CA2010141A1 - Compositions comprising polyphenylene ether-polyester copolymers from epoxytriazine-capped polyphenylene ethers - Google Patents

Abstract

CIP of RD-18777 COMPOSITIONS COMPRISING POLYPHENYLENE
ETHER-POLYESTER COPOLYMERS FROM
EPOXYTRIAZINE-CAPPED POLYPHENYLENE ETHERS

Abstract Copolymer-containing compositions are prepared by the reaction of an epoxytriazine-capped polyphenylene ether with another polymer containing carboxy end groups, especially a polyester. The compositions have excellent properties and find utility as molding compositions and as compatibilizers for blends of similar polymers. Suitable epoxytriazine-capped polyphenylene ethers may be prepared by reaction of a polyphenylene ether with an epoxychlorotriazine such as diglycidyl chlorocyanurate, n-butyl glycidyl chlorocyanurate or mesityl glycidyl chlorocyanurate.

Description

RD-~9372 CIP of RD-18777 CO~PQSITIONS CQ~RISING PO~YPHEN~LE~E
ETHER-POLY~S~ER ~QPQLYM~RS FROM
EPOX~TRIAZIN~-CAPPED POLYPH~NYLE~E ~TH~S

This application is a continuation-in-part of copending application Serial No. 210,266, filed June 23, 1988.
This invention relates to the preparation of polyphenylene ether-polyester copolymers.
The polyphenylene ethers are a widely used class of thermoplastic engineering resins characterized by excellent hydrolytic stability, dimensional stability, toughness, heat resistance and dielectric properties. However, they are de-ficient in certain other properties such as workability andsolvent resistance. Therefore, there is a con~inuing search for means for modifying polyphenylene ethers to improve these other properties.
A disadvantage of the polyphenylene ethers which militates against their use for molding such items as automo-tive parts is their low resistance to non-polar solvents such as gasoline. For increased solvent resistance, it would be desirable to form compositions in which polyphenylene ethers are combined with resins which have a high degree of crys-tallinity and therefore are highly resistant to solvents.Illustrative of such resins are the thermoplastic polyesters including poly(alkylene dicarboxylates), especially the poly(alkylene terephthalates). Other reasons exist for forming compositions comprising polyphenylene ethers and other polymers containing carboxy end groups, especially such polyesters as polyarylates and elastomeric polyesters.
~ owever, polyphenylene oxide-polyester blends fre-quently undergo phase separation and delamination. They typ-ically contain large, incompletely dispersed polyphenylene : .
~ .

