLES PRODUCED THEREFROM




Back~round of the Invention
Field of the Invention
This invention relates generally to compatibil-
izing two or more incompatible polymer systems. The
invention also relates to compounded, compatibilized
polyolefin-styrene copolymer or polymeric blend composi-
tions and articles of manufacture produced therefrom.
State of the Art
Polymeric blends have been known for years.
Typically, blends of polymers result in a material which
combines the poorest properties of the constituents.
This is a result of the incompatibility of the constitu-
ent polymers resulting in little, if any, adhesion at
the interface between the different constituent poly-
mers. Furthermore, this incompatibility stems in part
from the structure of the individual polymers. Thermo-
dynamically, one polymeric phase has more of an affinity
for itself than for the other polymeric phase so that




`~ !,

t~ r'~
-2-

intermolecular forces between the two polymers are weak.
For example, a b]end of a polar polymer ar.d a non-polar
polymer would result in an incompatible system demon-
strating poor physical properties for lack of wetting
and adhesion at the interface. Even in cases when the
polarity of the polymers in a blend is similar, compat-
ibility is generally not achieved because the entropy
change upon mixing of high polymers is not favorable.
Such incompatibility problems may be overcome
through the use of a compatibilizing agent. A compat-
ibilizing agent is a materi~l which, on a molecular
scale, has particular regions which are compatible with
each of the incompatible constituent polymers. Such
compatibilizing agents typically surround one polymeric
phase providing a chemical and/or physical bridge to the
other polymeric phase. Insomuch as portions of the
compatibilizing aqent are compatible with each of the
constituent polymers, the bonding between the two incom-
patible polymeric phases is effectively enhanced through
this intermediate compatibilizing phase. Such a system
of incompatible polymers coupled by a compatibilizing
agent results in a material which advantageously com-
bines the more desirable properties of the constituent
polymers. Lindsey et al, J. Appl. Polymer Sci., Vol.
26, 1-8 (1981) describe a method of reclaiming mixed
immiscible polymers by employing a compatibilizing
agent. The system studied was a high density polyethyl-
ene (HDPE) and polystyrene (PS) and a styrene-ethylene-
butene-1-styrene (SEBS3 copolymer (a linear triblock
copolymer) as the compatibilizing agent. These ternary
blends exhibited a considerable improvement in the
balance of mechanical properties over a binary blend of
high density polyethylene and polystyrene.

200~695


sartlett et al, Modern Plastics, Dec. 1981,
60-62 describes a system comprising polypropylene, poly-
styrene and styrene-ethylene-butene-1-styrene as a com-
patibilizer. This work focused on those parameters that
affected the extent of the polypropylene crystallinity.
Polystyrene homopolymers and copolymers compat-
ibilized with polyolefins have been available for sever-
al years. Furthermore, molded articles have been pro-
duced from such compatibilized polymer compositions.
For example, U.S. Patent Nos. 4,386,187 and 4,386,188
disclose a thermoformable polymer blend of a polyolefin,
a styrene polymer and styrenic diblock and triblock
copolymer rubbers. While a number of styrene polymers
and copolymers are disclosed, a copolymer of styrene and
maleic anhydride is not.
U.S. Patent 4,647,509 discloses a multilayer
thermoformable packaging material comprising a first
layer of (a) a vinylidene chloride polymer, (b) an
incompatible polymer, e.g., polyesters and nylons, and
(c) a compatibilizing agent, and a second layer of (a) a
blend of an olefin polymer, a styrenic polymer, and a
compatibilizing polymer, and (b) scrap material produced
from the first and second layers. The compatibilizing
polymers for the second layer are preferably block
copolymers of olefins and styrene such as copolymers of
styrene-butadiene, styrene-butadiene-styrene, styrene-
isoprene, etc.
U.S. Patent 4,107,130 discloses a multicompon-
ent polymer blend comprised of a polyolefin, a selective-
ly hydrogenated monoalkenyl arene-diene block copolymer,
and at least one dissimilar engineering thermoplastic
resin.

Summary of the Invention
Blended polymer compositions are described which
comprise (A) an olefin polymer, (B) at least one second polymer
having a glass transition temperature greater than the glass
transition temperature of olefin polymer (A) such as: copolymers
and terpolymers of styrene and maleic anhydride or a maleimide;
polystyrene blended with a polyarylene ether, and optionally an
elastomer; blends or reaction products of styrene-maleic
anhydride or maleimide copolymers or terpolymers with elastomers;
polycarbonates, etc., and (C) at least one compatibilizing agent
selected from the group consisting of various block copolymers
of vinyl aromatic compounds and conjugated dienes and/or their
partially hydrogenated derivatives.
The blended polymer compositions of the present
invention can be extruded, coextruded, thermoformed, compression
molded, blow-molded, injection-molded, calendered, laminated,
stamped, pultruded, foamed, or extrusion die coated onto
continuous fibres, to form shaped articles useful in a variety
of applications. The compatibilized and blended polymer
compositions of the present invention exhibit excellent heat
distortion properties as well as excellent strength, toughness,
stiffness, gloss, ease of processing, improved filler
interaction, hardness, adherability and shrinkage character-
istics, and they are retortable and microwaveable.
In a broad aspect, the present invention relates to a
polymer composition comprising: (a) from 1% by weight to 99% by
weight polypropylene; (b) from 1% by weight to 99% by weight of
a copolymer of styrene and maleic anhydride; and (c) from 1% by
weight to 15% by weight of a compatibilizing agent comprising a
multiblock styrene-butadiene copolymer.
Description of the Preferred Embodiments
The novel blended polymer compositions of the present
invention comprises a mixture of two or more polymers and a
compatibilizing agent as described in more detail herein. An
essential component of the blended polymer compositions of the
present invention is at least one olefin polymer.

2(:~02695

--5--

(A) The Olefin PolYmers.
The olefin polymers employed in the blends of
the present invention generally are semi-crystalline or
crystallizable olefin polymers including homopolymers,
copolymers, terpolymers, or mixtures thereof, etc.,
containing one or more monomeric units. Polymers of
alpha-olefins or 1-olefins are preferred in the present
invention, and these alpha-olefins may contain from 2 to
about 20 carbon atoms. Alpha-olefins containing 2 to
about 6 carbon atoms are preferred. Thus, the olefin
polymers may be derived from olefins such as ethylene,
propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,
1-octene, 1-decene, 4-ethyl-1-hexene, etc. Examples of
particularly useful olefin polymers include low-density
polyethylene, high-density polyethylene, linear low
density polyethylene, ultra low density polyethylene,
polypropylene, (high and low density) poly(1-butene),
ultra low molecular weight polyethylene, ethylene-based
ionomers, poly(4-methyl-1-pentene), ethylene-propylene
copolymers, ethylene-propylene-diene copolymers (EPDM)
copolymers of ethylene and/or propylene with other
copolymerizable monomers such as ethylene-1-butylene
copolymer, ethylene-vinyl acrylate copolymer, ethylene-
ethyl acetate copolymer, propylene-4-methyl-1-pentene
copolymer, ethylene-vinyl acetate, ethylene vinyl alco-
hol, ethylene-methyl acrylate-acrylic acid terpolymers,
etc. Halogenated olefins, polymers and copolymers may
also be used in this invention.
Olefin polymers having a semi-crystalline or
crystallizable structure are particularly useful in the
present invention since such polymers are capable of
forming a continuous structure with the other polymers
in the polymer blend of the present invention. The

Z0026~3Si


number average molecular weight of the polyolefins is
preferably above about 10,000 and more preferably above
about 50,000. In addition, it is preferred in one
embodiment that the apparent crystalline melting point
be above about 75C and preferably between about 75C
and about 250C. Most commercial polyethylenes have a
number average molecular weight of from about 50,000 to
about 500,000. The olefin polymers useful in preparing
the polymer blends of the present invention are well-
known to those skilled in the art and many are available
commercially. The olefin polymers may be homopolymers,
impact copolymers, block copolymers, random copolymers,
thermoplastic olefinic elastomers (TPO), etc., or
mixtures thereof. Polyethylene and polypropylene are
preferred olefin polymers, and polypropylelles such as
Himont's Profax 6523 (homopolymer) and Shell's 7C06 or
Exxon's PD7132 or Aristich's 4040F (polypropylene-ethyl-
ene copolymers) are particularly preferred.
(B) Hiqher Glass Transition TemPerature Second PolYmer.
The second polymer in the blended polymer compo-
sitions of the present invention is at least one polymer
having a glass transition temperature which is greater
than the glass transition temperature of the olefin poly-
mer (A). Generally, the glass transition temperature of
the second polymer will be above about 75C.
(B-1) CopolYmers of VinYl Aromatic ComPounds and Unsat-
urated DicarboxYlic Acid Anhydrides Imides. Metal
Salts or Partial Esters of the DicarboxYlic Acids.
A particularly preferred second polymer in the
blended polymer compositions of the present invention is
at least one copolymer of a vinyl aromatic compound and
unsaturated dicarboxylic acid anhydrides, imides, metal
salts and partial esters. Copolymers of a vinyl aroma-

2002695


tic compound and maleic anhydride, N-substituted male-
imide, metal salts or partial esters of maleic acid
derivatives are particular examples.
The vinyl aromatic compounds include styrene
and the various substituted styrenes which is represent-
ed by the following formula

R&=C~2
~Z)p

wherein R is hydrogen, an alkyl group containing from 1
to about 6 carbon atoms, or halogen; Z is a member sel-
ected from the group consisting of vinyl, halogen and
alkyl groups containing from 1 to about 6 carbon atoms;
and p is a whole number from 0 up to the number of
replaceable hydrogen atoms on the phenyl nucleus. Speci-
fic examples of vinyl aromatic compounds such as repre-
sented by the above formula include, for example, in
addition to styrene, alpha-methyl styrene, beta-methyl
styrene, vinyl toluene, 3-methyl styrene, 4-methyl sty-
rene, 4-isopropyl styrene, 2,4-dimethyl styrene, o-
chloro styrene' p-chloro styrene, o-bromo styrene,
2-chloro-4-methyl styrene, etc. Styrene is the prefer-
red vinyl aromatic compound.
The maleic anhydride and maleimide derivative
compounds utilized in the formation of the copolymers
with vinyl aromatic compounds may generally be
represented by the formula

