Note: Descriptions are shown in the official language in which they were submitted.
8CH--1931
~065089
This invention relates to thermopla~tic molding
compositions that are based on a copolymer of a vinyl aromatic
compound with an ~ unsaturated cyclic anhydride and a
hydrogenated, A-B-A block copolymer or a block copolymer of
the A'-B'-A' type or an acrylic graft polymerization copolymer
with or without a polyphenylene resin.
The term "polyphenylene ether resin" includes a family
of polymers well known to those skilled in the art, they are
made by a variety of catalytic and non-catalytic processes
from the corresponding phenols or reactive derivatives thereof.
By way of illustration, cartain of the following polyphenylene
ethers are discussed in Hay, U.S. Patents 3,306,874 and 3,306,875
issued February 28, 1967 and in Stamatoff, U.S. Patent 3,257,357
and 3,257,358 issued June 21, 1966. ~lso, the Bennett and
Cooper U.S. patents 3,639,656 issued February 1, 1972,
3,642,699 issued February 15, 1972 and 3,661,848 issued May 9,
1972 describe processes for the preparation of polyphenylene
ethers. In the Stamatoff patents, the polyphenylene ethers
are produced by reacting the corresponding phenolate ion with
an initiator, such as peroxy acid salt, an acid peroxide, a ~ ~ -
hypohalite, and the like, in the presence of a complexing
agent. Discloæures relating to non-catalytic proces6es, such
as oxidation with lead dioxide, silver oxide, etc., are
described in Price et al, U.S. patent 3,382,212 issued May 7,
1968.
The Cizek U.S. patent 3,383,435 issued May 14, 1968
discloses blends of polyphenylene ether resins and styrene
resins. The thermoplastic compositions disclosed by Cizek
- may include rubber-modified styrene resin, as well as crystal
polystyrene. The Carmelite, Kramer and Lee, Jr. U.S. patent
3,787,532 issued January 22, 1974, also discloses polypheny- -
lene ether containing compositions.
"
7F
8CH-1931
~065089
U.S. patent 3,660,531 - Shaw ,et al - issued May 2,
1972 discloses compositions of a polyphenylene ether styrene
resin and a styrene-butadiene-styrene block copolymer. These
~mpositions have a major proportion of polyphenylene ether
polymer.
There have been many attempts to upgrade the heat
distortion temperature and the impact resistance of vinyl
aromatic resins. One approach has been to provide copolymers
of the vinyl aromatic compounds with ~ unsaturated
cyclic anhydrides. In the case of styrene-maleic anhydride
` copolymers, a level of 20% of maleic anhydride increases the
heat distortion temperature but the resulting material is very
brittle.
Accordingly, it is a principla object to provide
improved compositions of vinyl aromatic resins that have higher
heat distortion temperatures and better impact strengths
; particularly as measured in terms of the Gardner impact tests.
According to the present invention, there is provided
a composition that is useful in the manufacture of thermo-
plastic molded articles. These thermoplastic molding compositions
comprise:
(a) from 40-95 parts by weight, preferably from 40-80
parts by weight of a copolymer of a vinyl aromatic compound
and an ~ , ~ -unsaturated cyclic anhydride;
(b) from 5-40 parts by weight, preferably 10-30 parts by
weight of a block copolymer selected from the group consisting
of:
i. hydrogenated block copolymers of the A-B-A type
wherein prior to hydrogenation; A is a polymerized mono-
alkenyl aromatic hydrocarbon block; B is a polymerized con-
jugated diene hydrocarbon block; the blocks A constituting
2-50 weight percent of the copolymer and the unsaturation of
- --2--
" .
,. : ~
8CH--1931
~o6S089
block B having been reduced by hydrogenation.
ii. block copolymers of the A'-B'-A' type wherein A
iæ a polymerized mono-alkenyl aromatic hydrocarbon block and
B ' is a polymerized conjugated diene block, the block B ' being
of higher molecular weight than that of the combined molecular
weight of terminal blocks A';
iii. emulsion graft polymerization product of an acrylic
monomer alone or in admixture with a styrene monomer on a
rubbery diene homopolymer of styrene-diene copolymer backbone;
and
iv. mixtures of the foregoing; and
(c) from 0-50 parts by weight, preferably 0-40 parts by
weight of a polyphenylene ether resin.
