Epoxide-functionalized polyphenylene ethers and method of preparation

Epoxide-functionalized polyphenylene ethers, which may be prepared by the reaction of various acid-functionalized polyphenylene ethers with functionalized epoxides, are useful in the preparation of polyphenylene ether copolymers. These copolymers are, in turn, useful for the compatibilization of blends of polyphenylene ethers with such other polymers as polyesters and polyamides.

This invention relates to functionalized polyphenylene ethers and their 
preparation and use. 
The polyphenylene ethers are a widely used class of thermoplastic 
engineering resins characterized by excellent hydrolytic stability, 
dimensional stability and dielectric properties. They are also resistant 
to high temperature conditions under many circumstances. Because of the 
brittleness of many compositions containing polyphenylene ethers, they are 
frequently blended with impact modifiers such as elastomers to form 
molding compositions. 
A disadvantage of the polyphenylene ethers which militates against their 
use for molding such items as automotive parts is their low resistance to 
non-polar solvents such as gasoline. For increased solvent resistance, it 
would be desirable to blend the polyphenylene ethers with resins which 
have a high degree of crystallinity and therefore are highly resistant to 
solvents. Illustrative of such resins are polyamides and linear 
polyesters, including poly(alkylene dicarboxylates). However, such blends 
frequently undergo phase separation and delamination. They typically 
contain large, incompletely dispersed polyphenylene ether particles and no 
phase interaction between the two resin phases. Molded parts made from 
such blends are typically characterized by extremely low impact strength. 
A principal object of the present invention, therefore, is to prepare novel 
polyphenylene ether compositions. 
A further object is to prepare functionalized polyphenylene ethers which 
are capable of compatibilizing blends of polyphenylene ethers with such 
polymers as polyamides and linear polyesters. 
A still further object is to prepare novel polyphenylene ether-polyamide 
compositions with desirable properties. 
Other objects will in part be obvious and will in part appear hereinafter. 
In one of its aspects, the present invention is directed to 
epoxide-functionalized polyphenylene ethers containing at least one moiety 
having the formula 
##STR1## 
wherein R.sup.1 is a divalent bridging radical containing at least one 
hydrocarbon group, R.sup.2 is a polyvalent bridging radical containing at 
least one hydrocarbon group, m is from 1 to about 5 and n is from 1 to 
about 10. 
The polyphenylene ethers (also known as polyphenylene oxides) used in this 
invention are a well known class of polymers. They are widely used in 
industry, especially as engineering plastics in applications requiring 
toughness and heat resistance. Since their discovery, they have given rise 
to numerous variations and modifications all of which are applicable to 
the present invention, including but not limited to those described 
hereinafter. 
The polyphenylene ethers comprise a plurality of structural units having 
the formula 
##STR2## 
In each of said units independently, each Q.sup.1 is independently 
halogen, primary or secondary lower alkyl (i.e., alkyl containing up to 7 
carbon atoms), phenyl, haloalkyl, amino-alkyl, hydrocarbonoxy, or 
halohydrocarbonoxy wherein at least two carbon atoms separate the halogen 
and oxygen atoms; and each Q.sup.2 is independently hydrogen, halogen, 
primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or 
halohydrocarbonoxy as defined for Q.sup.1. Examples of suitable primary 
lower alkyl groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, 
isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 
4-methylpentyl and the corresponding heptyl groups. Examples of secondary 
lower alkyl groups are isopropyl, sec-butyl and 3-pentyl. Preferably, any 
alkyl radicals are straight chain rather than branched. Most often, each 
Q.sup.1 is alkyl or phenyl, especially C.sub.1-4 alkyl, and each Q.sup.2 
is hydrogen. Suitable polyphenylene ethers are disclosed in a large number 
of patents. 
Both homopolymer and copolymer polyphenylene ethers are included. Suitable 
homopolymers are those containing, for example, 2,6-dimethyl-1,4-phenylene 
ether units. Suitable copolymers include random copolymers containing such 
units in combination with (for example) 2,3,6-trimethyl-1,4-phenylene 
ether units. Many suitable random copolymers, as well as homopolymers, are 
disclosed in the patent literature. 
Also included are polyphenylene ethers containing moieties which modify 
properties such as molecular weight, melt viscosity and/or impact 
strength. Such polymers are described iin the patent literature and may be 
prepared by grafting onto the polyphenylene ether in known manner such 
vinyl monomers as acrylonitrile and vinylaromatic compounds (e.g., 
styrene), or such polymers as polystyrenes and elastomers. The product 
typically contains both grafted and ungrafted moieties. Other suitable 
polymers are the coupled polyphenylene ethers in which the coupling agent 
is reacted in known manner with the hydroxy groups of two polyphenylene 
ether chains to produce a higher molecular weight polymer containing the 
reaction product of the hydroxy groups and the coupling agent. 
Illustrative coupling agents are low molecular weight polycarbonates, 
quinones, heterocycles and formals. 