R-C--C
Il \X
R-C--C. ~

2002695


wherein each R group is hydrogen or an aliphatic or
aromatic hydrocarbyl group or the two R groups are
joined together to form a fused ring derivative, X is
-O- or >NR2 where R2 is a hydrocarbyl group which
may be an aliphatic or an aromatic hydrocarbyl group
such as phenyl, methyl, ethyl, propyl, butyl, etc.
Preferably both R groups are hydrogen.
Examples of maleic derivatives which are cyclic
or bicyclic compounds include
~C~'



obtained by a Diels-Alder reaction of butadiene with
maleic anhydride or a maleimide

~ C~



obtained by a Diels-Alder reaction of cyclopentadiene
with maleic anhydride or maleimide, and

CH3 /~
¢L~/X




~0

2002695

g

obtained by a Diels-Alder reaction of isoprene with
maleic anhydride or an N-substituted maleimide male-
imide. These cyclic or bicyclic derivatives have high
glass transition temperatures.
Copolymers comprising a vinyl aromatic compound
and metal salts of maleic acid also are useful as the
second polymer in the blended polymer compositions of
the present invention. The metals present in the metal
salt of maleic acid may be Group I metals, Group II
metals or transition metals. Alkali metals and transi-
tion metals are preferred. Partial esters of the unsat-
urated anhydrides also can be used. These can be obtain-
ed, for example, by reacting or esterifying, maleic acid
or maleic anhydride with less than one equivalent of an
alcohol such as methanol, ethanol, propanol, etc.
The copolymers of the vinyl aromatic compounds
with maleic anhydride, N-substituted maleimides or metal
salts of maleic acid are obtained, in one embodiment, by
polymerizing equimolar amounts of styrene and the core-
actant, with or without one or more interpolymerizablecomonomers. In another embodiment, substantially homo-
geneous copolymers of styrene with maleic anhydride or
maleimide or metal salts of maleic acid can be obtained
by (1) heating a vinyl aromatic compound to a tempera-
ture at which the vinyl aromatic compound with polymer-
ize, (2) stirring the polymerizing vinyl aromatic com-
pound while (3) adding maleic anhydride, maleimide, or
the metal salt of maleic acid, or mixtures thereof at a
continuous and uniform rate. Generally, the addition of
the maleic anhydride, maleimide, or metal salts or
esters of maleic acid is made at a rate in moles per
unit time that is slower than the rate, in moles per
unit time at which the vinyl aromatic compound is poly-


- 1 o -

merizing. Procedures for preparing such copolymers are
known in the art and have been described in, for exam-
ple, U.S. Patent 2,971,939.
In one embodiment, the styrene-maleic anhydride
copolymers are preferred second polymers in the blended
polymer compositions of the present invention. The
styrene-maleic anhydride copolymers (SMA) are available
commercially from, for example, ARCO under the general
trade desi~nation Dylark. Examples include: Dylark
DsK-290 reported to comprise about 18% by weight of
maleic anhydride and about ~2% by weight of styrene;
Dylark 332 reported to comprise about 14% by weight of
maleic anhydride and 8~% by weight of styrene; and
Dylark 134 reported to comprise about 17% by weight of
maleic anhydride, the balance being styrene.
Other Dylark materials available include trans-
parent grades: Dylark* 132 (Vicat 109C), Dylark*232
(Vicat 123C), and Dylark* 332 (Vicat 130C). Impact
grades include Dylarks* 150, 250, 350 and 700 which are
believed to be blends and/or grafts of SMA with SBR.
Other examples of impact modified styrenic and
alpha-methyl styrene copolymers with maleic anhydride
and acrylonitrile include Arvyl*300 MR and 300 C~.
Low molecular wei~ht styrene-maleic anhydride
copolymers (Mw as low as 1500) also are useful and these
are available commercially such as from Monsanto under
the designation "Scripset"* and from Atochem under the
designation "SMA Resins". Sulfonated styrene-maleic
anhydride copolymers (and their metal salts) also are
available and useful in this invention. Two such pro-
ducts are available from Atochem:SSMA-1000 which is a
sulfonated copolymer of about 50% styrene and 50% maleic
anhydride; and SSMA 3000, a sulfonated SMA comprising
about 75% styrene and 25% maleic anhydride.
* Denotes Trade Mark

;

200Z69S


(B-2) TerpolYmers of Vinyl Aromatic ComPounds, ~nsatur-
ated DicarboxYlic Acid Anhvdrides, Imides Metal Salts
or Partial Esters of the Dicarboxvlic Acids, and CoPolY-
merizable Unsaturated Monomers.
The terpolymers useful in the present invention
comprise (1) a vinyl aromatic compound as described
above, (2) unsaturated dicarboxylic acid anhydrides,
imides, metal salts or partial esters as described
above; and (3) copolymerizable monomers. Examples of
copolymerizable monomers used to form the above-describ-
ed terpolymers include acrylic acid alkyl-substituted
acrylic acids, acrylic esters and alkyl-substituted
acrylic esters containing from 1 to 4 carbon atoms in
the ester moiety, acrylonitriles, and mixtures thereof.
Acrylates and methacrylates are preferred comonomers.
Examples of such comonomers include methy' acrylate,
ethyl acrylate, butyl acrylate, methyl methacrylate.
Other vinyl monomers can be utilized as the comonomers,
and these include vinyl acetate, vinyl methyl ether,
vinyl ethyl ether, vinyl chloride, isobutene, etc.
In one embodiment, the terpolymers comprise
about 45 to 83% (preferably 50 or 60 to 75%) by weight
of the vinyl aromatic monomer, from 15 to 35% (prefer-
ably 20-30%) by weight of an unsaturated dicarboxylic
acid anhydride and from 2 to about 20% (preferably 4-
10%) by weight of a C1_3 alkyl methacrylate ester.
Terpolymers of this type are available commercially from
Monsanto.
(B-3) Blends or Reaction Products of Elastomers and the
Co~olymer of (B-1) or Terpolymer of (B-2).
The second polymer utilized in the blended
compositions of the present invention may comprise a
blend or reaction product of an elastomer and the

-12--

copolymer of (s-1~ or the terpolymer of ~B-2) described '~
above. The elastomers utilized in this embodiment may
be polybutadienes, isobutylene-isoprene copolymers,
styrene butadiene copolymers, butadiene-acrylonitrile
copolymers, ethylene-propylene copolymers, polyiso-
prenes, ethylene-propylene diene monomer terpolymers
(EPDM), etc. Particularly preferred elastomers are the
so-called "high-cis" diene rubbers which contain at
least 90% by weight of cis-1,4-polybutadiene units. The
preferred rubbers generally have a Tg of less than
-20C.
The polymer component (B-3) may comprise blends
of the elastomers and the copolymers or terpolymers or
the elastomer may be grafted into the copolymer or
terpolymer. Alternatively, the polymer component (B-3)
may comprise a polymer wherein the elastomer is both
blended and grafted into the copolymer or terpolymer. A
typical method of preparinq the elastomer modified graft
copolymers is found in U.S. Patent 3,9l9,354. Elastomer-
modified styrenic terpolymers such as the terpolymers (B-2)
are described in U.S. Patent 4,341,695.

The amount of elastomer incorporated into the
blends or grafts of this embodiment may be up to about
50% by weight of elastomer in the total blend or graft.
Elastomer-modified graft vinyl aromatic maleic anhydride
copolymers are available commercially from ARCO Polymers
Inc. (ARCO) under the general designations Dylark and
Arvyl. Examples of such elastomer-modified copolymers
include Dylark DKB-218 which is reported to comprise
about 10~ by weight of elastomer in the total graft
copolymer, 17~ by weight of maleic anhydride and 83% by


weight of styrene in the resin phase; Dylark 338S
reported to comprise 4% by weight of elastomer in the
total graft copolymer, and 14~ by weight of maleic
anhydride and 86% by weight of styrene in the resin
phase; Dylark 350 reported to comprise 15% by weight of
rubber in the total graft polymer and 13% by weight of
maleic anhydride and 87~ by weight of styrene in the
resin phase.
Blends or reaction products of SMA copolymers
and polybutylene terephthalate (PBT) (50:50) are useful,
and these are available from Arco under the general
designation Dylark DPN-500 series. Blends of SMA with
polycarbonates are available under the designation
Arloy.*~
Blends or reaction products of elastomers with
terpolymers (B-2) also are available from the Monsanto
Chemical Company under the general trade designation
"Cadon".* Cadon*is reported to be a blend of a reaction
product of polybutadiene with a styrene:maleic anhy-
dride:methyl methacrylate terpolymer.
(B-4) Blends Com~risinq a Polvmer of a VinYl Aromatic
ComPound and a PolYarvlene Ether and, OPtionallY an
Elastomer.
Blends comprising a polymer of a vinyl aromatic
compound and a polyarylene ether are also useful as the
second polymer in the blended polymer compositions of
the present invention. Among the preferred polyarylene
ethers are polyphenylene ethers which may be represented
by the following formula
R~ R1

n
R1 R1
* Denotes Trade Mark

-14-

wherein the oxygen ether atom of one unit is connected
to the phenyl nucleus of the next adjoining unit; each
R1 is independently a monovalent substituent selected
from the group consisting of hydrogen, halogen, hydro-
carbon groups free of a tertiary alpha-carbon atom,
halohydrocarbon groups having at least 2 carbon atoms
between the halogen atom and the phenyl nucleus and also
being free of a tertiary alpha-carbon ator.l, hydrocarbon-
oxy groups free of aliphatic, tertiary alpha-carbon
atoms and halohydrocarbonoxy groups containing at least
2 carbon atoms between the halogen atom and the phenyl
nucleus and being free of an aliphatic, tertiary alpha-
carbon atom; n is an integer of at least about 50 such
as from about 50 to about 800 and preferably from about
100 to about 300. Such polyarylene ethers may have mole-
cular weights in the range of between 1000 and 100,000
and more preferably between about 6000 and 100,000. A
preferred example of a polyarylene ether is poly(2,6-di-
methyl-1,4-phenylene)ether. Examples of polyphenylene
ethers useful in the blended polymer compositions of the
present invention and methods for their preparation are
described in, for example, U.S. Patents 3,306,874;
3,306,875; 3,257,357; and 3,257,358,

