Blends of polyketones and carboxylated, hydrogenated block copolymers

Polymer blends comprising a major proportion of linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, a minor proportion of a carboxylated, partially hydrogenated two-block copolymer of an alkenyl arene and a conjugated alkadiene and, optionally, a minor proportion of an .alpha.-olefin/.alpha.,.beta.-ethylenically unsaturated carboxylic acid polymer, demonstrate improved properties of low temperature toughness.

FIELD OF THE INVENTION 
The present invention relates to improved polymer blends comprising 
predominantly a linear alternating polymer of carbon monoxide and at least 
one ethylenically unsaturated hydrocarbon. More particularly, the 
invention relates to a blend of the linear alternating polymer with a 
minor proportion of a carboxylated, partially hydrogenated two-block 
copolymer and, optionally, a polymer of ethylene and 
.alpha.,.beta.-ethylenically unsaturated carboxylic acid. 
BACKGROUND OF THE INVENTION 
The class of polymers of carbon monoxide and olefin(s) has been known for 
some time. Brubaker, U.S. Pat. No. 2,495,286, produced such polymers of 
relatively low carbon monoxide content in the presence of free radical 
initiators, e.g., peroxy compounds. U.K. 1,081,304 produced similar 
polymers of higher carbon monoxide content in the presence of 
alkylphosphine complexes of palladium. Nozaki extended the process of 
arylphosphine complexes of palladium moieties and certain inert solvents. 
See, for example, U.S. Pat. No. 3,694,412. 
More recently, the class of linear alternating polymers of carbon monoxide 
and at least one ethylenically unsaturated hydrocarbon, also known as 
polyketones or polyketone polymers, has become of greater interest in part 
because of the greater availability of the polymers. The more recent 
general processes for the production of the polyketone polymers are 
illustrated by a number of published European Patent Applications 
including 121,965, 181,014, 213,671, and 257,663. The processes involve 
the use of a catalyst composition formed from a compound of a Group VIII 
metal selected from palladium, cobalt or nickel, the anion of a 
non-hydrohalogenic acid having a pKa below about 6, preferably below 2, 
and a bidentate ligand of phosphorus, arsenic or antimony. 
The resulting polymers are relatively high moleclar weight thermoplastics 
having established utility in the production of shaped articles such as 
containers for the food and drink industry which are produced by 
processing the polymers according to the methods conventional for the 
processing of thermoplastics. For some particular applications, however, 
it has been found to be desirable to have properties somewhat different 
from those of the polyketone polymers. It would be of advantage to retain 
the desirable properties of the polyketone polymer and yet improve other 
properties. These advantages are often obtained through the provision of a 
polymer blend. 
In copending U.S. patent application Ser. No. 203,975, filed June 8, 1988, 
there are disclosed blends of polyketone polymers and maleated, partially 
hydrogenated block copolymers. In copending U.S. patent application Ser. 
No. 203,960, filed June 8, 1988 there are described blends of polyketone 
polymers and copolymers of ethylene and .alpha.,.beta.-ethylenically 
unsaturated carboxylic acids. 
SUMMARY OF THE INVENTION 
The present invention provides improved blends of carbon monoxide and 
ethylenically unsaturated hydrocarbon with other polymeric material. More 
particularly, the present invention provides blends of the linear 
alternating polymer with certain carboxylated, partially hydrogenated 
two-block copolymers and, optionally, copolymer of .alpha.-olefin and 
.alpha.,.beta.-ethylenically unsaturated carboxylic acid. Such blends 
demonstrate improved physical properties of low temperature toughness, 
without undue loss of stiffness or tensile strength.