The polyphenylene ether generally has a number average molecular weight 
within the range of about 3,000-40,000 and a weight average molecular 
weight within the range of about 20,000-60,000, as determined by gel 
permeation chromatography. Its intrinsic viscosity is most often in the 
range of about 0.35-0.6 dl./g., as measured in chloroform at 25.degree. C. 
The polyphenylene ethers are typically prepared by the oxidative coupling 
of at least one corresponding monohydroxyaromatic compound. Particularly 
useful and readily available monohydroxyaromatic compounds are 2,6-xylenol 
(wherein each Q.sup.1 is methyl and each Q.sup.2 is hydrogen), whereupon 
the polymer may be characterized as a poly(2,6-dimethyl-1,4-phenylene 
ether), and 2,3,6-trimethylphenol (wherein each Q.sup.1 and one Q.sup.2 is 
methyl and the other Q.sup.2 is hydrogen). 
A variety of catalyst systems are known for the preparation of 
polyphenylene ethers by oxidative coupling. There is no particular 
limitation as to catalyst choice and any of the known catalysts can be 
used. For the most part, they contain at least one heavy metal compound 
such as a copper, manganese or cobalt compound, usually in combination 
with various other materials. 
A first class of preferred catalyst systems consists of those containing a 
copper compound. Such catalysts are disclosed, for example, in U.S. Pat. 
Nos. 3,306,874, 3,306,875, 3,914,266 and 4,028,341. They are usually 
combinations of cuprous or cupric ions, halide (i.e., chloride, bromide or 
iodide) ions and at least one amine. 
Catalyst systems containing manganese compounds constitute a second 
preferred class. They are generally alkaline systems in which divalent 
manganese is combined with such anions as halide, alkoxide or phenoxide. 
Most often, the manganese is present as a complex with one or more 
complexing and/or chelating agents such as dialkylamines, alkanolamines, 
alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds and 
.omega.-hydroxyoximes. 
Among the polyphenylene ethers which are useful for the purposes of this 
invention are those which comprise molecules having at least one of the 
end groups of the formulas 
##STR3## 
wherein Q.sup.1 and Q.sup.2 are as previously defined; each R.sup.3 is 
independently hydrogen or alkyl, with the proviso that the total number of 
carbon atoms in both R.sup.3 radicals is 6 or less; and each R.sup.4 is 
independently hydrogen or a C.sub.1-6 primary alkyl radical. Preferably, 
each R.sup.3 is hydrogen and each R.sup.4 is alkyl, especially methyl or 
n-butyl. 
Polymers containing the aminoalkyl-substituted end groups of formula III 
may be obtained by incorporating an appropriate primary or secondary 
monoamine as one of the constituents of the oxidative coupling reaction 
mixture, especially when a copper- or manganese-containing catalyst is 
used. Such amines, especially the dialkylamines and preferably 
di-n-butylamine and dimethylamine, frequently become chemically bound to 
the polyphenylene ether, most often by replacing one of the 
.alpha.-hydrogen atoms on one or more Q.sup.1 radicals. The principal site 
of reaction is the Q.sup.1 radical adjacent to the hydroxy group on the 
terminal unit of the polymer chain. During further processing and/or 
blending, the aminoalkyl-substituted end groups may undergo various 
reactions, probably involving a quinone methide-type intermediate of the 
formula 
##STR4## 
with numerous beneficial effects often including an increase in impact 
strength and compatibilization with other blend components. Reference is 
made to U.S. Pat. Nos. 4,054,553, 4,092,294, 4,477,649, 4,477,651 and 
4,517,341, the disclosures of which are incorporated by reference herein. 
Polymers with 4-hydroxybiphenyl end groups of formula IV are typically 
obtained from reaction mixtures in which a by-product diphenoquinone of 
the formula 
##STR5## 
is present, especially in a copper-halide-secondary or tertiary amine 
system. In this regard, the disclosures of U.S. Pat. Nos. 4,477,649 is 
again pertinent as are those of U.S. Pat. Nos. 4,234,706 and 4,482,697, 
which are also incorporated by reference herein. In mixtures of this type, 
the diphenoquinone is ultimately incorporated into the polymer in 
substantial proportions, largely as an end group. 
In many polyphenylene ethers obtained under the above-described conditions, 
a substantial proportion of the polymer molecules, typically constituting 
as much as about 90% by weight of the polymer, contain end groups having 
one or frequently both of formulas III and IV. It should be understood, 
however, that other end groups may be present and that the invention in 
its broadest sense may not be dependent on the molecular structures of the 
polyphenylene ether end groups. 
It will be apparent to those skilled in the art from the foregoing that the 
polyphenylene ethers contemplated for use in the present invention include 
all those presently known, irrespective of variations in structural units 
or ancillary chemical features. 