Typical styrene polymers which can be blended
or reacted with the polyphenylene ethers include, for
example, homopolymers such as polystyrene and polychloro-
styrene, modified polystyrenes such as rubber-modified
polystyrenes (high impact styrenes) and the styrene-
containing copolymers such as the styrene-acrylonitrile
copolymers (SAN), styrene-butadiene copolymers, styrene-
acrylonitrile-alpha-alkyl styrene copolymers, styrene-


c~r; . I

2002695


acrylonitrile-butadiene copolymers (ABS), poly-alpha-
methyl styrene, copolymers of ethyl vinyl benzene and
divinyl benzene, etc.
Blends of styrene resins with these polyarylene
ethers such as polyphenylene ethers are particularly
useful in this invention and are available commercially.
Eor example, blends comprising polystyrene and poly-
phenylene ether typically containing from about 25 to
about 50~ by weight of polystyrene units are commercial-
ly available from the General Electric Company under thetradename NORYL~ thermoplastic resin. The molecular
weight of such blends may range from about 10,000 to
about 50,000 and more often will be about 30,000.
The elastomers which may be included in the
blends of or reacted with the polymer of a vinyl aroma-
tic compound and a polyarylene oxide include the
elastomers described above with respect to polymer type
(B-3)-
(B-5) Co~olYmers and TerpolYmers of a Vinvl Aromatic
Com~ound With an AcrYlic Ester and/or AlkYl-Substituted
Acrylic Ester.
The second polymer utilized in the blended
polymer compositions of the present invention may com-
prise terpolymers of a vinyl aromatic compound with an
acrylic ester and/or an alkyl-substituted acrylic ester.
Vinyl aromatic compounds such as those described above
and including styrene and substituted styrenes may be
utilized in the preparation of these particular copoly-
mers. The acrylic ester and alkyl-substituted acrylic
esters useful in preparing these polymers include esters
characterized by the following formula

CH2=C(Rl)COOR2

-16-

wherein R1 is hydrogen, a lower alkyl group containing
from 1 to 4 carbon atoms, or a halogen; and R2 is a
lower alkyl group containing from 1 to about 4 carbon
atoms. Specific e~amples of esters characterized by the
above Formula I include methyl acrylate, ethyl acrylate,
butyl acrylate, methyl methacrylate, ethyl methacrylate,
ethyl ethacrylate, etc.
The polymers of a vinyl aromatic compound such
as styrene with an acrylic ester and/or an alkyl-substi-
tuted acrylic ester can be prepared by procedures well-
known to those skilled in the art. The mole ratio of
vinyl aromatic compound to acrylic ester and/or alkyl-
substituted ester may vary over a wide range such as
from about 10:90 to about 90:10. Such terpolymers are
available commercially from CYRO under the designations
"XT* Polymer Series" and "Cyrolite G-Series". These
terpolymers are referred to as acrylic-based multipoly-
mer products. They are believed to be terpolymers of
styrene, methyl methacrylate and ethyl acrylate. Some
of the products may be impact modified with polybuta-
diene during copolymerization.
Other acrylic based multipolymer products are
available from Polysar under the designation "Zylar*
90". This product is believed to comprise styrene,
butadiene and methyl methacrylate.
(B-6) Product of the Reaction of an Alpha~Beta-Olefinic-
allY _Unsaturated Carboxvl c Reaaent and a Hvdroqenated
Block CoPolvmer.
Also useful in the blended polymer compositions
of the present invention are polymeric products of the
reaction of an alpha,beta-olefinically unsaturated car-
boxylic reagent in a hydrogenated block copolymer of a
vinyl aromatic compound and an aliphatic conjugated
* Denotes Trade Mark
Bl-

200Z695
-17-

diene. The hydrogenated block copolymers of a vinyl
aromatic compound and an aliphatic conjugated diene may
be either normal block copolymers (true block copoly-
mers) or random block copolymers, although the normal
block copolymers are preferred. The vinyl-substituted
aromatic compounds generally contain from about 8 to
about 12 carbon atoms and preferably about 8 or 9 carbon
atoms. Examples of such vinyl aromatic compounds
include styrene and the various substituted styrenes
described above. The conjugated dienes used to form the
block copolymers generally contain from about 4 to about
carbon atoms, and preferably from 4 to about ~ carbon
atoms. Examples of such conjugated dienes include a
2,3-dimethyl-1,3-butadiene, chloroprene, isoprene, and
1,3-butadiene. Isoprene and 1,3-butadiene are particu-
larly preferred, and mixtures of such conjugated dienes
may be used.
The normal block copolymers have a total of
from 2 to about 5, and preferably 2 or 3 polymer blocks
of the vinyl-substituted aromatic and the conjugated
diene, with at least one polymer block of said vinyl-sub-
stituted aromatic and at least one polymer block of said
conjugated diene being present. The vinyl substituted
aromatic content of these copolymers is in the range of
from about 20% to about 70% by weight and preferably
from about 40~ to about 60% by weight. The block copoly-
mers can be prepared by conventional methods well-known
to those in the art, and these copolymers usually are
prepared by anionic polymerization using, for example,
an alkali metal hydrocarbon such as sec-butylithium as a
polymerization catalyst.
The block copolymers of the vinyl aromatic
compound and a conjugated diene are hydrogenated prior

2002~95
-18-

to reaction with the olefinically unsaturated carboxylic
acid to remove virtually all of the olefinic double
bonds. Techniques for accomplishing this hydrogenation
are well-known to those skilled in the art. Generally,
hydrogenation is accomplished by contacting the copoly-
mers with hydrogen at superatmospheric pressure in the
presence of a metal catalyst such as colloidal nickel,
palladium supported on charcoal, etc. These block
copolymers typically have number average molecular
weights in the range of about 10,000 to about 500,000,
and preferably from about 30,000 to about 200,000.
The alpha,beta-olefinically unsaturated carbox-
ylic reagent includes the carboxylic acids per se and
functional derivatives thereof such as anhydrides,
esters, amides, imides, salts, acyl halides, etc. The
carboxylic acid reagents may be either monobasic or
polybasic in nature, and when polybasic, they are prefer-
ably dicarboxylic acids. The monobasic alpha,beta-ole-
finic unsaturated carboxylic acid reagents are carbox-
ylic acids corresponding to the formula

RCH=C ( R~ ) COOH

wherein R iS hydrogen or a saturated aliphatic or ali-
cyclic, aryl, alkaryl or heterocyclic group. Preferably,
R iS hydrogen or an alkyl group containing from 1 to
about 10 carbon atoms; R1 is hydrogen or an alkyl
group containing from about 1 to about 10 carbon atoms.
The total number of carbon atoms in R and R1 should
not exceed 18 carbon atoms. Specific examples of useful
monobasic alpha,beta-olefinic unsaturated carboxylic
acids include acrylic acid, methacrylic acid, cinnamic
acid, crotonic acid, etc.

2002695
--1 9--

As noted above, the olefinic unsaturated carbox-
ylic acid reagent may be a dibasic acid. Examples of
useful dibasic acids include maleic acid, fumaric acid,
mesaconic acid, itaconic acid and citraconic acid. A
preferred alpha,beta-olefinically unsaturated carboxylic
acid reagent is maleic anhydride.
The amount of alpha,beta-olefinically unsatur-
ated carboxylic reagent reacted with the block copoly-
mers is an amount which is effective to modify the pro-
perties of the block copolymers in a desired manner.
Generally, the amount of reagent will be from about 0.2
to about 20% by weight and preferably from about 0.5 to
about 5% by weight based on the total weight of the
block copolymer and the reagent.
In order to promote the reaction to generate
reaction cites, free radical initiators are utilized,
and these initiators usually are either peroxides or
various organic azo compounds. The amount of initiator
utilized generally is from about 0.01% to about 5% by
weight based on the combined weight of the block copoly-
mer in the carboxylic reagent. The amount of carboxylic
reagent incorporated into the block copolymers can be
measured by determining the total acid number of the
product.
(B-7) PolYcarbonates.
The polycarbonates utilized in the preparation
of the blends of this invention may be characterized by
the formulae

( Ar-A-Ar-O-C(O)O ) n

and

2002695

-20-

~ Ar-O-C(O)O ~ n

wherein Ar is selected from the group consisting of
phenylene and alkyl, alkoxyl, halogen and nitro-substi-
tuted phenylene; A is selected from the group consisting
of carbon-to-carbon bonds, alkylidene, cycloalkylidene,
alkylene, cycloalkylene, azo, imino, sulfur, oxygen,
sulfoxide and sulfone, and n is at least 2.
The preparation of the polycarbonates is well-
known and the details thereof need not be delineated
herein. There are a variety of preparative procedures
set forth in ChemistrY and PhYsics of Polvcarbonates by
Herman Schnell, Interscience Division of John Wiley &
Company, New York, (1964), first edition, as well as in
U.S. Patent 3,028,365. In general, a preferred reaction
is carried out by dissolving a dihydroxy component in a
base such as pyridine and bubbling phosgene into the
stirred solution at the desired rate. Tertiary amines
may be used to catalyze the reaction as well as to act
as acid acceptors throughout the reaction. Since the
reaction is normally exothermic, the rate of phosgene
addition can be used to control the reaction tempera-
ture. The reactions generally utilize equimolar amounts
of phosgene and dihydroxy reactants, however, the molar
ratios can be varied dependent upon the reaction condi-
tions.
A preferred polycarbonate utilized in this
invention is obtained when Ar is p-phenylene and A is
isopropylidene. This polycarbonate is prepared by
reacting para, para'-isopropyldienediphenol with phos-
gene and is sold by General Electric Company under thetrademark LEXAN~ and by Mobay under the trademark
MERLON~. This commercial polycarbonate typically has a