DESCRIPTION OF THE INVENTION 
The polyketone polymers which are employed as the major component of the 
blends of the invention are linear alternating polymers of carbon monoxide 
and at least one ethylenically unsaturated hydrocarbon. Suitable 
ethylenically unsaturated hydrocarbons for use as precursors of the 
polyketone polymers have up to 20 carbon atoms inclusive, preferably up to 
10 carbon atoms inclusive, and are aliphatic such as ethylene and other 
.alpha.-olefins including propylene, 1-butene, isobutylene, 1-hexene, 
1-octene and 1-dodecene, or are arylaliphatic having an aryl substituent 
on an otherwise aliphatic molecule, particularly an aryl substituent on a 
carbon atom of the ethylenic unsaturation. Illustrative of this latter 
class of ethylenically unsaturated hydrocarbons are styrene, 
p-methylstyrene, m-isopropylstyrene and p-ethylstyrene. The preferred 
polyketone polymers are copolymers of carbon monoxide and ethylene or are 
terpolymers of carbon monoxide, ethylene and a second ethylenically 
unsaturated hydrocarbon of at least 3 carbon atoms, particularly an 
.alpha.-olefin such as propylene. 
The structure of the polyketone polymers is that of a linear alternating 
polymer and the polymer will contain substantially one molecule of carbon 
monoxide for each molecule of hydrocarbon. When the preferred terpolymers 
are utilized in the blends of the invention there will be within the 
terpolymer at least two units incorporating a moiety of ethylene for each 
unit incorporating a moiety of the second hydrocarbon. Preferably there 
will be from about 10 units to about 100 units incorporating a moiety of 
ethylene for each unit incorporating a moiety of the second hydrocarbon. 
The polymer chain is therefore represented by the following repeating 
formula 
EQU --CO--CH.sub.2 --CH.sub.2)].sub.x [CO--G)].sub.y (II) 
wherein G is the moiety of the second ethylenically unsaturated hydrocarbon 
of at least 3 carbon atoms polymerized through the ethylenic unsaturation. 
The --CO--CH.sub.2 CH.sub.2 -- units and any --CO--G-- units are found 
randomly throughout the polymer chain and the ratio of y:x is no more than 
about 0.5. In the modification where the preferred copolymers of carbon 
monoxide and ethylene are employed there will be no second hydrocarbon 
present and the copolymers are represented by the above formula I wherein 
y is 0. When y is other than 0, i.e., terpolymers are employed, the 
preferred ratio of y:x is from about 0.01 to about 0.1. The end groups or 
"caps" of the polymer chain will depend upon what materials are present 
during the production of the polymer and whether or how the polymer has 
been purified. The precise properties of the polymers do not appear to 
depend upon the end groups to any considerable extent so that the polymers 
are fairly represented by the above formula for the polymeric chain. Of 
particular interest are the polyketone polymers of number average 
molecular weight from about 1000 to about 200,000, particularly those of 
number average molecular weight from about 20,000 to about 90,000, as 
determined by gel permeation chromatography. The physical properties of 
the polyketone polymers will depend in part on the molecular weight, 
whether the polymer is a copolymer or a terpolymer and, in the case of 
terpolymers, the nature of and the proportion of the second hydrocarbon 
present. Typical melting points of the polymers are from about 175.degree. 
C. to about 300.degree. C. with polymers of melting points from about 
210.degree. C. to about 270.degree. C. being preferred. The polymers will 
have a limiting viscosity number (LVN), measured in dl/g in m-cresol at 
60.degree. C. in a standard capillary viscosity measuring device, from 
about 0.5 to about 10, preferably from about 0.8 to about 4. 
The method for the production of the polyketone polymers is illustrated by 
the above published European Patent Applications. In a typical 
modification, the carbon monoxide and hydrocarbon monomers are contacted 
under polymerization conditions in a reaction diluent in the presence of a 
catalyst composition formed from a palladium compound, the anion of a 
non-hydrohalogenic acid having a pKa below 2 (measured in water at 
18.degree. C.) and a bidentate ligand of phosphorus. The scope of the 
polymerization process is extensive but, without wishing to be limited, a 
preferred catalyst composition is formed from a palladium alkanoate, 
preferably palladium acetate, the anion of trifluoroacetic acid or 
p-toluenesulfonic acid and a bidentate phosphorus ligand selected from 
1,3-bis(diphenylphosphino)propane or 
1,3-bis[di(2-methoxyphenyl)phosphino]-propane. 