The polyphenylene ether is linked to the structure shown in formula I. The 
R.sup.1 values in that formula may be polyvalent (i.e., divalent or 
greater) aliphatic, alicyclic or aromatic hydrocarbon radicals, 
substituted hydrocarbon radicals or radicals containing at least one 
non-carbon linking atom, provided they contain at least one hydrocarbon 
group. Illustrative linking atoms are oxygen and sulfur, with oxygen being 
preferred. Illustrative substituents are hydroxy, halo, nitro, alkoxy, 
carboxy, carbalkoxy and carbaryloxy. They may be relatively low molecular 
weight radicals or polymeric radicals, the formula weight of the latter 
typically being up to about 500. 
The R.sup.2 values may be generically defined in a manner similar to 
R.sub.1. They may also be low molecular weight or polymeric radicals, the 
latter generally having a formula weight up to about 1000. 
The value of m may be from 1 to about 5. It is usually 1, but values higher 
than 1 are possible by reason, for example, of the possibility of grafting 
involving more than one maleic anhydride moiety at a single site on the 
polyphenylene ether molecule. Similarly, n may be greater than 1 when the 
epoxide reactant is a polyepoxy compound such as an epoxy novolak resin. 
Most often, n is from 1 to 5. 
The moieties of formula I may be linked to the polyphenylene ether in 
various ways, depending on reactants and conditions as described 
hereinafter. For example, reactions involving the use of such compounds as 
terephthaloyl chloride or trimellitic anhydride acid chloride will result 
in a bond with one or both terminal oxygen atoms of the polyphenylene 
ether. The compositions thus obtained, which are often preferred for the 
purposes of the invention, may be represented by the formula 
##STR6## 
wherein A is a polyphenylene ether moiety, R.sup.2 is as previously 
defined, R.sup.5 is a divalent aliphatic, alicyclic or aromatic 
hydrocarbon or substituted hydrocarbon radical and p is 1 or 2. 
Compositions of formula VII are frequently preferred, especially when 
R.sup.2 is C.sub.1-4 alkylene and most desirably methylene and R.sup.5 is 
an aromatic hydrocarbon radical and most desirably p-phenylene. 
Maleic anhydride and fumaric acid, on the other hand, are believed to react 
with polyphenylene ethers via grafting on the Q.sup.1 groups or the 
aromatic rings, forming one or more aliphatic groups attached to the 
polyphenylene ether by carbon-carbon bonds. In general, an average of 
about 1-5 moieties of formula I are then present per polyphenylene ether 
molecule. 
The epoxide-functionalized polyphenylene ethers of this invention may be 
prepared by the reaction of an acid-functionalized polyphenylene ether 
with a functionalized epoxide. Suitable functionalized epoxides include, 
for example, hydroxy-substituted compounds of the formula 
##STR7## 
Glycidol is a particularly preferred functionalized epoxide. 
Also suitable as functionalized epoxides are polyepoxy compounds such as 
bisphenol A diglycidyl ether, glycidyl methacrylate polymers and epoxy 
novolaks. Their use may result in the formation of a composition 
containing moieties of formula I wherein n is greater than 1, and wherein 
R.sup.2 is a polymeric moiety. 
For example, "D.E.N. 485" is the designation of an epoxy novolak 
commercially available from Dow Chemical Company, which may be represented 
by the formula 
##STR8## 
Its reaction with a maleic anhydride-functionalized polyphenylene ether 
produces a composition in which a portion of the R.sup.2 moiety is derived 
from the epoxy novolak of formula IX and the remainder from the maleic 
anhydride. 
The term "acid-functionalized polyphenylene ether", as used herein, 
generically denotes the reaction product of a polyphenylene ether with any 
of various carboxylic acids or functional derivatives thereof, including 
salts, esters, anhydrides, amides and imides. One method of preparing 
acid-functionalized polyphenylene ethers is by reaction of the polymer 
with at least one compound containing (a) a carbon-carbon double or triple 
bond, hydroxy group, alkoxy group, aryloxy group or acyl halide group, and 
also (b) a carboxylic acid, acid salt, acid anhydride, acid amide, acid 
ester or imido group. A wide variety of such compounds are suitable for 
this purpose. Many illustrative compounds are listed in U.S. Pat. No. 
4,315,086, the disclosure of which is incorporated by reference herein. 
They include maleic, fumaric, itaconic and citraconic acids and their 
derivatives, various unsaturated fatty oils and the acids derived 
therefrom, relatively low molecular weight olefinic acids such as acrylic 
acid and its homologs, and the like. 
Another class of acid-functionalized polyphenylene ethers is disclosed in 
copending, commonly owned application Ser. No. 780,151, filed Sept. 26, 
1985, the disclosure of which is also incorporated by reference herein. 
The compositions in this class are prepared by reaction of the 
polyphenylene ether with a compound of the formula 
##STR9## 
wherein R.sup.6 is an aromatic or saturated aliphatic radical, X.sup.1 is 
halogen (especially chlorine) and X.sup.2 is one or two carboxylic acid, 
acid salt, acid amide or acid ester groups or a dicarboxylic acid 
anhydride or imide group. Illustrative compounds of this type are 
carboxymethylsucinic anhydride acid chloride and trimellitic anhydride 
acid chloride (TAAC). 