The preferred compositions will include 5-20 parts
by weight of the polyphenylene ether resin. The PPO containing
compositions will have a ratio of the copolymer of the vinyl
compound and the ~ , ~ -unsaturated cyclic anhydride to
polyphenylene ether resin that is greater than one. The
polyphenylene ether resins are preferably of the formula: ;~
` Q
~
n
; wherein the oxygen ether atom of one unit is connected to the
benzene nucleus of the next adjoining unit, n is a positive
integer and is at least 50, and each Q is a monovalent sub-
stituent selected from the group consisting of hydrogen,
halogen, hydrocaxbon radicals, halohydrocarbon radicals having
at least two carbon atoms between the halogen atom and the
phenyl nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy
', , .~, :
8CH-1931
~065089
radicals havinq at least two carbon atoms between the halogen
atom and phenyl nucleus, said radicals being free of a tertiary
alpha-carbon atom. The preparation of polyphenylene ether
resins corresponding to the above formula is described in
the above-mentioned patents of Hay and Stamatoff. Especially
preferred polyphenylene ether resins for purposes of the
present invention are those having alkyl substitution in the
two positions ortho to the oxygen ether atom -- i.e., where
each Q is alkyl, most preferably, having from 1 to 4 carbon
atoms. The most preferred polyphenylene ether resin for
purposes of the present invention is poly(2,6-dimenthyl-1,4-
phenylene) ether (each Q is methyl)~
The copolymers of the vinyl aromatic compounds and
the ~ , ~ -unsaturated cyclic anhydride are well known and
are described in the literature. The vinyl aromatic component
may be derived from compounds of the formula:
CRl = CHR2
R5 ~ R3
-~ ~ ~ R4
, R6 ~
wherein Rl and R2 are selected from the group consisting of
lower alkyl or alkenyl groups of from 1 to 6 carbon atoms and
hydrogen; R3 and R4 are selected from the group consisting of
chloro, bromo, hydrogen and lower alkyl of from 1 to 6 carbon
atoms; R5 and R6 are selected from the group consisting of
hydrogen and lower alkyl and alkenyl groups of from 1 to 6
-i carbon atoms or R5 and R6 may be concatenated together with
hydrocarbyl groups to form a naphthyl group. These compounds
are free of any substituent that has a tertiary carbon atom.
Styrene is the preferred vinyl aromatic compound. The
-4-
8CH--1931
.
1065089
unsaturated cyclic anhydrides include maleic anhydride,
citraconic anhydride, itaconic anhydride, aconitic anhydride
and the like. The preferred ~ unsaturated cyclic anhy-
dride is maleic anhydride.
These polymers may comprise 40 to 1 mole percent
of the ~ , ~ -unsaturated cyclic anhydride and from 60 to ~9
mole percent of a vinyl aromatic compound. The preferred
polymers will contain about 25-5 mole percent of the ~ ,
-unsaturated cyclic anhydride and 75-95 mole percent of
the vinyl aromatic compound. The preparation of these copoly-
mers are described in U.S. patent 2,971,939 - Baer - issued
February 14, 1961; U.S. Patent 3,336,267 - Zimmerman, et al
issued August 15, 1967; and U.S. Patent 2,769,804 - Hanson -
issued November 6, 1956.
With respect to the hydrogenated block copolymers
of the A-B-A type, they are made by means known in the art
~- and they are commercially available.
These materials are described in U,S. Patent
. .. . .
3,421,323 - Bennett Jr. - issued January 14, 1969.
Prior to hydrogenation, the end blocks of these
copolymers comprise homopolymers or copolymers preferably
prepared from alkenyl aromatic hydrocarbons and particularly
vinyl aromatic hydrocarbons wherein the aromatic moiety may
be either monocyclic or polycyclic. Typical monomers include
styrene, alpha methyl styrene, vinyl xylene, ethyl vinyl
xylene, vinyl naphthalene and the like or mixtures thereofO
The end blocks may be the same or different. The center block
may be derived from, for example, polyisoprene or poly-
butadiene.