The reaction diluent in which the polymerization is conducted is preferably 
a lower alkanol, e.g., methanol or ethanol, and methanol is particularly 
preferred. The reactants, catalyst composition and reaction diluent are 
contacted during polymerization by conventional methods such as shaking or 
stirring in a suitable reaction vessel. The polymerization conditions 
include a reaction temperature from about 20.degree. C. to about 
150.degree. C. with temperatures in the range from about 50.degree. C. to 
about 135.degree. C. being preferred. Typical reaction pressures are from 
about 1 atmosphere to about 200 atmospheres with pressures from about 10 
atmospheres to about 100 atmospheres being more commonly employed. 
Subsequent to reaction the reactor and contents are cooled and the 
pressure released. The polyketone polymer is generally obtained as a 
suspension in the reaction diluent and is recovered by well known 
procedures such as filtration or decantation. The polyketone product is 
employed in the blends of the invention as recovered or the polymer 
product is purified as by contact with a solvent or extracting agent which 
is selective for catalyst residues. 
A minor component of the blends of the invention is a carboxylated, 
partially hydrogenated diblock copolymer. The block copolymers from which 
the blend component is produced is a two-block polymer containing one 
block of polymerized at least predominantly alkenyl arene and one block of 
polymerized at least predominantly conjugated alkadiene. The alkenyl arene 
portion of the block copolymer is preferably polymerized styrene or 
alkylated styrene including ring alkylated styrene and side chain 
alkylated styrene. Such alkenyl arenes are illustrated by styrene, 
p-methylstyrene, 1,3-dimethylstyrene, .alpha.-methylstyrene, 
o-ethylstyrene, p-t-butylstyrene and m-i-propylstyrene. Of these, styrene 
and .alpha.-methylstyrene are preferred, especially styrene. The 
polymerized alkenyl arene portion of the block copolymer, commonly termed 
an "A" block in terminology associated with block copolymers, is a 
polymerized segment of one or more alkenyl arenes. 
The second block of the block copolymer used as precursor of the blend 
component, commonly termed a "B" block, is polymerized conjugated 
alkadiene wherein the alkadiene preferably has from 4 to 8 carbon atoms 
inclusive. Illustrative of such conjugated alkadienes are 1,3-butadiene 
(butadiene), 2-methyl-1,3-butadiene (isoprene), 
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene) and 1,3-hexadiene. 
The preferred conjugated alkadiene monomers are butadiene and isoprene. 
The B block suitably contains one or more alkadienes but preferably only a 
single conjugated alkadiene. 
The production of the two-block or diblock polymer is accomplished by 
polymerization procedures which are well known in the art. In a generally 
preferred procedure, alkenyl arene is polymerized through the use of an 
alkyl lithium initiator, preferably a secondary-alkyl lithium initiator. 
The conjugated alkadiene is then added to the resulting mixture to form 
the polymerized alkadiene portion of the block copolymer. If the 
polymerization of the alkenyl arene is essentially complete before the 
conjugated alkadiene is introduced, each block will be a substantially 
homopolymer block of the monomer employed in its production. 
Alternatively, if the conjugated alkadiene is introduced before the 
polymerization of alkenyl arene is complete, each of the resulting blocks 
is termed "tapered" and contains a relatively small proportion of the 
monomer of the other block. The production of homopolymeric or tapered 
block copolymers is well known in the art and both types of diblock 
copolymers are usefully employed in the production of the component of the 
blends of the invention, provided that each block is polymerized at least 
predominantly alkenyl arene or conjugated alkadiene. 