Particularly preferred functionalizing agents are maleic acid and its 
derivatives (especially maleic anhydride), fumaric acid, trimellitic 
anhydride acid chloride and terephthaloyl chloride. 
These functionalizing agents may be reacted with the polyphenylene ether by 
heating a mixture thereof, typically at a temperature within the range of 
about 80.degree.-390.degree. C., in solution or in the melt and preferably 
the latter. In general, about 0.01-2.0, most often about 0.3-1.0 and 
preferably about 0.5-1.0 parts (by weight) of said functionalizing agent 
is employed per 100 parts of polyphenylene ether. The reaction may 
conveniently be carried out in an extruder or similar equipment. 
The reaction of the acid-functionalized polyphenylene ether with the 
functionalized epoxide takes place under conditions known in the art for 
the type of reaction involved. For example, acid-functionalized 
polyphenylene ethers containing acyl chloride groups react with glycidol 
at temperatures as low as -50.degree. C. under certain conditions; in any 
event, temperatures in the range of about 20.degree.-50.degree. C. are 
satisfactory. On the other hand, reaction of an epoxy novolak with a 
carboxylic acid or anhydride may require temperatures in the range of 
about 100.degree.-250.degree. C. 
The proportion of functionalized epoxide is generally about 1-10 and 
preferably about 3-6 parts by weight per 100 parts of acid-functionalized 
polyphenylene ether. The reaction is generally conveniently conducted in a 
solvent, suitable solvents being aromatic hydrocarbons such as toluene and 
xylene, chlorinated aromatic hydrocarbons such as chlorobenzene, and 
compounds having solvent properties similar thereto.

The preparation of the epoxide-functionalized polyphenylene ethers of this 
invention is illustrated by the following example. The polyphenylene ether 
use in the examples herein was an unfunctionalized 
poly-(2,6-dimethyl-1,4-phenylene ether) having a number average molecular 
weight of about 20,000, an intrinsic viscosity (IV) in chloroform at 
25.degree. C. of 0.48 dl./g. and 0.084% (by weight) hydroxy groups. 
EXAMPLE 1 
To a solution of 325 grams of polyphenylene ether in 3 liters of toluene 
was added a solution of 16.53 grams (81.4 mmol.) of terephthaloyl chloride 
in 250 ml. of toluene. The mixture was stirred for 16 hours, after which 
16.7 grams (165 mmol.) of triethylamine was added. Stirring was continued 
for 4 hours, after which 15.3 grams (207 mmol.) of glycidol was added and 
stirring was continued for 3 days. The product was precipitated by 
addition of methanol, redissolved in toluene and reprecipitated, and dried 
under reduced pressure. It was shown by infrared spectroscopy to be the 
desired epoxide-functionalized polyphenylene ether, and by analysis to 
contain 0.0014% (by weight) hydroxy groups. 
EXAMPLE 2 
A mixture of 99 parts of polyphenylene ether and 1 part of maleic anhydride 
is extruded on a single-screw extruder at temperatures in the range of 
120.degree.-330.degree. C. The extrudate, comprising the desired maleic. 
anhydride-functionalized polyphenylene ether, is quenched in water, 
pelletized, dissolved in chloroform, precipitated with methanol, filtered 
and vacuum dried at 60.degree. C. 
A solution in 85 ml. of 1, 2, 4-trichlorobenzene of 5 grams of the maleic 
anhydride-functionalized polyphenylene ether and 5 grams of "D. E. N. 485" 
is heated at 200.degree. C., under nitrogen, for 16 hours. Toluene, 100 
ml., is added and the mixture was heated under reflux for 1/2 hour and 
cooled. The solids are removed by centrifugation, washed with toluene and 
again centrifuged and dried. The product is the desired 
epoxide-functionalized polyphenylene ether. 
As previously indicated the epoxide-functionalized polyphenylene ethers of 
this invention are useful in the preparation of compatibilized blends of 
polyphenylene ethers with such polymers as polyamides and linear 
polyesters. In particular, said functionalized polyphenylene ethers form 
copolymers with polyesters and polyamides, which may be used for 
compatibilization of such blends. Compositions comprising polyphenylene 
ether-polyester copolymers are disclosed and claimed in the aforementioned 
application Ser. No. 866,661, filed May 27, 1986. 
Another aspect of the invention is resinous compositions comprising at 
least one polyphenylene ether and at least one polyamide, at least a 
portion of said polyphenylene ether being an epoxide-functionalized 
polyphenylene ether of this invention. It is within the scope of the 
invention to include both functionalized and unfunctionalized 
polyphenylene ether in said composition, the latter being present in an 
amount up to about 90% by weight of total polyphenylene ether. 