The ratio of the copolymers and the average
molecular weights can vary broadly although the molecular
weight of center block should be greater than that of the
--5--
.. . . .
',' - -' ' " ' ''' .' .'' ~
.. ,: ,. . . .
8CH-1931
~065~89
combined terminal blocks. It is preferred to form terminal
blocks A having average molecular weights of 4,000-115,000
and center block B e.g., a polybutadiene block with an average
molecular weight of 20,000 - 450,000. Still more preferably,
the terminal blocks have average molecular weights of 8,000 -
60,000 while the polybutadiene polymer blocks has an average
molecular weight between 50,000 and 300,000. The terminal
blocks will preferably comprise 2-50% by weight, or more
preferably, 5-30% by weight of the total block polymer. The
preferred copolymers will be those formed from a copolymer
having a polybutadiene center block wherein 35-55%, or more
preferably, 40-50% of the butadiene carbon atoms are vinyl
side chains.
The hydrogenated copolymers may have the average
unsaturated reduced to from 95 to 5% of the original value.
It is preferred to have the unsaturation of the center block
B reduced to 10%, or more preferably, 5% of its original value~
The block copolymers are formed by tenchiques well
- known to those skilled in the art. Hydrogenation may be
conducted utilizing a variety of hydrogenation catalysts such
as nickel or kieselguhr, Raney nickel, copper chromate,
molybdenum sulfide and finely divided platinum or other noble
metals on a low surface area carrier.
Hydrogenation may be ~ nducted at any desired
temperature or pressure, from atmospheric to 300 p.s.i.g.
the usual range being between 100 and 1000 p.s.i.g. at
temperatures from 750F to 600 F for times between 0.1 to
24 hours, preferably from 0.2-8 hours.
Hydrogenated block copolymers such as Kraton
G-GXT-0650, Kraton G-GXT-0772 and Kraton G-GXT-0782 from
Shell Chemical Compahy, Polymers Division have been found
useable according to this invention.
With respect to the A'-B'-A' block copolymers,
.
. . , ': .- - . ,
8CH-1931
10651~89
they may be made by means well known in the art and are also
available commercially from a number of sources.
Block copolymers of vinyl aromatic compounds and
conjugated dienes are described in Kennedy, et al Editor,
Polymer Chemistry of Synthetic Elastomers, Interscience,
Vol. 23, Part II, 1969, pages 553-559. In general, they will
be of the A-s-A' type in which the center and end blocks
can vary. In the compositions of this invention, the central
block B, will preferably be that of a conjugated diene, e.g,,
butadiene; isoprene; 1,3-pentadiene: 2,3-dimethyl-butadiene,
and the like or mixtures of the foregoing. The terminal
blocks A and A'~ will be the same or different, but will
always be derived from a vinyl aromatic compound, e.g.,
styrene, ~-methyl styrene, vinyl toluene, vinyl xylene, vinyl
naphthalene, or mixtures of any of the foregoing. In the most
preferred compositions, the block copolymer will have terminal
. .
; blocks A and A' comprised of polystyrene and center block B
comprised o$ polybutadiene.
The ratio of the comonomers can vary broadly, so
long as the molecular weight center block is greater than
that of the combined terminal blocks. Preferably, with the ~ -
above limitation, the molecular weight of the terminal blocks
each will range from about 2000 to about 100,000 while that
of the center block will range from about 25,000 to about
1,000,000.
The block copolymers are made by an organometallic
initiated polymerization process using, for example sodium
or lithium metal an organic derivative thereof. The diene
monomers can be polymerized with a monofunctional or di-
functional initiator, as is described in Kennedy et al,
mentioned above.
In one process, the block copolymer is prepared by
-7-
... . . ..
,-., .' .' ...", ', ' ., ~, ,.
8CH-1931
106S~)89
dissolving the conjugated diene, e.g., butadiene, in an aro-
matic hydrocarbon solvent, e.g., xylene, toluene, etc., and
adding 0.3 to 7.5 millimoles/100 parts of monomer of an
organodilithium initiator, e.g., dilithiobutane, dilithio-
stilbene, etc. Polymerization of the diene is completed and
then the vinyl aromatic compound is added and polymerization
of this is completed to form the block copolymer. The product
is precipitated and deactivated, e.g., with alcohol, such
as ethanol or isopropanol and purified by redissolving in
hydrocarbon and reprecipitating with alcohol.