20026~ ~


molecular weight of around 18,Q00, and a melt tempera-
ture of over 230C. Other polycarbonates may be pre-
pared by reacting other dihydroxy compounds, or mixtures
of dihydroxy compounds, with phosgene. The dihydroxy
compounds may include aliphatic dihydroxy compounds
although for best high temperature properties aromatic
rings are essential. The dihydroxy compounds may include
within the structure diurethane linkages. Also, part of
the structure may be replaced by siloxane linkage. These
and other variations of polycarbonate structure are des-
cribed in the Schnell reference cited above. The same
reference presents a long list of monomers (particularly
dihydroxy compounds) that may be used in polycarbonate
synthesis.
(8-8) Graft CopolYmer of a MonoethYlenicallY Unsatur-
ated Resin Forminq Monomer and EPDM TYpe Elastomers.
The blended polymer compositions of the present
invention may contain a graft copolymer of a monoethylen-
ically unsaturated resin forming monomer on an EPDM type
of rubber. The monoethylenically unsaturated resin-form-
ing monomers include monomers such as styrene, halo sty-
rene, alpha-methyl styrene, para-methyl styrene, acrylo-
nitrile, methacrylonitrile, acrylic acid, methacrylic
acid, maleic anhydride, the lower (1-8 carbon atoms),
alkyl esters of acrylic acid and methacrylic acid, etc.
Monomers of particular interest are styrene, methyl
methacrylate, mixtures of styrene and acrylonitrile,
mixtures of styrene and methyl methacrylate, etc.
The terpolymers or rubbery polymers comprise
two different linear alpha-monoolefins and a non-conju-
gated diene. One of the alpha-olefins is ethylene and
the other is a higher alpha-monoolefin containing 3 to
16 carbon atoms such as propylene, 1-butene, 1-octene,

-22-

etc. Examples of useful non-conjugated dienes include
the 5-methylene-2-norbornene, 5-ethylidene-2-norbornene,
5-isopropylidene-2-norbornene, etc. The weight ratio of
the ethylene to the higher alpha-monoolefin in the
terpolymer is ordinarily within the range of from 20:80
to 80:20. The amount of diene should be such that the
iodine number of the terpolymer is in the range of from
about 15 to about 40, preferably from about 20 to about
which corresponds generally to about 7 to 20 weight
percent and preferably from 9 to 17 weight percent of
the diene monomer units in the terpolymer.
The weight ratio of the monoethylenically
unsaturated resin-forming monomer to the terpolymer is
from about 95:5 to 30:7. In one embodiment, the resin
forming monomer is polymerized in situ in the presence
of the terpolymer. The specific example of a graft
copolymer is a graft copolymer of styrene and acrylo-
nitrile on ethylene-propylene-5-ethylidene-2-norbornene
terpolymer wherein the terpolymer comprises 60 weight
percent ethylene, 30 weight percent propylene and 10% of
the norbornene monomer. Graft copolymers of the type
useful in the present invention, and methods of prepar-
ing such graft copolymers are described in, for example,
U.S. Patent 4,202,948 and 4,l66,08l. Graft copolymers are
commercially available such as from Dow Chemical Company
under the trade designation "Rovel"*.
(B-9) Acryllc Polymers.
The blended polymer compositions of the present
lnvention may contain acrylic polymers including acrylic
polymers derived from acrylic esters and methacrylic
esters. Generally acrylic polymers are based on methyl
methacrylate monomer (MMA). The acrylic monomers may be

* Denotes Trade Mark
~''

Z002695

-23-

polymerized by free radical processes using peroxides.
MMA may be homopolymerized or copolymerized with other
acrylates such as methyl or ethyl acrylate. Acrylic
polymers which have been modified with various ingredi-
ents also can be utilized, and these various ingredients
include butadiene, styrene, vinyl and butyl acrylate
which increase impact strength of the acrylics.
(B-10) Nitrile Resins.
Nitrile resins also may be used as the second
polymer in the blended compositions of the present inven-
tion. Nitrile resins or polymers based upon acryloni-
trile, and the polymers have moderately high tensile
properties, good impact properties when modified with
rubber or oriented, good gas barrier properties, good
chemical resistance and good taste and odor-retention
properties.
The nitrile resins (B-10) are preferably those
thermoplastic materials having an alpha,beta-olefinical-
ly unsaturated mononitrile content of 50% by weight or
greater. These nitrile barrier resins may be copoly-
mers, grafts of copolymers onto a rubbery substrate, or
blends of homopolymers and/or copolymers.
The alpha,beta-olefinically unsaturated mono-
nitriles encompassed herein have the structure

CH2=C(R)CN

where R is hydrogen, an alkyl group having from 1 to 4
carbon atoms, or a halogen. Such compounds include
acrylonitrile, alpha-bromoacrylonitrite, alpha-fluoro-

acrylonitrile, alpha-methacrylonitrile, alpha-ethacrylo-
nitrile, and the like. The most preferred olefinically
unsaturated nitriles in the present invention are acrylo-
nitrile, methacrylonitrile and mixtures thereof.

~002695

-24-

These nitrile resins may be divided into sever-
al classes on the basis of complexity. The simplest
molecular structure is a random copolymer, predominantly
acrylonitrile or methacrylonitrile. The most common
example is a styrene-acrylonitrile copolymer. Block
copolymers of acrylonitrile, in which long segments of
polyacrylonitrile alternate with segments of polysty-
rene, or of polymethyl methacrylate, are also known.
Simultaneous polymerization of more than two
comonomers produces an interpolymer, or in the case of
three components, a terpolymer. A large number of
comonomers for the acrylonitrile are possible. These
include lower alpha olefins of from 2 to 8 carbon atoms,
e.g., ethylene, propylene, isobutylene, butene-1, pen-
tene-1, and their halogen and aliphatic-substituted
derivatives as represented by vinyl chloride, vinylidene
chloride, etc.; monovinylidene aromatic hydrocarbon
monomers of the general formula

Ar-c(R1)=cH2

wherein R1 is hydrogen, chlorine or methyl and Ar is
an aromatic group of 6 to 10 carbon atoms which may also
contain substituents such as halogen and alkyl groups
attached to the aromatic nucleus, e.g., styrene, alpha
methyl styrene, vinyl toluene, alpha chlorostyrene,
ortho chlorostyrene, para chlorostyrene, meta chlorosty-
rene, ortho methyl styrene, para methyl styrene, ethyl
styrene, isopropyl styrene, dichloro styrene, vinylnaph-
thalene, etc. Especially preferred comonomers are iso-
butylene and styrene.
Another group of comonomers are vinyl ester
monomers of the general formula

Z002~9S


R3C(H)=C(H)-OC(O)R3
wherein each R3 is independently selected from the
group comprising hydrogen, alkyl groups of from 1 to 10
carbon atoms, aryl groups of from 6 to 10 carbon atoms
including the carbon atoms in ring-substituted alkyl
substituents; e.g., vinyl formate, vinyl acetate, vinyl
propionate, vinyl benzoate and the like.
Similar to the foregoing and also useful are
the vinyl ether monomers of the general formula

H2C=C(H)-OR4

wherein R4 is an alkyl group of from 1 to 8 carbon
atoms, an aryl group of from 6 to 10 carbon atoms, or a
monovalent aliphatic radical of from 2 to 10 carbon
atoms, which aliphatic radical may be hydrocarbon or
oxygen-containing, e.g., an aliphatic radical with ether
linkages, and may also contain other substituents such
as halogen, carbonyl, etc. Examples of these monomeric
vinyl ethers include vinyl methyl ether, vinyl ether
ether, vinyl n-butyl ether, vinyl 2-chloroethyl ether,
vinyl phenyl ether, vinyl isobutyl ether, vinyl cyclo-
hexyl ether, 4-butyl cyclohexyl vinyl ether or p-chloro-
phenyl glycol, etc.
Other comonomers are those comonomers which
contain a mono- or dinitrile function. Examples of
these include methylene glutaronitrile, (2,4-dicyano-
butene-1), vinylidene cyanide, crotonitrile, fumarodi-
nitrile, maleodinitrile.
Other comonomers include the esters of olefin-
ically unsaturated carboxylic acids, preferably the
lower alkyl esters of alpha,beta-olefinically unsatur-


2002695

-26-

ated carboxylic acids and more preferred the esters
having the structure

C~2=C ( R1 ) COOR2
wherein R1 is hydrogen, a halogen, or an alkyl group
having 1 or 2 carbon atoms and R2 is hydrogen or an
alkyl group having from 1 to 8 carbon atoms. Compounds
of this type include methyl acrylate, ethyl acrylate,
methyl methacrylate, ethyl methacrylate, methyl alpha-
chloroacrylate, and the like. Most preferred are methyl
acrylate, ethyl acrylate, methyl methacrylate, ethyl
methacrylate, butyl acrylate and butyl methacrylate.
Another class of nitrile resins are the graft
copolymers which have a polymeric backbone on which
branches of another polymer chain are attached or graft-
ed. Generally the backbone is preformed in a separate
reaction. Polyacrylonitrile may be grafted with chains
of styrene, vinyl acetate, or methyl methacrylate, for
example. The backbone may consist of one, two, three,
or more components, and the grafted branches may be
composed of one, two, three or more comonomers.
The methods of forming these various nitrile
resins and examples of these resins can be found in the
following U.S. Patents 3,325,458; 3,336,276; 3,426,102;
3,451,538; 3,540,577; 3,580,974; 3,586,737; 3,634,547;
3,652,731; and 3,671,607.
The chemical composition of the nitrile resins
in general useful as resin (B-10) may be varied consi-
derably, but in general, useful nitrile resins will
include about 70% by weight of acrylonitrile monomer, 20
to 30% methyl acrylate or styrene as a comonomer and
from 0 to about 10% butadiene as the impact-modifying

termpolymer. Nitrile polymers of these types are
offered commercially under the trade designation Barex* ;
resins supplied by BP Chemicals International.
(B-11) Acr~lic-Styrene-AcrYlonitrile PolYmers.
The blended polymer compositions of the present
invention may contain one or more acrylic-styrene-acrylo-
nitrile polymers. These terpolymers are often referred
to as "ASA". The ASA polymers are generally similar to
ABS resins with regard to properties. The type and
amount of the monomers used to prepare these terpolymers
may be varied, and the choice will be dependent in part
on the properties desired. Various acrylic monomers,
styrene monomers and acrylonitrile monomers can be used
in various combinations. For example, alpha-methylsty-
rene or methacrylonitrile also can be used. An example
of a commercially available acrylic-styrene-acryloni-
trile terpolymer is the polvmer available from General
Electric Company under the designation Geloy. Other
examples include an acrylic:styrene:methacrylonitrile
terpolymer.
(s-12) AcrYlonitrile-Haloqenated PolYolefin-Stvrene Ter-
polymers.
The blended polymer compositions of the inven-
tion also may include at least one acrylonitrile-halogen-
ated polyolefin-styrene terpolymer. These terpolymers
often are referred to as ACS polymers when the halogen
is chlorine. A commercially available example of such
terpolymers is an acrylonitrile-chlorinated polyethyl-
ene-styrene terpolymer which is available in three
grades: flame retardant, weather resistant, and optical
reflector. These terpolymers are manufactured by the
Specialty Plastics Division of Showa Denko K.K.
* Denotes Trade Mark