Polyamides suitable for use in said compositions may be made by any known 
method, including the polymerization of a monoamino-monocarboxylic acid or 
a lactam thereof having at least 2 carbon atoms between the amino and 
carboxylic acid group, of substantially equimolar proportions of a diamine 
which contains at least 2 carbon atoms between the amino groups and a 
dicarboxylic acid, or of a monoaminocarboxylic acid or a lactam thereof as 
defined above together with substantially equimolar proportions of a 
diamine and a dicarboxylic acid. (The term "substantially equimolar" 
proportions includes both strictly equimolar proportions and slight 
departures therefrom which are involved in conventional techniques for 
stabilizing the viscosity of the resultant polyamides.) The dicarboxylic 
acid may be used in the form of a functional derivative thereof, for 
example, an ester or acid chloride. 
Examples of the aforementioned monoamino-monocarboxylic acids or lactams 
thereof which are useful in preparing the polyamides include those 
compounds containing from 2 to 16 carbon atoms between the amino and 
carboxylic acid groups, said carbon atoms forming a ring with the 
--CO--NH-- group in the case of a lactam. As particular examples of 
aminocarboxylic acids and lactams there may be mentioned 
.epsilon.-aminocaproic acid, butyrolactam, pivalolactam, 
.epsilon.-caprolactam, capryllactam, enantholactam, undecanolactam, 
dodecanolactam and 3- and 4-aminobenzoic acids. 
Diamines suitable for use in the preparation of the polyamides include the 
straight chain and branched chain alkyl, aryl and alkaryl diamines. Such 
diamines include, for example, those represented by the general formula 
EQU H.sub.2 N(CH.sub.2).sub.n NH.sub.2 
wherein n is an integer of from 2 to 16. Illustrative diamines are 
trimethylenediamine, tetramethylenediamine, pentamethylenediamine, 
octamethylenediamine, hexamethylenediamine (which is often preferred), 
trimethylhexamethylenediamine, m-phenylenediamine and m-xylylenediamine. 
The dicarboxylic acids may be represented by the formula 
EQU HOOC--Y--COOH 
wherein Y is a divalent aliphatic or aromatic group containing at least 2 
carbon atoms. Examples of aliphatic acids are sebacic acid, 
octadecanedioic acid, suberic acid, glutaric acid, pimelic acid and adipic 
acid. Aromatic acids, such as isophthalic and terephthalic acids, are 
preferred. 
Typical examples of the polyamides or nylons, as these are often called, 
include, for example, polyamide-6, 66, 11, 12, 63, 64, 6/10 and 6/12 as 
well as polyamides from terephthalic acid and/or isophthalic acid and 
trimethylhexamethylenediamine; from adipic acid azelaic acid and 2, 
2-bis-(p-aminocyclohexyl) propane and from terephthalic acid and 4, 
4'-diaminodicyclohexylmethane. Mixtures and/or copolymers of two or more 
of the foregoing polyamides or prepolymers thereof, respectively, are also 
within the scope of the present invention. Preferred polyamides are 
polyamide-6, 66, 11 and 12, most preferably polyamide-66. 
Among the linear polyesters which are useful in preparing copolymers with 
the epoxide-functionalized polyphenylene ethers are the poly(alkylene 
dicarboxylates). They typically comprise at least 30 and most often at 
least 50 structural units, usually of the formula 
##STR10## 
wherein R.sup.7 is a divalent aliphatic or alicyclic radical containing 
about 2-10 carbon atoms and R.sup.8 is a divalent aliphatic, alicyclic or 
aromatic radical containing about 2-10 and usually about 6-10 carbon 
atoms. 
Such polyesters are typically prepared by the known reaction of dihydroxy 
compounds with dicarboxylic acids or functional derivatives thereof such 
as anhydrides, acid chlorides or lower alkyl (especially methyl) esters, 
preferably the esters. 
The R.sup.7 radicals may be one or more aliphatic or alicyclic hydrocarbon 
radicals, alicyclic radicals being known to those skilled in the art to be 
equivalent to aliphatic radicals for the purposes of the invention. They 
may be derived from such dihydroxy compounds as ethylene glycol, 
1,4-butanediol (both of which are preferred), propylene glycol, 
1,3-propanediol, 1,6-hexanediol, 1,10-decanediol, 
1,4-cyclohexanedimethanol and 2-butene-1,4-diol. They may also be radicals 
containing substituents which do not substantially alter the reactivity of 
the dihydroxy compound (e.g., alkoxy, halo, nitrile) or hetero atoms 
(e.g., oxygen or sulfur). The R.sup.7 radicals are usually saturated. 
The R.sup.8 radicals may be derived from such acids as succinic, adipic, 
maleic, isophthalic and terephthalic acids or similar substituted and 
hetero atom-containing acids. 
Most often, R.sup.7 and R.sup.8 are hydrocarbon radicals, typically 
containing about 2-10 carbon atoms. Preferably, R.sup.7 is aliphatic and 
R.sup.8 is aromatic. The polyester is most desirable a poly(alkylene 
terephthalate), particularly poly(ethylene terephthalate) or 
poly(1,4-butylene terephthalate) (hereinafter sometimes simply 
"polyethylene terephthalate" and "polybutylene terephthalate", 
respectively) and especially the latter. Such polyesters are known in the 
art as illustrated by the following U.S. Pat. Nos. 2,465,319; 3,047,539; 
2,720,502; 3,671,487; 2,727,881; 3,953,394; 2,822,348; 4,128,526. The 
polyesters most often have number average molecular weights in the range 
of about 10,000-70,000, as determined by intrinsic viscosity (IV) at 
30.degree. C. in a mixture of 60% (by weight) phenol and 40% 
1,1,2,2-tetrachloroethane. 