Within the B block of the block copolymer, several modifications of 
structure are possible. In what is termed 1,2-polymerization, the 
polymerization of the conjugated alkadiene involves only a single 
carbon-carbon double bond of the conjugated alkadiene and the resulting 
polymeric chain contains pendant alkenyl groups. Alternatively, in 
1,4-polymerization, the polymerization of the conjugated alkadiene 
involves both carbon-carbon double bonds with all four carbon atoms of the 
conjugated double bonds being incorporated within the polymer chain which 
then contains residual ethylenic unsaturation. The extent of 1,2- or 
1,4-polymerization and the control of the ratio of these polymerization 
types is conventional and well known in the art. 
Preferably, the blend components of the invention are produced from diblock 
polymers having elastomeric properties. These polymers will contain B 
blocks having a 1,2-structure content of from about 40% to about 98%, 
preferably from about 60% to about 98% . The proportion of A block within 
the diblock polymer is from about 2% to about 60% based on total polymer, 
with A block contents of from about 2% by weight to about 40% by weight, 
same basis, being preferred. 
The average molecular weight of the diblock copolymers and the individual 
blocks thereof will vary within certain limits. The average molecular 
weight of the diblock copolymers is from about 11,000 to about 700,000. 
The A block will suitably have an average molecular weight of from about 
1,000 to about 125,000, preferably from about 1,000 to about 60,000 while 
the B block will have an average molecular weight from about 10,000 to 
about 450,000, preferably from about 10,000 to about 150,000. The 
molecular weights are most accurately determined by gel permeation 
chromatography or by gel permeation-low angle light scattering. The 
production and characterization of these diblock or A-B copolymers is well 
known and certain of the polymers are commercially available being 
marketed under the trademark KRATON.RTM. by Shell Chemical Company. 
To prepare the component of the blends of the invention, the diblock 
copolymers are hydrogenated and carboxylated. The hydrogenation of the A-B 
polymers is conducted by a number of well established procedures including 
hydrogenation in the presence of catalysts such as Raney nickel, noble 
metals such as platinum or palladium and soluble transition metal 
catalysts. The hydrogenation processes which are suitably employed to 
produce precursors of the blend components are those which hydrogenate a 
substantial proportion of the aliphatic, i.e., ethylenic, unsaturation 
while hydrogenating at most a small and generally negligible proportion of 
the aromatic unsaturation. These hydrogenation processes typically include 
dissolving the block copolymer in an inert hydrocarbon diluent such as 
cyclohexane and contacting the polymer with molecular hydrogen in the 
presence of a soluble transition metal hydrogenation catalyst. Such a 
procedure is entirely conventional and results in the production of 
partially hydrogenated block copolymers having no more than about 20% 
residual ethylenic unsaturation in the aliphatic block. Preferred 
partially hydrogenated polymers have less than 10% of the original 
ethylenic unsaturation and preferably less than 2% of the original 
ethylenic unsaturation. These partially hydrogenated block copolymers are 
conventional and certain of the partially hydrogenated polymers are 
commercial, being marketed under the trademark SHELLVIS.RTM. by Shell 
Chemical Company. 
The component of the blends of the invention is produced from the partially 
hydrogenated diblock copolymer by a two-step process of metalation and 
carboxylation. The metalation step serves to incorporate a metallic 
species as a substituent on a carbon atom of an aromatic ring of the block 
copolymer and to a lesser extent upon a benzylic carbon atom of the 
aromatic portion of the copolymer molecule. This step is accomplished by 
contacting the partially hydrogenated diblock copolymer with a reactive 
metal compound and an amine promoter. A variety of metal compounds of 
alkali metals and alkaline earth metals are suitable in the metalation but 
compounds of alkali metals are preferred. Compounds of sodium, potassium, 
rubidium or cesium are satisfactory but largely because of availability 
the compounds most frequently used are lithium compounds. Although other 
compounds such as the hydrides are useful, the preferred lithium compounds 
are lithium alkyls wherein the alkyl has up to about 10 carbon atoms. 