2(~02695

-28-

(C) Compatibilizinq Aqent.
The polymer blends of the present invention
also contain at least one compatibilizing agent which
may be block copolymers selected from the group consist-
ing of diblock, triblock, multiblock, starblock, poly-
block or graftblock copolymers of a vinyl aromatic
compound and a conjugated diene, or their partially
hydrogenated derivatives and mixtures thereof. The
choice of compatibilizing agent included in the blended
lOpolymer compositions of the in~ention may depend upon
the type of polymers (A) and (s) included in the blend.
In one preferred embodiment, the compatibiliz-
ing agent is at least one multiblock, starblock, poly-
block or graftblock copolymer with multiblock copolymers
being particularly preferred. In another preferred
embodiment, the compatibilizing agent is a multiblock
copolymer as described above comprising at least about
40% by weight of styrene, and more often, from about 40
to about 75% by weight of styrene. Many of the charac-
20teristics of the block copolymers can be varied and
controlled by balancing between the hard (polystyrene)
and rubber (polydiene) components, and utilizing linear
or branched structures with different molecular weights.
Throughout this specification and claims, the
terms diblock, t.riblock, multiblock, polyblock, and
graft or grafted-block with respect to the structural
features of block copolymers are to be given their
normal meaning as defined in the literature such as in
the Encyclopedia of Polymer Science and Engineering,
30Vol. 2, (1985) John Wiley & Sons, Inc., New York, pp.
325-326, and by J.E. McGrath in Block CopolYmers, Sci-
ence TechnoloqY, Dale J. Meier, Ed., Harwood Academic
Publishers, 1979, at pages 1-5. In particular, the

~0026~5

-29-

structure of the various block copolymers may be
illustrated as follows:

TABLE 1
Block Co~olymers
diblock copolymer A-B or
triblock copolymer A-B-A A ~
B-A-B ~,v,_----~4~~~-
multiblock copolymer (A-B)n ~ ~ ~ n

A
starblock copolymer3 B-A-X-A-B ~ ~-
A ~
B ~3
graft- or grafted-block
copolymer 8

2 hard -~ soft.
Sometimes designated segmented or poly block copoly-
mers, n is >1.
3 X is a junction unit, also called radial block.

It will be understood that blocks A and B and C
may be either homopolymer or random copolymer blocks as
long as each block predominates in at least one class of
the monomers characterizing the blocks and as long as
the A block is predominantly a vinyl aromatic compound
and the B block is predominantly a diene or its hydrog-
enated derivatives. The vinyl aromatic compounds which
may be present in the block copolymers utilized in the
present invention may be any of the vinyl aromtic
compounds described above with respect to polymer
component (B-1) and (B-2). Preferred vinyl aromatic

2002695


-30-

compounds are styrene and alpha-methyl styrene with
styrene being particularly preferred. The conjugated
dienes may contain from 4 to 10 carbon atoms and more
generally contain from about 4 to about 6 carbon atoms.
Butadiene and isoprene are particularly preferred conju-
gated dienes useful in preparing the block copolymer
compatibilizers useful in the present invention.
Partially hydrogenated block copolymer deriva-
tives also are useful as compatibilizers in the polymer
compositions of the present invention. The conjugated
diene portion of the block copolymer is at least 90%
saturated and more often at least 95% saturated while
the vinyl aromatic portion is not significantly hydrog-
enated. More particularly useful hydrogenated block
copolymer is the block copolymer of polystyrene-polyiso-
prene-polystyrene which has been hydrogenated to a
polystyrene-poly(ethylene/propylene)-polystyrene block
polymer. When a polystyrene-polybutadiene-polystyrene
block copolymer is hydrogenated, it is desirable that
the 1,2-polybutadiene to 1,4-polybutadiene ratio in the
polymer is from about 30:70 to about 70:30. When such a
block copolymer is hydrogenated, the resulting product
resembles a regular copolymer block of ethylene and
butene-1 (EB). As noted above, when the conjugated
diene employed as isoprene, the resulting hydrogenated
product resembles a regular copolymer block of ethylene
and propylene (EP).
Hydrogenation of the precursor block copolymers
can be effected by known techniques such as by the use
of a catalyst comprising the reaction product of an
aluminum alkyl compound with nickel or cobalt carboxyl-
ates or alkoxides under conditions which result in
substantial complete hydrogenation of at least 80% of

-31-

the aliphatic double bonds while hydrogenating 25% of
the vinyl aromatic double bonds remaining in the poly-
mer. Preferred hydrogenated copolymers of those wherein
at least 99% of the aliphatic double bonds are hydrogen-
ated while less than 5% of the aromatic double bonds are
hydrogenated.
The average molecular weights of the individual
blocks within the copolymers may vary within certain
limits. In most instances, the vinyl aromatic block
will have a number average molecular weight in the order
of about 5000 to about 125,000, and preferably between
about 7000 and 60,000. The conjugated diene blocks
either before or after hydrogenation will have number
average molecular weights in the order of about 10,000
to about 3C0,000 and more preferably from about 30,000
to 150,000. The total number average molecular weight
of the block copolymers is typically in the order of
about 25,000 to about 250,000.
Specific examples of diblock copolymers include
styrene-butadiene, styrene-isoprene, and the hydrogen-
ated derivatives thereof. Examples of triblock polymers
include styrene-butadiene-styrene, styrene-isoprene-sty-
rene alpha-methylstyrene-butadiene-alpha-methylstyrene,
alpha-methylstyrene-isoprene-alpha-methylstyrene, and
their partially hydrogenated derivatives. The diblock
and triblock polymers are commercially available from a
variety of sources under various tradenames. Examples
of commercially available diblock resins include Sol-
prene* 314D (Phillips) and K Resin 04 (Phillips). A
number of styrene-butadiene-styrene triblock copolymers
are sold by the Shell Chemical Company under the trade-
marks "Kraton* 2103", "Kraton* 2104", and "Kraton*2113".
Such thermoplastic rubbery block copolymers are made by
* Denotes l'rade Mark
B~


-32-

anionic polymerization, and the above three identified
Shell Kratons differ in molecular weight and viscosity,
and also in the ratio of butadiene to styrene. For
example, "Kraton 2103" and "Kraton 2113" have a styrene
to butadiene ratio of 28:72 while "Kraton 2104" as a
styrene to butadiene ratio of 30:70. Blends of diblock
and triblock copolymers are also available. Kraton 1118
(Shell) is a blend of SB diblock and SBS triblock copoly-
mers. A Kraton G-1652 is a hydrogenated SBS triblock
comprising 30% styrene end blocks and a midblock equiva-
lent to a random copolymer of ethylene and 1-butene
(EB). This copolymer is sometimes designated as SEBS.
Functionalized block copolymers such as those
obtained by reacting a block copolymer with maleic
anhydride also are useful in this invention. Kraton FG
1901X is a maleated SEBS block copolymer available from
Shell.
Multiblock copolymers of styrene and either
isoprene or butadiene also are commercially available.
Commercially available and preferred styrene-butadiene
multiblock copolymers include Stereon*840A, Stereon*841A
and Stereon* 845A which are available from The Firestone
Tire & Rubber Company.
Starblock copolymers of styrene and isoprene or
styrene and butadiene are commercially available from
Phillips Petroleum Company under such designations as
"K-Resin". Generally, the K-Resins have a high polysty-
rene content such as about 75%, and these resins are
transparent and rigid. One particularly preferred star-
block copolymer is K-Resin KR03 from Phillips. A
similar material (75% styrene:25% butadiene) is avail-
able from Fina under the designation "Finaprene*520".
Radial or starblock copolymers also are available from
* Denotes Trade Mark

2002695

-33-

Fina under the general designation "Finaprene SBS
Polymer1'. Various grades are available containing from
20% to 40% of styrene.
The relative amounts of the two or more poly-
mers and compatlbilizers utilized in the blended polymer
compositions of the present invention may vary over a
relatively wide range depending on the specific mater-
ials used, the desired properties, and particular end
use for the blended polymer compositions of the inven-
tion. Thus, the blended polymer compositions of the
present invention may comprise
(A) from 1 to about 99% by weight of at least
one olefin polymer;
(s) from 1 to about 99% by weight of at least
one styrenic polymer or any of the polymers and polymer
blends identified herein as components (s-1) through
(B-12); and
(C) from 1 to about 40% by weight and more
generally from 1 to about 15% of the compatibilizer.
In one embodiment of the invention, the compositions of
the present invention comprise from about 49 to about
90% by weight of polyolefin (A), 10 to about 30~ of the
polymer or polymer blend (B-1) through (B-12), and from
about 2 to about 10% by weight of the compatibilizing
agent.
Generally, the order of mixing of the polymers
(A) and (B) and the compatibilizers (C) is not critical.
Accordingly, it is possible to mix the compatibilizer
with the polyolefin and other polymers by mixing all of
the components at the same time. Alternatively, the
order of mixing can be varied in order to match the
relative viscosities of the various components. The
blended polymer compositions of the present invention