It is also contemplated to employ elastomeric polyesters. Such polyesters 
are known in the art; they are exemplified by compositions in which a 
portion of the R.sup.7 values are soft segment radicals such as 
polyoxyalkylene (typically polyoxyethylene or polyoxytetramethylene) and 
units derived from lactones such as .epsilon.-caprolactone. Numerous 
elastomeric polyesters of this type are commercially available; they 
include those sold by DuPont under the trademark HYTREL and by General 
Electric under the trademark LOMOD. 
To prepare the copolymer compositions, the epoxide-functionalized 
polyphenylene ether and polyester or polyamide are heated together in 
solution or in the melt. The reaction temperature is typically within the 
range of about 100.degree.-350.degree. C., preferably about 
150.degree.-290.degree. C. for polyesters. The proportions of 
epoxide-functionalized polyphenylene ether and polyester or polyamide are 
not critical and may be adjusted over a wide range to yield copolymer 
compositions having the desired properties. The polyphenylene 
ether-polyamide compositions, however, generally contain about 5-75% by 
weight polyphenylene ether and about 25-95% polyamide. 
In general, the copolymer compositions comprise only partially copolymer, 
with the balance being a polyphenylene ether-polyester or polyamide blend. 
The approximate proportion of copolymer in the composition may often be 
conveniently expressed as the percentage of copolymerized polyphenylene 
ether based on total polyester or polyamide. It may be determined by 
extracting unreacted polyphenylene ether with a suitable solvent, 
typically toluene or chloroform, and analyzing the insoluble residue 
(copolymer and residual polyester or polyamide) by proton nuclear magnetic 
resonance. 
It is frequently preferred to maximize the proportion of carboxy end groups 
in the polyester. This may frequently be accomplished by preextruding the 
polyester, typically at a temperature in the range of about 
250.degree.-300.degree. C. Under these conditions, there is apparently a 
loss by degradation and volatilization of hydroxy end group functionality, 
producing a polymer with a high proportion of carboxy end groups. 
The preparation of polyphenylene ether-polyester copolymer compositions is 
illustrated by the following examples. 
EXAMPLE 3 
A solution of 250 grams of a poly(butylene terephthalate) having a number 
average molecular weight of about 40,000 and a carboxy end group 
concentration of 24.7 micro-equivalents per gram in 3.8 liters of 
1,2,4-trichlorobenzene was heated to 200.degree. C. and 250 grams of the 
epoxide-functionalized polyphenylene ether of Example 1 was added under 
nitrogen, with stirring. Stirring at 200.degree. C. was continued for 60 
hours, after which the copolymer composition was precipitated by pouring 
into acetone, extracted with methanol and dried under vacuum. Analysis 
showed the presence of 28% copolymerized polyphenylene ether. 
EXAMPLE 4 
The procedure of Example 3 was repeated, using a polyester which had been 
preextruded on a twin-screw extruder at about 260.degree. C., and which 
had a carboxylate end group concentration of 34.3 microequivalents per 
gram. Analysis showed the presence of 39% copolymerized polyphenylene 
ether. 
As previously mentioned, the above-described copolymer compositions, and 
polyphenylene ether-poly(ester or amide) blends in which they are 
incorporated, have high impact strength, good solvent resistance and other 
advantageous properties. These properties make them useful for the 
preparation of molded and extruded articles. 
The weight ratio of polyester or polyamide to total polyphenylene ether in 
the copolymer-containing blend is generally in the range of about 
0.5-3.0:1, most often about 0.9-2.5:1. The proportion of copolymerized 
polyphenylene ether therein is capable of wide variation, essentially any 
quantity thereof affording some improvement in properties. For the most 
part, said proportion is in the range of about 10-80% by weight of total 
resinous components. 
The blends may also contain ingredients other than the copolymer, 
polyphenylene ether and polyester or polyamide. A particularly useful 
other ingredient in many instances is at least one elastomeric impact 
modifier which is compatible with the polyphenylene ether. It is generally 
present in the amount of about 5-25% by weight of resinous components. 
Impact modifiers for polyphenylene ether-polyester or polyamide 
compositions are well known in the art. They are typically derived from 
one or more monomers selected from the group consisting of olefins, vinyl 
aromatic monomers, acrylic and alkylacrylic acids and their ester 
derivatives as well as conjugated dienes. Especially preferred impact 
modifiers are the rubbery high-molecular weight materials including 
natural and synthetic polymeric materials showing elasticity at room 
temperature. They include both homopolymers and copolymers, including 
random, block, radial block, graft and core-shell copolymers as well as 
combinations thereof. 