Full descriptive details of such a process are
given in Zelinski, U.S. patent 3,251,905 issued May 17, 1966.
- In another process, the block copolymer is built up
sequentially using, e.g., a secondary or tertiary alkyl
lithium compound at about 100-2000 parts per million based on
the total weight of the monomers and a polymerization
temperature in the range 20-65C. For example, styrene is
dissolved in cyclohexane at 32C. and treated with 5530 parts
per million of secondary butyl lithium. After polymerization
~ 20 is complete, isoprene is injected and polymerization is
`~ continued at 55-57C. Finally styrene is added and the third
block is polymerized. The product can be recovered as
described above. Full descriptive details of such a process
are given in Holden et al, U.S. patent 3,231,635- issued
January 25, 1966. These materials are commercially available
as Kraton resins.
The graft polymerization product of an a¢rylic
monomer and a diene rubber preferably comprises (1) from
~ about 20-80% by weight of a backbone polymer of the units of
i 30 butadiene or butadiene and styrene, wherein the butadiene
units are present in quantities of at least 40% by weight of
the backbone polymer, (2) 80-20% by weight of an acrylic
-8-
8CH-1931
1065089
monomer graft polymerlzed to (l); said acrylic monomer units
being selected from the group consisting of lower alkyl meth-
acrylates, alicyclic methacrylates and alkyl acrylates, and
(3) 0 to 60% by weight of a styrene monomer graft polymerized
to (1) or (2); sequ~ntially or simultaneously with the
polymerization of (2).
The graft polymerization product of an acrylic
monomer alone or with styrene monomer and the rubbery diene
polymer or copolymer may be prepared by known techniques,
typically by emulsion polymerization. They may be formed from
a styrens-butadiene copolymer latex and a monomeric material
such as methyl methacrylate alone or with another compound
having a single vinylidene group copolymerizable therewith,
e.g., styrene~ For example, in the preparation of a re-
presentative material, 85-65 parts by weight of monomeric
methyl methacrylate or monomeric methyl methacrylate to the
extent of at least 55% and preferably as much as 75% by
weight in admixture with another monomer which copolymerizes
therewith, such as ethyl acrylate, acrylonitrile, vinylidene
chloride, styrene, and similar ungaturated compounds containing
a single vinylidene group, is added to 15-35 part~ by weight
of solids in a styrene-butadiene copolymer latex. The co
polymer solids in the latex comprise about 10-50% by weight
of styrene and about 90-50% by weight of butadiene and the
molecular weight thereof is within the range of about 25,000
to l,S00,000. The copolymer latex of solids in water contains
a dispersing agent such as sodium oleate or the like to
maintain the copolymer in emulsion. Interpolymerization of
the monomer or monomeric mixture with the copolymer solids
emulsified in water is brought about in the presence of a
free-radical generating catalyst and a polymerization
- regulator which serves as a chain transfer agent, at a
8CH-1931
106508~
temperature of the order of 15C to 80C . Coagulation of the
interpolymerized product is then effected with a calcium
chloride solution, for instance, whereupon it is filtered,
washed and dri~d. Other graft copolymers and differing from
the above only in the ratio of monomeric material solely or
preponderantly of methyl methacrylate to the butadiene-
styrene copolymer latex in the presence of which it is poly-
merized extends from 85-25 parts by weight of the former to
15-75 parts by weight of the latter. These materlals may
extend in physical properties from relatively rigid compositions
to rubbery compositions. A preferred commercially available
material is Acryloid KM 611 which is sold by Rohm ~ Haas.
Also, U.S. patent 2,943,074 - Feuer - issued June 28, 1960 and
U.S. patent 2,857,360 - Feuer-- issued October 21, 1958,
contain additional information as to the preparation of these
materials. A preferred material is described in U.S. patent
2,943,074, column 4, preparation "D" and converted to
emulsified polymer "B" as described therein.