Representative lithium alkyls are methyllithium, isopropyllithium, 
t-butyllithium and n-dodecyllithium. Sec-butyllithium is a preferred alkyl 
lithium compound. Metalation takes place in the presence of a reaction 
promotor to reduce the severity of the conditions under which metalation 
takes place. The metalation promotor is suitably a diamine having all 
valences of each nitrogen atom substituted with an alkyl group. Cyclic 
diamines such as the N,N,N',N'-tetraalkyldiaminocyclohexanes, e.g., 
N,N,N'N'-tetramethyl-1,2-diaminocyclohexane or 
N,N,N',N'-tetraethyl-1,4-diaminocyclohexane are suitable, but the 
preferred amine metalation promoters are the so-called "bridgehead" 
diamines such as sparteine and triethylenediamine. 
The amine metalation promoter is employed in a quantity of from about 0.01 
equivalent to about 100 equivalents per equivalent of lithium alkyl, 
preferably from about 0.1 equivalent to about 10 equivalents of promoter 
per equivalent of alkyl lithium. The lithium alkyl is employed in a 
quantity of from about 0.001 equivalent to about 3 equivalents per 
equivalent of aromatic moiety present in the partially hydrogenated 
diblock polymer. Quantities of lithium alkyl from about 0.01 equivalent to 
about 1 equivalent of aromatic moiety are preferred. The metalation 
reaction is carried out in the liquid phase in an inert reaction diluent 
which preferably is a saturated aliphatic hydrocarbon such as cyclohexane. 
Reaction temperatures are generally from about -70.degree. C. to about 
150.degree. C. with the range of reaction temperatures from about 
25.degree. C. to 75.degree. C. being preferred. The reaction pressure is 
sufficient to maintain the reaction mixture in the liquid phase. Such 
pressures are typically up to about 10 atmospheres. 
The metalated polymers are recoverable by conventional methods but are 
customarily further reacted with carbon dioxide in the carboxylation step 
without isolation. The carboxylation of the metalated, partially 
hydrogenated diblock copolymer is most easily accomplished by passing 
gaseous carbon dioxide into the mixture in which the metalated polymer is 
produced. Reaction conditions similar to those of the metalation process 
are utilized and carbon dioxide is typically added until no further 
reaction takes place. The resulting polymer product is the lithium salt of 
the carboxylated, partially hydrogenated diblock copolymer which is 
generally soluble in the medium of its production. The carboxylated 
polymer is obtained upon acidification of the salt. Although a variety of 
acids both inorganic acid and organic are suitable for this purpose, the 
preferred acids are organic acids such as acetic acid or citric acid. 
Acidification of the product mixture containing the salt of the 
carboxylated polymer produces the carboxylated polymer in the acid form 
which is generally insoluble and is recovered by conventional methods such 
as filtration and decantation. The carboxylated polymer is used as 
recovered and is purified to remove any occluded salt if desired, by 
conventional methods. 
The chemistry of the formation of the carboxylated polymer is not easily 
depicted because of the complexity of the reaction. However, the overall 
reaction scheme and illustrative products are illustrated by the following 
sequence. 
##STR1## 
wherein the products are exemplary of principal reaction types and the 
wavy lines represent uninvolved portions of the polymer molecule. It 
should be appreciated that the depicted products are illustrative only and 
other products may and often do occur in minor amounts in which (a) 
metalation/carboxylation has taken place in the aliphatic portion of the 
polymer molecule on carbon atoms allylic to residual unsaturation, (b) 
more than one carboxyl group is introduced onto a single aromatic ring or 
(c) more than one of the above reaction types has taken place. The 
carboxylation process generally introduces from about 0.1% by weight of 
carboxyl group to about 10% by weight of carboxyl group, based on 
carboxylated, partially hydrogenated diblock polymer. Carboxylated 
polymers having from about 1% by weight to about 5% by weight on the same 
basis are preferred. 