20~269S

-34-

may be true blends of the polymers and compatibilizers,
or some grafting of the compatibilizers to either or
both of the polymers or another compatibilizer are
possible.
The blended polymer compositions of the present
invention may contain, in addition to the components
identified above as components (A), (s) and (C) other
components added to modify the properties of the blended
polymer composition. The blended polymer compositions
of the invention may be compounded further with other
polymers (e.g., barrler resins), oils, fillers, coupling
agents, reinforcements, antioxidants, stabilizers, fire-
retardants, foaming agents, colorants, processing aids,
etc. Such additives are selected to provide or modify
desirable characteristics of the products prepared from
the compositions.
(D) sarrier-Resins.
The blended polymer compositions of the present
invention may contain at least one resin referred to in
the art as a barrier resin. Barrier resins are charac-
terized as having low gas and vapor transmission proper-
ties. Any of the known barrier resins may be utilized
as component (D) in the blended polymer compositions of
the present invention. Particular examples of useful
barrier resins (D) include resins selected from the
group consisting of vinylidene chloride polymers, and
copolymers of vinylidene chloride with one or more mono-
ethylenically unsaturated monomers which are copoly-
merizable with the vinylidene chloride; copolymers of
ethylene and vinyl alcohol (EVOH), polyamides, and
nitrile resins comprising alpha,beta-olefinically unsat-
urated aliphatic mono-nitrile polymers and copolymers.
When utilized in the blended polymer compositions of the

Z002695

-35-

invention, the barrier resin (D) generally is present in
amounts of from 0.1 to about 20% by weight based on the
total weight of polymer and resin. It should be noted
that polymer (s-10) has previously been described as a
nitrile resin. Thus, when the blended polymer composi-
tions include a nitrile resin (B-10) as the second poly-
mer (B), it is generally not necessary to add additional
nitrile resin as a barrier component, and it may not be
necessary to add any additional barrier resin to the
blended polymer composition.
Vinylidene chloride polymers and copolymers are
useful barrier materials. Copolymers are particularly
useful and these include copolymers having polymerized
therein vinylidene chloride in an amount of from about
40 to about 98% by weight and at least one monoethylenic-
ally unsaturated monomer which is copolymerizable with
the vinylidene chloride in an amount of from about 60~
to about 2% by weight. The copolymerizable monomer may
be a vinyl functional monomer such as vinyl chloride;
alkyl esters of acrylic and methacrylic acids such as
alkyl acrylates and alkyl methacrylates; ethylenically
unsaturated mono- and dicarboxylic acids such as acrylic
acid, methacrylic acid, and itaconic acids; and cyano-
functional monomers such as acrylonitrile and methacrylo-
nitrile.
Ethylene vinyl alcohol copolymers (EVOH) that
are useful as barrier resins in the compositions of the
present invention generally will contain at least about
55% and as much as 80% by weight of vinyl alcohol, and
the remainder of the molecule consists essentially of
ethylene. These copolymers generally are prepared by
hydrolysis of ethylene vinyl acetate copolymers, and,
therefore, some vinyl acetate may remain in the resin.

2002695

-36-

The EVOH copolymers typically have molecular weights in
the range of from about 20,000 to 30,000. The EVOH
copolymers useful as barrier resins in the compositions
of the present invention are commercially available such
as from the EVAL Company of America.
Polyamides may also be incorporated into the
blended polymer compositions of the present invention to
serve as barrier compositions. The polyamides are
condensation products which contain recurring aromatic
and/or aliphatic amide groups in integral parts of the
main polymer chain. Such polyamide products are known
generically as "nylons". These polyamides may be pre-
pared by polymerizing a monoamino carboxylic acid or an
internal lactam thereof having at least 2 carbon atoms
between the amino and the carboxylic acid groups. Alter-
natively, the polyamides may be obtained by a polymeriz-
ing dicarboxylic acid with a diamine which contains at
least 2 carbon atoms between the amino groups. Another
procedure for preparing polyamides is to polymerize a
monoamino carboxylic acid or an internal lactam thereof
with a substantially equimolar portion of a diamine and
a dicarboxylic acid. Examples of amino carboxylic acids
and lactams include epsilon-amino caproic acid, butyro-
lactam, pivalolactam, caprolactam, capryllactam, undec-
anolactam and 3- and 4-aminobenzoic acids. Examples of
diamines include diamines containing up to 16 carbon
atoms such as trimethylenediamine, tetramethylenedia-
mine, pentamethylenediamine, octamethylenediamine,
decamethylenediamine, hexadecamethylenediamine and in
particular, hexamethylenediamine. Aromatic amines such
as p-phenylenediamine, 4,4'-diaminodiphenylsulfone,
etc., may be utilized.

ZOOZ695

-37-

The dicarboxylic acids used to form the nylons
may be aromatic, for example, isophthalic or terephthal-
ic acids or aliphatic dicarboxylic acids represented by
the formula HOOCYCOOH wherein Y represents a divalent
aliphatic group containing at least 2 carbon atoms.
Examples of such aliphatic dicarboxylic acids include
sebacic acid, octadecanoic acid, suberic acid, azelaic
undecanedioic acid, glutaric acid, pimelic acid, and
especially adipic acid. Specific examples of polyamides
l~ useful as barrier compounds in the present invention
include:
polyhexamethylene adipamide (nylon 6:6),
polypyrrolidone (nylon 43,
polycaprolactam (nylon 6),
polyheptolactam (nylon 7),
polycapryllactam (nylon 8), etc.
The number average molecular weights of the polyamides
used in the polymer blends of the present invention are
generally above about 10,000.
The nitrile barrier resins may be any of the
resins identified earlier as polymer (s-10).
Commercial examples of nitrile barrier resins
include BAREX~ 210 resin by BP Chemicals International,
an acrylonitrile-based high nitrile resin containing
over 65~ nitrile, and Monsanto's LOPAC0 resin containing
over 70% nitrile, three-fourths of it derived from
methacrylonitrile.
(E) Fillers and Fibers.
The blended polymer compositions of the present
invention may contain one or more fillers of the type
used in the polymer art. Examples of fillers employed
in a typical compounded polymer blend according to the
present invention include talc, calcium carbonate, mica,

2002695

-38-

wollastonite, dolomite, glass fibers, boron fibers,
carbon fibers, carbon blacks, pigments such as titanium
dioxide, or mixtures thereof. Preferred fillers are a
commercially available talc such as R.T. Vanderbilt's
Select-O=~orb and glass fibers. The amount of filler
and fibers included in the blended polymers may vary
from about 1% to about 70% of the combined weight of
polymer and resin. Generally amounts of 5% to 30% are
included.
The fillers and fibers may be treated with
coupling agents to improve the bond between the fillers
and fibers to the resin. For example, the fillers can
be treated with materials such as fatty acids (e.g.,
stearic acid), silanes, maleated polypropylene, etc.
The amount of coupling agent used is an amount effective
to improve the bond between the fillers and fibers with
the resin.
The blended polymer compositions of the present
invention comprising the olefin polymer, the second poly-
mers as described herein as components (B-1) through
(B-12), the compatibilizer (C) and other resins such as
barrier resins and additives can be prepared by tech-
niques well known to those skilled in the art. For exam-
ple, a particularly useful procedure is to intimately
mix the polymers using conventional mixing equipment
such as a mill, a Banbury, a Brabender, a single or twin
screw extruder, continuous mixers, kneaders, etc. For
example, the polymers may be intimately mixed in the
form of granules and/or powder in a high shear mixer.
One preferred process for preparing the blended polymers
utilizes the Farrell Continuous Mixer (FCM), CP-23.
Short residence times and high shear are readily
obtained in a CP-23. "Intimate" mixing means that the

200X695
-39-

mixture is prepared with sufficient mechanical shear and
thermal energy to produce a dispersed phase which is
finely divided and homogeneously dispersed in the
continuous or principal phase.
Improved mixing is often obtained when the
viscosities of the olefin polymer (A) and polymer (B~
are similar at the temperature and shear stress of the
mixing process. The chance for formation of cocontin-
uous interlocking networks on cooling is increased when
approximately equal molar ratios of polymers (A) and (B)
are utilized; for example a 50:50 molar ratio of styrene
maleic anhydride copolymer and polyolefin.
The polymer blends of the present invention are
characterized as having excellent heat distortion proper-
ties as well as excellent strength, toughness, stiff-
ness, gloss, ease of processing and fabrication, improv-
ed filler interaction, and shrinkage characteristics,
hardness, adherability, moldability, formability, and
they are retortable and microwaveable. Another advant-

age of the blended polymer compositions of the presentinvention is that they can be recycled in conventional
procedures whereby the scrap is comminuted and dry-
blended or extrusion-blended with fresh blended polymer,
and the polymer blended with scrap does not lose its
desirable properties. Accordingly, in one embodiment,
the blend of fresh or virgin blended polymers of the
invention and scrap polymer is extruded into a sheet
which can be used in a multilayer structure, preferably
as an inner layer, with sheets of virgin blended poly-
mers of the invention, and/or other layers of, e.g.,barrier materials, polyolefins, aliphatic or aromatic
polyolefins, etc. The blends of fresh and scrap polymer
blends of the invention also can be coextruded into

2002695

~o--

multilayer structures with any of the other polymer
materials discussed above.
In some instances, the low temperature impact
strength of materials prepared from the blended polymer
compositions of the present invention is improved when
compared to the typical performance of olefin polymers
such as polyethylene and polypropylene, and, therefore,
the blended polymer compositions of the present inven-
tion possess the required low temperature impact perform-
ance and other physical characteristics required for
many applications for which polyolefins cannot be used.
The polymer blends of the present invention also exhibit
excellent food, oil and fat-resistance and are therefore
particularly suited for packaging food products. The
polymer blends of the invention can be formed into pack-
ages, containers, cups, and other products.
It also has been observed that the blended
polymer compositions of the present invention can be
processed into shaped articles by extrusion, coextru-
sion, ther~oforming, blow molding, injection molding,
compression molding, calendering, laminating, stamping,
pultrusion, foaming or die coating of continuous fibers.
In particular, shaped articles can be prepared by thermo-
forming sheets of the blended polymer compositions of
the present invention. Sheets of the blended polymer
compositions of the present invention can be prepared on
an extruder such as a 3.5-inch HPM extruder with a two-
stage screw of 30:1 L/D ratio and at a melt temperature
of about 445F (230C). The extrudate is subsequently
passed through polished rolls with a center roll heated
to an elevated temperature to form a sheet which exhi-
bits low sag since the polymers are appropriately compat-
ibilized. The blended polymer compositions of the