The compositions of this invention will preferably
include deom 40-80 parts of the copolymer of a vinyl aromatic
compound and a ~ , ~ -unsaturated cyclic anhydride, and most
preferably from 60-75 parts by weight of this material. The
block copolymer of the A-B-A type or A'-B'~A' type, or the -
- acrylic graft polymerization product, will preferably be
present at from 10-40 parts by weight and most preferably at
20-30 parts by weight. If employed, the polyphenylene ether
resins are preferably present at a level of from 1-40 parts by
weight and preferably at a level of from 5-30 parts by weight.
~he compositions of the invention may also include
reinforcing fillers, such as aluminum, iron or nickel, and
the like, and non-metals, such as carbon filaments, silicates,
such as acicular calcium silicate, asbestos, titanium dioxide,
--10--
~ . '' ' '
8CH--1931
~065089
potassium titanate and titanate whiskers, glass flakes and
fibers. It is also to be understood that, unless the filler
adds to the strength and stiffness of the composition, it is
only a filler and not a reinforcing filler,as contemplated
herein. In particular, the reinforcing fillers increase the
flexural strength, the flexural modulus, the tensile strength
and the heat distortion temperature.
Although it is only necessary to have at least a
reinforcing amount of the reinforcement present, in general,
the combination of components (a) and tb) will comprise from
about 10 to about 90 parts by weight and the filler will com-
prise from a~out 10 to about 90 parts by weight of the total
composition.
In particular, the preferred reinforcing fillers
-- are of glass and it is preferred to use fibrous glass filaments
comprised of line-aluminum borosilicate glass that is
relatively soda free. This is known as "E" glass. However,
other glasses are useful where electrical properties are not so
important, e.g., the low soda glass known as "C" glass. The
filaments are made b~y standard processes, e.g., by steam or
air blowing, flame blowing and mechanical pulling. The pre-
ferred filaments for plastics reinforcement are made by
mechanical pulling. The filament diameters range from about
- 0.000112 to 0.00075 inch, but this is not critical to the
present invention.
In general, best properties will be obtained if the
sized filamentous glass reinforcement comprises from about 1
to about 80% by weight based on the combined weight of glass
'`A and polymers and preferably from about 10 to about 50% by
weight. Especially preferably the glass will comprise from
about 10 to about 40% by weight based on the combined weight
of glass and resin. Generally, for direct molding use, up to
.
8CH- 1 9 31
~()6S~9
about 60% of glass can be present without causing flow problems.
However, it is useful also to prepare the compositions con-
taining substantially greater quantities, e.g., up to 70-80%
by weight of glass. These concentrates can then be custom
blended with blends of resins that are not glass reinforced to
provide any desired glass content of a lower value.
The length of glass filaments and whether or not
they are bundled into fibers and the fibers bundled in turn
to yarns, ropes or rovings, or woven into mates, and the like,
are also not critical to the invention. However, in pre-
paring the present compositions it is convenient to use the
filamentous glass in form of chopped strands of from about
1/8" to about 1" long, preferably less than 1/4" long. In
articles molded from the compositions, on the other hand, even
shorter lengths will be encountered because, during compounding,
considerable fragmentation will occur. This is desirable,
however, because the best properties are exhibited by thermo-
plastic injection molded articles in which the ~ilament
lengths lie between about 0.000005" and 0.125 (1/8").
It is a preferred feature of this invention also
to provide flame retardant thermoplastic compositions of vinyl
aro~atic~ -unsaturated cyclic anhydrides as defined
above by modifying said compositions to include a flame-
retardant additive in a minor proportion but in an amount at
least sufficient to render the composition non-burning or
self-extinguishing.
Particular glame retardants which may be used are
well known and are described in the literature.
The compositions may be prepared by tumbling the
components, extruding the mixed powders into a continuous strand,
chopping the ~trands into pellets and thereafter molding the
pellets into the desired shape. These techniques are well
known to those skilled in this are and are not a critical
--12--
' ~ ' '
8CH-1931
1~65~89
feature of the invention.
The present invention is further illustrated in
the following examples which are set forth as further descrip-
tions of the invention, but are not to be construed as limiting
the invention thereto.