The production of carboxylated polymers by general processes of metalation 
and carboxylation are broadly well known and conventional. A general 
overall process by which these blend components are produced is included 
within copending U.S. patent application Ser. No. 152,705, filed Feb. 5, 
1988, which also provides general statements about incorporation of 
functionalized, partially hydrogenated block copolymers in engineering 
thermoplastics. 
In the blends of the invention, a third component is optionally present. 
This optional component is a polymer of an .alpha.-olefin and an 
.alpha.,.beta.-ethylenically unsaturated carboxylic acid. The 
.alpha.-olefin portion of the optional blend component is an 
.alpha.-olefin of up to 10 carbon atoms inclusive such as ethylene, 
propylene, 1-butene, isobutylene, 1-octene and 1-decene. Preferred 
.alpha.-olefins are straight-chain .alpha.-olefins of up to 4 carbon atoms 
inclusive, especially ethylene or propylene. Ethylene is particularly 
preferred. The .alpha.,.beta.-ethylenically unsaturated carboxylic acid is 
a 2-alkenoic acid of up to 10 carbon atoms and is illustrated by acrylic 
acid, methacrylic acid, 2-hexenoic acid and 2-decenoic acid. The preferred 
unsaturated carboxylic acids have up to 4 carbon atoms inclusive and these 
acids are acrylic acid, methacrylic acid and crotonic acid, of which 
acrylic acid and methacrylic acid are particularly preferred. The 
.alpha.,.beta.-ethylenically unsaturated carboxylic acid is present in the 
polymer with .alpha.-olefin in an amount from about 1% by mol to about 30% 
by mol, based on total polymer. Amounts of unsaturated acid from about 1% 
by mol to about 15% by mol on the same basis are preferred. 
The optional blend component is suitably a copolymer of the .alpha.-olefin 
and the .alpha.,.beta.-ethylenically unsaturated carboxylic acid and in 
general such copolymers are preferred. On occasion, however, it is useful 
to include within the polymer as an optional additional monomer a 
non-acidic, low molecular weight polymerizable monomer of up to 8 carbon 
atoms inclusive. Such optional monomers may be additional .alpha.-olefins 
such as propylene or styrene when ethylene is the major .alpha.-olefin, 
unsaturated esters such as vinyl acetate, methyl methacrylate and butyl 
acrylate, unsaturated halohydrocarbons such as vinyl fluoride and vinyl 
chloride and unsaturated nitriles such as acrylonitrile. As previously 
stated, the presence of this third non-acidic polymerizable monomer is 
optional and is not required. The third component is provided in amounts 
up to about 5% by mol, based on total polymer, with amounts up to 3% by 
mol on the same basis being preferred. 
The production of the optional third blend component is by well known 
methods. A number of the ethylene/unsaturated acid copolymers are 
commercial, being marketed under the trademark NUCREL.RTM. by DuPont and 
under the trademark PRIMACORE.RTM. by Dow Chemical Company. 
The blends of the invention comprise a major proportion of the linear 
alternating polymer of carbon monoxide and at least one ethylenically 
unsaturated hydrocarbon, a minor amount of the carboxylated, partially 
hydrogenated diblock copolymer and, optionally, a minor amount of the 
.alpha.-olefin-unsaturated acid polymer. The precise quantity of the 
carboxylated, partially hydrogenated diblock copolymer is not critical and 
quantities of this component from about 0.5% by weight to about 35% by 
weight, based on total polymeric blend, are satisfactory. Amounts of the 
carboxylated polymer from about 1% by weight to about 20% by weight on the 
same basis are preferred. The presence of the .alpha.-olefin/unsaturated 
acid polymer component is optional and is not required. If present, 
amounts of the .alpha.-olefin/unsaturated acid polymer up to about 10% by 
weight based on total polymer blend are satisfactory and when present the 
.alpha.-olefin/unsaturated acid polymer is preferably present in an amount 
from about 0.1% by weight to about 5% by weight on the same basis. 