;~00269S

-41-

invention also can be used to form an extrusion coating
on lony fiber reinforcements such as used in long fiber
reinforced thermoplastics.
Scrap material produced from processing of the
blended polymer compositions of the present invention
such as scrap material produced from thermoforming the
multilayer structures of the present invention, may be
recovered, reground and recycled for use as a component
in the polyolefin-containing layer of the multilayer
structures. Such scrap material may contain components
from the various layers including the polyolefin-contain-
ing layer and barrier layer when present. The amount of
scrap utilized in the polyolefin-containing layer may
vary widely, and may comprise from 1 to about 99% by
weightj and more preferably from about 10 to about 60%
by weight of the polyolefin-containing layer.
In one embodiment of the present invention,
thermoformable multilayer structures can be prepared
which comprise
(I) at least one layer of a blended polymer
composition according to the present invention; and
(II) at least one layer of an olefin polymer
composition which may comprise any of the olefin poly-
mers and olefin copolymers mentioned previously. In a
preferred embodiment, the layer of olefin polymer compo-
sition is a layer of filled or unfilled polyethylene or
polypropylene.
In another embodiment, the multilayer structure
may comprise
(III) at least one layer of a barrier resin such
as the high nitrile barrier resins described above.
Thus, in one embodiment, a thermoformable multilayer
structure may comprise a layer of the polymer blend

-42-

composition of this invention and a cap layer on one
side of an olefin polymer such as polyethylene or
polypropylene or a cap layer of a barrier material (D~
as described above, or a cap layer of an aliphatic or
aromatic vinyl resin such as polystyrene or polymers and
copolymers of acrylic esters and acrylonitrile. In
another embodiment a multilayer structure comprises a
central layer of the polymer blend composition of the
present invention, a cap layer on one side comprising an
olefin polymer such as polyethylene or polypropylene and
a cap layer on the other side of a barrier material, or
vinyl polymer.
The cap layers such as the layers of barrier
resin, vinyl polymers, etc., can be applied by coextru-
sion, laminating, etc., or the second layer can be
applied from a solution or a dispersion of the barrier
resin or vinyl polymer in water or an organic liquid
such as acetone. On drying, a film or cap layer is left
on the layer comprising the composition of the inven-
tion.
Molded articles having desired shapes can be
produced from each of the blended polymer compositions
of the present invention by
(A) Eeeding a sheet of the blended polymer
composition of the invention to a heating station;
(B) heating the sheet to its softening point;
and
(C) feeding the softened sheet to a forming
station where it is molded înto articles of the desired
shape.
In another embodiment, coextruded multilayered
structures can be prepared wherein at least one layer
comprises the blended polymer compositions of the pre-

200269S


sent invention. In other embodiments, at least one
additional layer comprises a polyolefin such as poly-
ethylene or propylene.
Various features and aspects of the present
invention are illustrated further in the examples that
follow. While these examples are presented to show one
skilled in the art ~how to operate within the scope of
this invention, they are not to serve as a limitation on
the scope of the invention where such scope is only
defined in the claims. Moreover, in the following
examples, preparation of blends, compounds, injection
molded specimens, mono layer or laminated sheets are
illustrated. These examples serve merely as illustra-
tive embodiments of the present invention and are not to
be considered limiting.
Unless otherwise indicated in the following
examples and elsewhere in the specification and claims,
all parts and percentages are by weight, temperatures
are in degrees centigrade and pressures are at or near
atmospheric. The physical properties described in the
following examples are measured in accordance with ASTM
Standard Test Procedures as identified in the following
Table 3.

20026~5

-44-

TABLE 3
Property ASTM Method
Melt Flow Rate D-1238*
Tensile Strength D-638
Elongation D-638
Flexural Strength D-790
Flexural Modulus (tangent) D-790
Izod Impact (notched) D-256**
Izod Impact (unnotched) D-256
Gardner Impact D-3209
Heat Deflection Temperature D-648
Instrumented Impact D-3763
* Condition 230C/2.16 kg.
** Method A.
Example 1
The compatible blend of polypropylene (PP), a
styrene maleic anhydride copolymer (SMA) and a multi-
block styrene-butadiene copolymer (SBR) is prepared on a
laboratory Banbury mixer (Farrel) at about 155C, ground
and injection-molded ('Van Dorn 110' at about 230C
stock temperature) into test specimens. The make-up of
the composition and its properties are summarized in
Table 4. A control is also summarized.

~002695

-45-

TABLE 4
Composition* Control Example 1
Himont Profax 6523 (PP) 100 87.5
Arco Dylark 332 (SMA) --- 10.0
Phillips K-Resin KR03 (SBR) --- 2.5
Properties
Melt Flow g/10 min. (Cond. L) 4.5 4.1
Tensile Strength, psi 4990 5070
Flexural Modulus, psi 230,000 274,000
Flexural Strength, psi 7360 8490
Notched Izod Impact, ft.lb./in~ 0.52 0.74
Gardner Impact, (RT) in.lb. 21 16
HDT at 66 psi, C 84 104
Linear Shrinkage, in./in. % 1.6 1.3
* % by weight.

In addition, the molded specimens of Example 1 have
excellent surface characteristics with respect to
appearance and hardness.
Example 2
A blended polymer composition in accordance
with the present invention is prepared on a Farrel
Continuous Mixer (FCM), CP-23 at a mixer speed of 1000
rpm and extruded at about 220C into strands which are
passed through a water bath prior to pelletizing. The
pellets are injection molded (220C stock temperature
and 30C mold temperature) into test specimens. The
makeup of the composition and its physical properties
are summarized as follows:

2~)02695

-46-

TAsLE 5
Composition ~/wt.
Shell 7C06 (PP copolymer) 52.45
Arco Dylark 332 (SMA) 20.00
Firestone Stereon 840A (SBR) 5.00
RT Vanderbilt Select-O-Sorb (talc) 20.00
CR-834 (TiO2) 2.50
Ciba~Geigy Irganox 1010 (Stabilizer) 0.05
Properties
Melt Flow, g/10 min. 2.0
Tensile Strength, psi 4036
Flexural Modulus, psi 373,000
Flexural Strength, psi 5967
Izod, Notched, ft.lb./in. 0.71
Izod, Unnotched, ft.lb./in. 8.40
Gardner Impact, in.lb. 27
HDT at 66 psi, C 118
Linear Shrinkage, in./in. % 0.7

In addition to the high-heat distortion tempera-
ture and low shrinkage characteristics of the above com-
pound, the molded specimens also exhibit high gloss and
scratch resistant surface characteristics.
Example 3
A sheet is formed from the composition prepared
in Example 2 on a 3.5-inch HPM extruder, with a two-
stage screw of 30:1 L/D ratio and at a melt temperature
of about 230C. The extrudate is passed through polish-
ed rolls with a center roll temperature of about 94C to
form a sheet which is 48 inches wide. The sheet is cut
into about 12-inch squares and the squares are then fed
to a CAM thermoformer. When the squares are heated to
their softening point, they are advanced to a forming

200Z695

-47-

station where the squares are molded into the shape of a
cup by a pressure-forming technique. The resulting cups
are excellent in appearance and detail. The excellent
thermoformability of the composition of Example 2 is
similar to that obtained by commercial styrenics, and
the talc-filled cups have superior gloss characteristics
compared to a typically filled polypropylene compound.
Example 4
An extruded sheet prepared as in Example 3 with
the composition of Example 2 is laminated on both sides
with the polypropylene and/or a 20% talc-filled polypro-
pylene sheet and subsequently thermoformed into cups in
a single operation. The cups exhibit good adhesion
between the layers of sheets, and the cups are of high
quality.
Examples 5-9
Blends containing polypropylene, styrene maleic
anhydride copolymer, talc and Phillips K-Resin KR03 (a
multiblock copolymer) are prepared in a Banbury mixer
(Farrel) at about 55C and extruded at about 220C into
strands which are passed through a water bath prior to
pelletizing. The pellets are injection-molded (220C
stock temperature) into test specimens. Table 6 identi-
fies the various compositions of Examples 5-9 and a con--
trol sample identified as Control-2. Properties of
these reinforced compositions also are listed in the
table.

-48 -




o .. C~ ~ C~ V~
cn ¦ N O O N .J 1~1 r- ~ O
C\~
.DI
a~ o N C
EI ~ N ~ I~ ~ d 1~1 ~~
v
~1 N
O Nl cn
r~ I cno v . ~ ~ ~ O ~
¦ 1~`1N ~ID .-- ~ " ) ~ O
~D
N O 1--
~O N~ 1 c:n ~ o
~1 u~
L O + ¦ Il~
cC I CO C~ O ~ O
N




O O
c o .- cn
O oo I I . o ~^V U~
C_~ CO N I I ~-- ~ N (~


O r
C o C~
c V
C~ 0 N r E C Vl CD
0 C~ ; 0
N ~Y ~ 0
~ ~ 0 U~ ~ O v~
O ~c~.~ L L r- C ~D . +' L
CL_ ~~ O ~ O C O ~I 0
~ ~L~~O ~ c c ~ c _
X(D L_C L ~ 0 0 0 C O ~

-49-

As can be seen from the results summarized in
Table 6, the blended compositions of the present inven-
tion exhibit superior linear shrinkage, modulus and
tensile strength compared to Control Example 2.
Examples 10-12
Blended polymer compositions in accordance with
the present invention are prepared utilizing the general
procedure of Example 2 and with the components identi-
fied in the following Table 7. Examples 11 and 12
contain mixtures of two different compatibilizers and
Example 12 also contains EVOH as a barrier polymer
component. The properties of the blended polymer compo-
s~tions of Examples 10-12 are summarized in Table 7.