Polyolefins or olefin-based copolymers employable in the invention include 
low density polyethylene, high density polyethylene, linear low density 
polyethylene, isotactic polypropylene, poly(1-butene), 
poly(4-methyl-1-pentene), propylene-ethylene copolymers and the like. 
Additional olefin copolymers include copolymers of one or more 
.alpha.-olefins, particularly ethylene, with copolymerizable monomers 
including, for example, vinyl acetate, acrylic acids and alkylacrylic 
acids as well as the ester derivatives thereof including, for example, 
ethylene-acrylic acid, ethyl acrylate, methacrylic acid, methyl 
methacrylate and the like. Also suitable are the ionomer resins, which may 
be wholly or partially neutralized with metal ions. 
A particularly useful class of impact modifiers are those derived from the 
vinyl aromatic monomers. These include, for example, modified and 
unmodified polystyrenes, ABS type graft copolymers, AB and ABA type block 
and radial block copolymers and vinyl aromatic conjugated diene core-shell 
graft copolymers. Modified and unmodified polystyrenes include 
homopolystyrenes and rubber modified polystyrenes, such as butadiene 
rubber-modified polystyrene (otherwise referred to as high impact 
polystyrene or HIPS). Additional useful polystyrenes include copolymers of 
styrene and various monomers, including, for example, 
poly(styrene-acrylonitrile) (SAN), styrene-butadiene copolymers as well as 
the modified alpha- and para-substituted styrenes and any of the styrene 
resins disclosed in U.S. Pat. No. 3,383,435, herein incorporated by 
reference. ABS types of graft copolymers are typified as comprising a 
rubbery polymeric backbone derived from a conjugated diene alone or in 
combination with a monomer copolymerizable therewith having grafted 
thereon at least one monomer, and preferably two, selected from the group 
consisting of monoalkenylarene monomers and substituted derivatives 
thereof as well as acrylic monomers such as acrylonitriles and acrylic and 
alkylacrylic acids and their esters. 
An especially preferred subclass of vinyl aromatic monomer-derived resins 
is the block copolymers comprising monoalkenyl arene (usually styrene) 
blocks and conjugated diene (e.g., butadiene or isoprene) or olefin (e.g., 
ethylene-propylene, ethylene-butylene) blocks and represented as AB and 
ABA block copolymers. The conjugated diene blocks may be partially or 
entirely hydrogenated, whereupon the properties are similar to the olefin 
block copolymers. 
Suitable AB type block copolymers are disclosed in, for example, U.S. Pat. 
Nos. 3,078,254; 3,402,159; 3,297,793; 3,265,765 and 3,594,452 and UK Pat. 
No. 1,264,741, all incorporated herein by reference. Exemplary of typical 
species of AB block copolymers there may be given: 
polystyrene-polybutadiene (SBR) 
polystyrene-polyisoprene and 
poly(alpha-methylstyrene)-polybutadiene. 
Such AB block copolymers are available commercially from a number of 
sources, including Phillips Petroleum under the trademark SOLPRENE. 
Additionally, ABA triblock copolymers and processes for their production as 
well as hydrogenation, if desired, are disclosed in U.S. Pat. Nos. 
3,149,182; 3,231,635; 3,462,162; 3,287,333; 3,595,942; 3,694,523 and 
3,842,029, all incorporated herein by reference. 
Examples of triblock copolymers include: 
polystyrene-polybutadiene-polystyrene (SBS), 
polystyrene-polyisoprene-polystyrene (SIS), 
poly(.alpha.-methylstyrene)-polybutadiene-poly-(.alpha.-methylstyrene) and 
poly(.alpha.-methylstyrene)-polyisoprene-poly(.alpha.-methylstyrene). 
Particularly preferred triblock copolymers are available commercially as 
CARIFLEX.RTM., KRATON D.RTM. and KRATON G.RTM. from Shell. 
Another class of impact modifiers is derived from conjugated dienes. While 
many copolymers containing conjugated dienes have been discussed above, 
additional conjugated diene modifier resins include, for example, 
homopolymers and copolymers of one or more conjugated dienes including, 
for example, polybutadiene, butadiene-styrene copolymers, 
butadiene-glycidyl methacrylate copolymers, isoprene-isobutylene 
copolymers, chlorobutadiene polymers, butadiene-acrylonitrile copolymers, 
polyisoprene, and the like. Ethylene-propylene-diene monomer rubbers may 
also be used. These EPDM's are typified as comprising predominantly 
ethylene units, a moderate amount of propylene units and up to about 20 
mole percent of non-conjugated diene monomer units. Many such EPDM's and 
processes for the production thereof are disclosed in U.S. Pat. Nos. 
2,933,480; 3,000,866; 3,407,158; 3,093,621 and 3,379,701, incorporated 
herein by reference. 
Other suitable impact modifiers are the core-shell type graft copolymers. 
In general, these have a predominantly conjugated diene rubbery core or a 
predominantly cross-linked acrylate rubbery core and one or more shells 
polymerized thereon and derived from monoalkenylarene and/or acrylic 
monomers alone or, preferably, in combination with other vinyl monomers. 