CIP o~ RD-18777 ether particles and no phase interaction between the two resin phases. Molded parts made from such blends are typi-cally characterized by extremely low impact strength, brit-tleness, delamination and the like.
Numerous methods for compatibilizing polyphenylene ether-polyester compositions have been de~eloped. For exam-ple, PCT published application 87/~50 describes blends com-patibilized by the addition of an aromatic polycarbonate.
Said blends are extremely versatile in numerous critical ap-plications such as the fabrication of automobile body parts.
However, the presence of polycarbonate may result in degra-dation of certain other properties such as heat distortion temperature.
In addition, a problem sometimes arises by virtue 15 of the presence of aminoalkyl-substituted end groups on -certain commercially available polyphenylene ethers, as described in more detail hereinafter. For optimum impact strength, it is frequently necessary to remove said aminoalkyl-substituted end groups and other amine constituents frequently present as impurities in the polyphenylene ether. Such expedients as the use of amine quenchers and/or vacuum venting of the polyphenylene ether are effective in decreasing amino nitrogen content, but add a step to the processing operation which may be undesirable under certain circumstances.
Various methods are also known for preparing copolymers of polyphenylene ethers with polyesters. Such copolymers are often effective as compatibilizers for blends of the same resins. To facilitate copolymer formation, it is frequently advisable to employ a polyphenylene ether containing functional groups. For example, epoxy groups can react with such nucleophllic groups in polyesters and RD-l9372 CIP of RD-18777 polyamides as amino, hydroxy and carboxy groups, leading to copolymer formation.
Several methods of preparing epoxy-functionalized polyphenylene ethers are disclosed in various patents and publications. For example, U.S. Patent 4,460,743 describes the reaction of a polyphenylene ether with epichlorohydrin, to produce an epoxy-functionalized polymer. However, this method requires dissolution of the polyphenylene ether in a large excess of epichlorohydrin, a relatively expensive 10 reagent which is also a strong skin irritant and can cause kidney injury.
PCT published application 87/7279 describes the reaction of polyphenylene ethers with terephthaloyl chloride and glycidol to form an epoxy-functionalized polyphenylene 15 ether useful, for example, for the preparation of copolymers with polyesters, but copolymer formation with polyesters by this method requires a solution reaction in relatively expensive and high boiling solvents such as trichlorobenzene and is very slow.
In the same application are described reactions of various epoxy-functionalized ethylenic monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether with polyphenylene ethers in the presence of free radi-cal initiators. The resulting epoxy-functionalized materials 25 are useful as intermediates for the preparation of copolymers by melt reaction with polyamides. However, functionalization of the polyphenylene ether by this method most often requires large quantities of the monomer, and certain of such mono-mers, including glycidyl me~hacrylate, are toxic. Moreover, 30 the reaction is generally accompanied by homopolymerization of the epoxy-functionalized monomer, and it is then necessary to remove the homopolymer by such complicated operations as dissolution of the crude polymeric product followed by forma-~ ~ , CIP of RD-18777 tion and decompositlon of a polyphenylene ether-methylene chloride complex. Thus, these materials may not be readily adaptable to copolymer preparation on an industrial scale.
The present in~ention provides compositions comprising polyphenylene ether-polyester copolymers formed from highly reactive epoxy-functionalized polyphenylene ethers which may be prepared under simple solution or interfacial conditions using relatively inexpensive reagents.
Said compositions have excellent physical properties, particularly when blended with conventional impact modifiers for polyphenylene ethers. They also compatibilize blends containing unfunctionalized polyphenylene ethers.
Accordingly, the invention includes compositions comprising polyphenylene ether copolymers prepared by the reaction of an epoxytriazine-capped polyphenylene ether with at least one condensation polymer containing carboxy end groups.
Epoxytriazine-capped polyphenylene ethers suitable for use in the preparation of the compositions of this inven-tion, as well as methods for their preparation, are disclosedand claimed in copending, commonly owned application Serial No. 210,547, filed June 23, 1988. They comprise polymer molecules having end groups of the formula Q2 Ql OX
~ N ~ ?

Q2 ~ Q O-R -CH-CH2 wherein:
each Ql is independently halogen, primary or sec-ondary lower alkyl (i.e., alkyl containing up to 7 carbon .
. ~ . ~ ..

. . . . .

- 5 ~

CIP of RD-18777 atoms), phenyl, haloalkyl, aminoallcyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
each Q2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Ql;
X is an alkyl, cycloalkyl or aromatic radical or ~0 (II) -R -CH-CH2 ; and Rl is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical.
Said epoxytria~ine-capped polyphenylene ethers may be prepared as described hereinafter from the polyphenylene ethers known in the art. The latter encompass numerous vari-ations and modifications all of which are applicable to the present invention, including but not limited to those de-scribed hereinafter.
The polyphenylene ethers comprise a plurality of structural units having the formula ~ Ql (III) -O
Q2 Ql and in each of said units independently, each Ql and Q2 is as previously defined. Examples of primary lower alkyl groups suitable as Ql and Q2 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 ~ ::
.: . : :

.

- 6 - 2~

CIP of RD-18777 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 of-ten, each Ql is alkyl or phenyl, e!~pecially Cl_4 alkyl, and each Q2 is hydrogen. Suitable polyphenylene ethers are dis-closed 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 de-scribed in the patent literature and may be prepared by grafting onto the polyphenylene ether in ~nown manner such vinyl monomers as acrylonitrile and vinylaromatic compounds (e.g., styrene), or such polymers as polystyrenes and elas-tomers. The product typically contains both grafted and un-grafted 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, provided substantial proportions of free hy-droxy groups remain present. Illustrative coupling agents are low molecular weight polycarbonates, quinones, heterocy-cles and formals.
The polyphenylene ether generally has a number av-erage molecular weight within the range of about 3,000-40,000 and a weight average molecular weight within the range of : . ' .
., , , ~ . .. : ..