TABLE 7
Example
1~ 12
Shell 7C06 (PP copolymer) 75.45 65.45 43.95
Arco Dylark 332 (SMA) 9.60 9.60 14.50
Cain talc 4590 (talc) 10.00 10.00 15.00
White Pigment (TiO2) 2.50 2.50 2.50
Irganox*1010 (Stabilizer) 0.05 0.05 0.05
Firestone Stereon 840A (SBR) 2.50 2.40 3.70
Shell Kraton G 1652 (SEBS) --- 10.00 10.00
EVOH Copolymer --- --- 10.00
Pro~erties
Melt Flow, g/10 min 1.5 1.5 1.0
Tensile Strength, psi 3840 3262 3265
Flexural Strength, psi 5334 4081 4477
Tangent Modulus, Kpsi 2.54 1.89 2.35
Izod, Notched, ft.lb./in. 1.07 2.4 0.75
Izod, Unnotched, ft.lb./in. 12.57 --- 7.99
HDT at 66 psi, C 93 89 92
Linear Shrinkage, in/in % 1.0 0.8 0.6
* Denotes Trade Mark
l ~,, ~ i,

zooz6gs

-50-

Example 13
A two-layer laminate is prepared in the follow-
ing manner. A 40 mil sheet of the composition of Exam-
ple 2 is prepared by extrusion. To this sheet of Exam-
ple 2 there is heat laminated a 12 mil polypropylene cap
layer (Shell 7C06). The original sheet prepared from
the product of Example 2 and the two layer laminate are
evaluated for impact strength in an Instrumented Impact
Tester, (Rhemetrics Model RDT-S000). This test provides
information on the amount of force (in pounds) required
to rupture the test specimen at a certain preset velo-
city of a falling weight. The rating for the sheet
- prepared with the product of Example 2 is 64.7 pounds,
and the value for the laminate is 144.2 pounds, a
signi~icant increase. Improved Gardner gloss also is
observed. The Gardner gloss measured at a 60 angle.
For the laminate, the Gardner reading is 61 on the
Example 2 sheet side and 76 for the polypropylene
side. In addition, taste and odor characteristics of
the two-layer laminate is better with respect to the
monolayer sheet.
Examples 14-15
These examples illustrate the use of a poly-
ethylene/polypropylene mixture as the polyolefin in the
compositions of the invention. The blends are prepared
in accordance with the general procedure of Example 2
utilizing the ingredients and the amounts identified in
Table 8. The properties of the blended polymer composi-
tions thus obtained are also summarized in Table 8.

;~002695



TABLE 8
Inqredients Example 14 ExamPle 15
Shell 7C06 52.5 47.4
Dylark 332 20.0 20.0
Stereon 840A 5.0 5.0
Cain (HDPE) 7030 --- 5.0
Select-A-Sorb 20.0 20.0
TiO2 (CR 834) 2.5 2.5
Properties
Flexural Strength, psi 7310 7110
Flexural Modulus, Kpsi 391 357
HDT at 66 psi, C 117 115
Gardner Impact, in.lb. 14 21
Shrinkage, in./in. % 0.65 0.59

The properties show improved impact for Example
15 without loss of other desirable properties.
Examples 16-18
These examples illustrate the use of multi-
block, linear triblock and hydrogenated triblock copoly-
mers. In this example, the blends are processed on a
Leistritz counter-rotating, twin-screw, and injection
molded. The types and amounts of polymers blended in
these examples are summarized in the following Table 9.
Some of the mechanical properties of the blended poly-
mers also are summarized in the table.

Z002695



TABLE 9
Inqredients Example 16 Example 17 ExamPle 18
Profax 6523 76 76 76
Dylark 332 19 19 19
Stereon 840A 5 -- --
Kraton D1102 -- S --
Kraton G1652 -- -- 5
Properties
Flexural Modulus, Kpsi 280 264 247
Gardner Impact, in.lb. 17.4 4.2 4.0

The results summarized in Table 9 demonstrated the multi-
block styrene butadiene copolymers provide better
impact/modulus balance than the triblock copolymers.
Examples 19-20
These examples illustrate the use of impact-
modified styrene maleic anhydride copolymers in the
blended polymer compositions of the present invention.
The blends were processed in accordance with the general
procedure of Example 2 and molded. The composition of
the formulations of these two examples and some of these
properties are summarized in the following Table 10.

Z002695


TABLE 10
In~redients Example 19 Example 20
Aristich 4O40F1 52.4 52.4
Dylark 332 12.5 --
Dylark 238 -- 12.5
Stereon 840A 12.5 12.5
Select-A-Sorb 20 20
TiO2 (CR 834) 2.5 2.5
B-2252 0.1 0.1
Properties
Flexural Modulus, Kspi 223 228
Izod Impact, notched
(ft.lb./in.) 1.8 2.2
Gardner Impact,in.lbs.
at RT 143 288
at -20C 112 125
Linear Shrinkage,
in./in., % 0.7 0.7


2 A polypropylene copolymer from Aristich.
A stabilizer from Ciba-Geigy.
Examples 21-22
These examples illustrate the use of another
impact-modified styrene maleic anhydride copolymer in a
formulation containing talc. A control formulation also
is prepared which does not contain a compatibilizer.
The blends are prepared on a Banbury mixer and injection
molded (Van Dorn) by the general procedure of Example
1. The formulations and some of the properties obtained
from the blended formulations are summarized in the
following Table 11.

2002695

-54-

TABLE 11
Inqredients Control-3 ExamPle 21 Example 22
Exxon PD 7132 (PP) 60 57 55
Arco Arvyl 300 MR 20 20 20
Stereon 840 -- 3 --
Jet Fill 500 (talc) 20 20 20
Phillips KR03 -- -- 5
Properties
Melt Flow, g/10 min
(Cond. L) 1.4 1.0 1.3
Tensile Strength, psi 3460 3550 3810
Flexural Strength, psi 6300 6440 6870
Flexural Modulus, Kpsi 348 338 352
Notched Izod Impact
ft.lb./in. 0.7 1.0 1.0
HDT at 66 psi, C 115 110 106
Gardner Impact
(RT) in.lbs. 5 21 23
Linear Shrinkage
in./in. % 0.69 0.65 0.59

The above results demonstrate the improved impact
strength obtained when compatibilizers in accordance
with the present invention are included in the formula-
tions.
Example 23
This example illustrates the use of a high-den-
sity polyethylene as the polyolefin. Control-4 does not
contain the compatibilizer. The formulation of Example
23 and of Control-3, and some of the properties of the
blended formulations are summarized in the following
Table 12.

2002695


TABLE 12
Inqredients Control-3 Exam~le 23
Cain 7820 59.9 56.2
Cain 7040 20.0 18.7
Dylark 332 20.0 20.0
Stereon 840 -- 5.0
B-225 Stabilizer 0.1 0.1
Properties
Flexural Strength, psi 6764 6042
Flexural Modulus, Kpsi 214 203
HDT at 66 psi, C 97 97
&ardner Impact 1 RT ),
in.lbs. 9 28
Linear Shrinkage
in./in. % 1.34 1.27

The above results demonstrate the improved
linear shrinkage and Gardner impact properties obtained
when the compatibilizer is included in the blend.
Examples 24-25
These examples illustrate the use of functional-
ized block copolymers such as maleated styrene-butadi-
ene-styrene triblock copolymers. The blends are prepared
in a twin screw extruder and molded. The formulations
of Examples 24 and 25 and some of the properties of the
blends are summarized in the following Table 13.

Z002695


TABLE 13
Inqredients Example 24 Examvle 25
Profax 6523 85.5 85.5
Dylark 332 9.5 9.5
Kraton G1652 5 --
Kraton FG1901X -- 5
Properties
Flexural Modulus, Kpsi 220 223
HDT at 66 psi,C 96 109
Gardner Impact (RT)
in.lb. 14.7 29

The above results demonstrate that the maleated
triblock copolymer FG1901X provides improvements with
respect to Gardner impact and HDT when compared to non-
functionalized SBS.
Examples 26-27
These examples illustrate the use of Barex, a
barrier resin in the formulations of the present inven-
tion. The polymer blend is prepared in a twin screw
extruder and molded. The formulation and some of the
properties of the blended formulation are summarized in
the followin~ Table 14.

2002695

-57-

TABLE 14
InqredientsControl-5 Example 26 Example 27
Profax 6523 76 76 76
Dylark 332 19 19 19
Stereon 840A -- 3 5
Barex 210 5 2 --
Properties
Flexural Modulus, Kpsi 282 251 235
Gardner Impact (RT)
(in.lb.) <2 8.0 11 .6
Linear Shrinkage,
in./in. % 1.07 1.10 1.11
Oxygen Permeation,***
cc/m2/day 539* 593* 703**
* 8 mil sheet
** 7 mil sheet
*** at 0% relative humidity and 25C
The above results demonstrate that the addition
of a small amount of Barex of the composition of this
invention (Example 26) significantly improv~s the oxygen
impermeability.
Foams of the blended polymer compositions of
the present invention may be prepared by mixing low
boiling foaming agents with the blended polymer composi-
tions at a temperature above the softening point of the
polymer temperature and under a pressure which prevents
foaming of the mixture, followed by extrusion of the
foamable mixture into a zone of lower pressure wherein
the foamable mixture foams to provide the desired foamed
body. Particularly suitable foaming agents include halo-
hydrocarbons containing 1 or 2 carbon atoms such as
methyl chloride, ethyl chloride, etc. Low boiling hydro-
carbons also are suitable, and these include propane,

200Z69S

-58-

butane, pentane, etc. Mixtures of the above described
blowing agents also can be used. The amount of blowing
agent included in the foamable compositions is from
about 5 to about 30% by weight based on the total weight
of the blended polymer composition of the invention.
The foamed articles prepared in this manner may be semi-
rigid to rigid foams having densities of from 10 to
about 200 g/l. By varying the temperature during
extrusion of the foamable mixture, and by varying the
expanding agent used, the foams produced have varying
properties of open and closed cells. The foams are
particularly useful in the building industry and as
insulation.
Other uses for the blended polymer compositions
of this invention include refrigeration parts such as
inner liners, inner door panels, inner gaskets and trim,
trays and shelves, etc. The blended polymers are useful
in preparing parts for: the automotive industry;
communications such as telephones, ratio, TV, cassettes,
etc.; power tools; appliances; business machines; toys;
furniture; etc. The properties of the blended polymer
compositions of this invention can be varied to satisfy
the requirements of these different applications.
While the invention has been described and
illustrated with reference to certain preferred embodi-
ments thereof, those skilled in the art will appreciate
that various changes, modifications and substitutions
can be made therein without departing from the spirit of
the invention. For example, processing and molding tech-
niques other than those preferred as set forth herein-
above may be applicable due to variations in the desired
end product and uses, etc. Moreover, the specific
results observed with respect to the physical properties

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may vary depending on the specific polymers and formula-
tions selected and whether same are used alone or in
combination with each other, i.e., mixture, or other
known agents. Accordingly, such expected changes and
variations in results are contemplated in accordance
with the objects and practices of the present invention.
It is intended therefore, that the invention be limited
only by the scope of the claims which follow.