Such core-shell copolymers are widely available commercially, for example, 
from Rohm and Haas Company under the trade names KM-611, KM-653 and 
KM-330, and are described in U.S. Pat. Nos. 3,808,180; 4,034,013; 
4,096,202; 4,180,494 and 4,292,233. 
Also useful are the core-shell copolymers wherein an interpenetrating 
network of the resins employed characterizes the interface between the 
core and shell. Especially preferred in this regard are the ASA type 
copolymers available from General Electric Company and sold as GELOY.TM. 
resin and described in U.S. Pat. No. 3,944,631. Especially for polyester 
blends, the core-shell elastomers containing, for example, a poly(alkyl 
acrylate) core attached to a polystyrene shell via an interpenetrating 
network are frequently useful; they are more fully disclosed in copending, 
commonly owned application Ser. No. 811,808, now U.S. Pat. No. 4,681,915, 
filed Dec. 20, 1985. 
In addition, there may be employed the above-described polymers and 
copolymers having copolymerized therewith or grafted thereon monomers 
having functional groups and/or polar or active groups. Finally, other 
suitable impact modifiers include Thiokol rubber, polysulfide rubber, 
polyurethane rubber, polyether rubber (e.g., polypropylene oxide), 
epichlorohydrin rubber, ethylene-propylene rubber, thermoplastic polyester 
elastomers and theremoplastic etherester elastomers. 
The preferred impact modifiers are block (typically diblock, triblock or 
radial teleblock) copolymers of alkenylaromatic compounds and olefins or 
dienes. Most often, at least one block is derived from styrene and at 
least one other block from at least one of butadiene, isoprene, ethylene 
and butylene. Especially preferred are the triblock copolymers with 
polystyrene end blocks and olefin- or diene-derived midblocks. When one of 
the blocks is derived from one or more dienes, it is frequently 
advantageous to reduce the aliphatic unsaturation therein by selective 
hydrogenation. The weight average molecular weights of the impact 
modifiers are typically in the range of about 50,000-300,000. Block 
copolymers of this type are commercially available from Shell Chemical 
Company under the trademark KRATON, and include KRATON D1101, G1650, 
G1651, G1652, G1657 and G1702. 
Other conventional ingredients which may be present in the 
copolymer-containing blends include fillers, flame retardants, colorants, 
stabilizers, antistatic agents, mold release agents and the like, used in 
conventional amounts. The presence of other resinous components is also 
contemplated. These include impact modifiers compatible with the 
polyester, such as various graft and core-shell copolymers of such 
monomers as butadiene, styrene, butyl acrylate and methyl methacrylate. 
The presence of such copolymers frequently improves the low-temperature 
ductility of the blends. 
The preparation of copolymer-containing blends is normally achieved under 
conditions adapted for the formation of an intimate resin blend. Such 
conditions often include extrusion, typically at temperatures in the range 
of about 100.degree.-300.degree. C. and otherwise under the conditions 
previously described. Extrusion may be conveniently effected in a 
screw-type or similar extruder which applies a substantial shearing force 
to the composition, thereby decreasing the particle size thereof. It is 
sometimes found that the impact strength of the composition is increased 
if it is extruded more than once, thereby insuring effective blending. 
The preparation and properties of polyphenylene ether-polyester and 
polyamide blend compositions are illustrated by the following examples. 
EXAMPLE 5 
A resin blend was prepared by extrusion, under conventional conditions in a 
twin-screw extruder, of a mixture of 75.4 parts of the composition of 
Example 3, 0.5 part of unfunctionalized polyphenylene ether, 14.1 parts of 
the poly(butylene terephthalate) used as a reactant in Example 3, and 10 
parts of a commercially available triblock copolymer in which the 
polystyrene end blocks have weight average molecular weights of 29,000 and 
the ethylene/butylene midblock has a weight average molecular weight of 
116,000. It had the following physical properties. 
Izod impact strength (notched)--753 joules/m. 
Tensile strength at yield--43.9 MPa. 
Tensile strength at break--40.9 MPa. 
Elongation at break--130% 
Tensile modulus--0.77 GPa. 
EXAMPLE 6 
A mixture of 49 parts of the epoxide-functionalized polyphenylene ether of 
Example 1, 41 parts of a commercially available polyamide-66 and 10 parts 
of an impact modifier was tumble mixed in a jar mill and extruded at 
120.degree.-330.degree. C. and 400 rpm., using a twin-screw extruder. The 
impact modifier was a commercially available styrene-ethylene/butylene 
styrene triblock copolymer in which the weight average molecular weights 
of the end blocks and midblock are 29,000 and 116,000, respectively. 
The extrudate was quenched in water, pelletized and dried in a vacuum oven 
at 100.degree. C. It was then injection molded into notched Izod test 
specimens at 300.degree. C. and 1100 psi. The Izod impact strength of the 
specimens was 144 joules/m.