EæAMPLE I
The compositions listed in Table 1 were prepared
by compounding the components on a 28 mm. W.P. extruder at
a feed temperature of 550F, a rear temperature of 570F, a
10front temperature of 580F, and a die temperature of 590F.
The materials were molded on a 3 oz. ~ewbury injection molding
machine at 400F cylinder temperature and 130F mold
temperature. The cycle time was 35 seconds.
.,. : -
- -13-
8CH--1931
1065089
o , o o
_, , ~ ~ , , I
o I o o I , I
0
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.: H ~ l O l O
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I O I O
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~. U ' N
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I I 0 .4 rl ~ U Ei
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,, o.4 I ~ ~ o u
ZI ~ O ~ ~::
u~ I ~ 1: 0 ,3~ us~
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. .
8CH-1931
~065089
0 o
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r~ o I I u~
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U~
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cn t~ R u ~ 0 4~ ~-
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1-1 H H 'H
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8CH-1931
106S~89
The compositions described in Table 1 were evaluated
for physical properties and the results are reported in
Table 2.
, .
~ .
., .
:
-16-
`` 8CH-1931
~065089
,~ o o~ , o ,,
a~ . ~ I o
~ ~ , U~
U~
:, 1 0 g ' o ~ :
r I H ~`1 I N
I O OD
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h
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H ~ H ~ U~ O
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$ ~ '~
8CH-1931
1065089
o ~ I o ~p
~0 ~ O O I O N
~1 ~ ~ ~ I 11')
0 ~0
O I aD I O O
t`~ d' ~ I O
_l
O CO
t~l D OD I O ~D
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CD C~ I O -I
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:.
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:,, i ~n ~ I I
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e
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- . ,- : . : ::: ~ :, -: , : : . :
8CH-1931
1~6~089
An analysis of this Table shows that the compositions
of this invention have good impact strengths and relatively
high heat dis~ortion temperature.
Other compositions may be prepared by using the
following materials:
A. styrene-maleic anhydride copolymer prepared
accoding to Example II, run 10 of U.S. 3,336,267.
B. A-B-A block copolymer prepared according to
run B of U.S. 3,431,323 - Jones - issued March 4, 1969.
c. A'-B'-A' block copolymer of ~tyrene-butadiene-
styrene prepared according to Example II of U.S. 3,265,765 -
Holden - issued August 9, 1966.
D. emulsion graft polymerization product of an
acrylic monomer and a rubbery diene copolymer as prepared in
U,S. 2,843,074, column 4, emulsified polymer "B" .
-~ EXAMPLE II
~;' The following compositions were prepared using
procedures analogous to those employed in Example I:
SamPle No. 19 20 21 _22 23 24
Components
(~arts bv weiaht)
I poly~2,6-dimethyl-
1,4-Ehenylene) ether
(PPO'~General Elec-
tric Co.) -- 10 -- 10 -- 10
II A-B-A copolymera 70 60 -- -- -- --
~;~ III A'-B'-A- copolymerb -- -- -- -- 30 30
- IV emulsion graft poly-
merization product of
an acrylic monomer on
a rubbery diene poly-
merC -- -- 25 25 -- -- -
V styrene-maleic 3nhy-
dride copolymer 30 30 75 65 70 60
a Kraton GXT-0650, Shell Chemical Co.
b Kraton 4119, Shell Chemical Co.
c Acryloid ~ 611 Rohm & Haas.
d Dylark 232, Sinclair Koppers; crystal grade.
--19--
.
~ ', , - ' ':
8CH-1931
1065~89
The compositions of Example II were evaluated for
physical properties and the results are reported in Table 3.
TABLE 3
19 2021 22 23 24
~otched Izod Imp.
(ft.lb./in.n) 1.3 7.70.40.4 2.4 5.5
H8at Distortion Temp. __ __ __ _
Gardner Impact (in./lb.) 63 155 10 10 65 81
- 10 Tensile Strength (p8i)5700 61008100850040004700
Obviously other modifications and variations of the
present invention are possible in the light of the above
teachings. It is, therefore, to be understood that changes
may be made in the particular embodiments of the invention
described which are within the full intended scope of the
invcntion as dofined by the appended cl~ims.
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