CIP of RD-18777 about 20,000-80,000, as determined by gel permeation chromatography. Its intrinsic viscosity is most often in the range of about 0.15-0.6 dl./g., as measured in chloroform at 25 C.
The polyphenylene ethers are typically prepared by the oxidative coupling of at least one corresponding monohy-droxyaromatic compound. Particularly useful and readily available monohydroxyaromatic compounds are 2,6-xylenol (wherein each Ql is methyl and each Q2 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 Ql and one Q2 is methyl and the other Q2 is hydrogen).
A variety of catalyst systems are known for the preparation of polyphenylene ethers by oxidative coupling.
lS 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 cop-per, manganese or cobalt compound, usually in combination with various other materials.
A first class of preferred catalyst systems con-sists of those containing a copper compoundO Such catalysts are disclosed, for example, in U.S. Patents 3,306,874, 3,306,875, 3,914,266 and 4,028,341. They are usually combi-nations 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 al-kaline 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 com-plexing and/or chelating agents such as dialkylamines, alka-nolamines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds, ~-hydroxyoximes tmonomeric and poly-, .

: . .
'~' . : ' ' - ' z~

CIP of RD-18777 merlc), o-hydroxyaryl oximes and ~-diketones. Also useful are known cobalt-containing catalyst systems. Suitable man-ganese and cobalt-containing catalyst systems for polypheny-l~ne ether preparation are known in the art by reason of dis-closure in numerous patents and publications.
The polyphenylene ethers which may be employed for the purposes of this invention include those which comprise molecules having at least one of the end groups of the formulas N(R3)2 Q2 ~(R2)2 (IV) -o - ~ OH and Q2 Ql (V) ~ ~ O ~ ~ OH

Ql 122 Q2 wherein Ql and Q2 are as previously defined; each R2 is inde-pendently hydrogen or alkyl, with the proviso that the total numbsr of carbon atoms in both R2 radicals is 6 or less; and each R3 is independently hydrogen or a C1_6 primary alkyl rad-ical. Preferably, each R2 is hydrogen and each R3 is alkyl, especially methyl or n-butyl.
Polymers containing the aminoalkyl-substituted end groups of formula IV are typically obtained by incorporating an appropriate primary or secondary monoamine as one of the . , ., ,~ : ~: . . .

.: . , . : . .
: . . . . .. .

,2~q~ 9~

CIP of RD-18777 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 a-hydrogen atoms on one or more Ql radicals. The principal site of reaction is the Ql 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 reac-tions, probably involving a quinone methide-type intermediate of the formula Q ~ C(R )2 (VI) -O ~ = O

with numerous beneficial effects often including an increase in impact strength and compatibilization with other blend components. Reference is made to U.S. Patents 4,054,553, 4,092,294, 4,477,649, 4,477,651 and 4,517,341, the disclo-sures of which are incorporated by reference herein.
Polymers with 4-hydroxybiphenyl end groups of for-mula V are often especially useful in the present invention.
They are typically obtained from reaction mixtures in which a by-product diphenoquinone of the formula Q

~VII) 0 .. . . . .
- . . ~
.

- - , . :
.

;~Q~

CIP o~ RD-18777 is present, especially in a copper--halide-secondary or ter-tiary amine system. In this regarcl, the disclosure of U.S.
Patent 4,477,649 is again pertinent as are those of U.S.
4,234,706 and 4,482,697, which are also incorporated by ref~
erence 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 IV and V. It should be under-stood, however, that other end groups may be present and that the invention in its broadest sense may no~ be dependent on the molecular structures of the polyphenylene ether end groups. It is, however, required that a substantial proportion of free, non~hydrogen bonded hydroxy groups be present; that is, that a substantial proportion of hydroxy-terminated end groups have structures other than that offormula IV.
The use of polyphenylene ethers containing substan-tial amounts of unneutralized amino nitrogen may afford compositions with undesirably low impact strengths. The possible reasons for this are explained hereinafter. The amino compounds include, in addition to the aforementioned aminoalkyl end groups, traces of amine ~particularly sec-ondary amine) in the catalyst used to form the polyphenylene ether. ~ -The present invention therefore includes the use of polyphenylene ethers in which a substantial proportion of amino compounds has been removed or inactivated. Polymers so treated contain unneutralized amino nitrogen, if any, in :: : i ,:. -~, ~. : : ~ .