The method of producing the blends of the invention is not material so long 
as an intimate mixture of the components, i.e., a uniform mixture that 
will not delaminate upon processing, is obtained. The blend of polyketone 
polymer, carboxylated polymer and optionally .alpha.-olefin/unsaturated 
copolymer will be a non-miscible blend with the carboxylated polymer and, 
if present, the olefin/unsaturated acid polymer existing as a discrete 
phase within a continuous polyketone polymer phase. The blend will not, of 
course, be homogeneous but good results are obtained if the distribution 
of the other blend component(s) throughout the polyketone polymer matrix 
is uniform. The method of blending the components is that which is 
conventional for the blending of non-miscible polymeric materials. In one 
modification the components are blended by passage through a co-rotating 
twin screw extruder operating at high RPM. In an alternate modification 
the components are blended in a mixing device exhibiting high thermal 
energy and shear. 
The blends of the invention may also contain conventional additives such as 
antioxidants, stabilizers, fillers, fire retardant materials, mold release 
agents or other substances which are added to improve the processability 
of the component polymers or to modify the properties of the resulting 
blend. Such additives are added prior to, together with, or subsequent to 
the blending of the components. 
The blends of the invention are thermoplastic materials having improved 
properties of low temperature toughness without undue loss of stiffness or 
tensile strength. The blends are processed by methods conventional for the 
processing of thermoplastics, e.g., extrusion, injection molding or 
thermoforming, into shaped articles of established utility. The advantages 
of the blends are most apparent when used to produce finished articles 
likely to be subjected to reduced temperatures, for example, containers 
for frozen or refrigerated food or drink. 
The invention is further illustrated by the following Illustrative 
Embodiments which should not be regarded as limiting the invention. 
ILLUSTRATIVE EMBODIMENT I 
A linear alternating terpolymer of carbon monoxide, ethylene and propylene 
was produced in the presence of a catalyst composition formed from 
palladium acetate, trifluoroacetic acid and 
1,3-bis[di(2-methoxyphenyl)phosphino]propane. The terpolymer had a melting 
point of 219.degree. C. and an LVN, measured in m-cresol at 60.degree. C., 
of 1.78 dl/g. 
ILLUSTRATIVE EMBODIMENT II 
Various blends were made of the following components: 
Component A: The terpolymer of Illustrative Embodiment I. 
Component B: A carboxylated, partially hydrogenated diblock copolymer of 
styrene and butadiene. The polymer is derived from SHELLVIS 50.RTM., a 
commercial partially hydrogenated diblock copolymer, is carboxylated to 
the extent of 1.5% by weight in the aromatic portion and is in the acid 
form. 
Component C: A copolymer of ethylene and methacrylic acid containing 94% by 
weight ethylene, marketed as NUCREL.RTM. 535 by DuPont. 
The blends were compounded on a Haake 30 mm twin screw co-rotating extruder 
with a L/D ratio of 13. Test specimens were prepared on a 25 mm Arburg 
injection molding machine with a L/D ratio of 18. Samples were stored over 
desiccant until testing. 
The impact properties of the blends were evaluated by determining notched 
Izod at room temperature and at 0.degree. C. by standard ASTM techniques. 
The results are shown in Table I. 
TABLE I 
______________________________________ 
Blend Component, pph 
IZOD (R.T.) IZOD (0.degree. C.) 
A B C ft lb/in ft lb/in 
______________________________________ 
100 4.2 1.5 
99 -- 1 4.7 1.6 
94 5 1 7.4 2.4 
79 20 1 4.9 2.4 
______________________________________ 
The modulus and strength of these blends was also determined by standard 
techniques. The results are shown in Table II. 
TABLE II 
______________________________________ 
Blend Component, pph 
Modulus Tensile Strength 
A B C (ksi) (psi) 
______________________________________ 
100 0 0 -- 8820 
100 0 1 217 8470 
95 5 1 216 8820 
80 20 1 176 6650 
______________________________________