4~
-CIP of RD-18777 amounts no greater than 800 ppm. and more preferably in the range of about lOG-800 ppm.
A preferred method of inactivation is by extrusion of the polyphenylene ether at a temperature within the range of about 230-350 C, with vacuum venting. This is preferably achieved in a preliminary extrusion step, by connecting the vent o~ the extruder to a vacuum pump capable of reducing the pressure to about 200 torr or less. There may also be advan-tages in employing vacuum venting during extrusion of the composition of this invention.
It is believed that this inactivation method aids in the removal by evaporation of any traces of free amines (predominantly secondary amines) in the polymer, including amines generated by conversion of aminoalkyl end groups to quinone methides of the type represented by formula VI.
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 Xnown, irrespective of variations in structural units or an-cillary chemical features.
The end groups on the epoxytriazine-capped polyphenylene ethers have formula I, in which Ql and Q2 are as previously defined. X may be an alkyl or cycloalkyl radical, typically lower alkyl and especially pri~ary or secondary lower al~yl; an aromatic radical, typically monocyclic and containing 6-lO carbon atoms and especially an aromatic hy-drocarbon radical; or a radical of formula II. In formulas I
and II, Rl may be aliphatic, alicyclic, aromatic (including aromatic radicals containing art-recognized substituents) or heterocyclic. It is usually lower alkylene and especially methylene.
The above-described epoxytriazine-capped polypheny-lene ether compositions may be prepared by contacting under .

. : . ~ , :

,. . . . ,:

CIP of RD-18777 reactive conditions, in the presence o~ a basic reagent, at least one polyphenylene ether with an epoxychlorotriazine of the formula N ~ N
(VIII) ~oJ

X0 N \\ 1 ~~
O-R -CH-CHz wherein R1 and X are as previously defined.
Typical epoxychlorotriazines of formula VIII in-clude 2-chloro-4,6-diglycidoxy-1,3,5-triazine (hereinafter "DGCC"), 2-chloro-4-methoxy-6-glycidoxy-1,3,5-triazine, 2-chloro-4-(n-butoxy)-6-glycidoxy-1,3,5-triazine (hereinafter "BGCC") and 2-chloro-4-(2,4,6-trimethylphenoxy)-6-glycidoxy-1,3,5-triazine (hereinafter "MGCC"). These compounds may also be named as though derived from cyanuric acid and designated diglycidyl chlorocyanurate, n-butyl glycidyl chlorocyanurate and 2,4,~-trimethylphenyl glycidyl chlorocya-nurate, respectively. They may be prepared, for example, by the reaction of 2,4,6-trichlorotriazine (cyanuric chloride~
with glycidol or combinations thereof with n-butanol or mesi-tol. Cyanuric chloride and n-butyl dichlorocyanurate are both commercially available.
Intermediates such as DGCC, BGCC and MGCC and the method for their preparation are disclosed and claimed in copending, commonly owned application Serial No. 144,901, filed January 19, 1988. Their preparation is illustrated by the following examples.

.. - , :
.

.
-,, . :- : .
- : ~ : , .

RD-~9372 CIP of RD-18777 Example 1 To a mechanically stirred solution of 220.8 g. (1.2 moles) cyanuric chloride in 1500 ml. chloroform, cooled to 0-lO C, was added 266.4 g. (3.6 moles) glycidol in one portion.
Aqueous sodium hydroxide ~50% solution; 192 g.) was added to the mixture dropwise with stirring over about 3 hours main-taining the reaction temperature below lO C and preferably around 0-5 C. The reaction mixture was allowed to warm slowly to room temperature. The chloroform layer was washed with distilled water until neutral and dried over magnesium sulfate. The reaction product was found by carbon-13 nuclear magnetic resonance to be 2-chloro-4,6-diglycidoxy-1,3,5-tri-azine (DGCC). Analysis by liquid chromatography showed about 95% (by weight) chlorodiglycidoxytria~ine. The reaction mix-ture also was found to contain small amounts of triglycidoxy-triazine and dichloroglycidoxytriazine.

Exa~ple 2 To a magnetically stirred solution of 250 g. (1.125 moles) n-butyl dichlorocyanurate in 757 ml. chloroform, cooled to 0-lO C, was added 250 g. (3.375 moles) glycidol in one portion. Aqueous sodium hydroxide (50% solution; 90 g.) was added to the mixture dropwise with stirring over about 2 hours, maintaining the reaction temperature below lO C and preferably around 0-5 C. The reaction mixture was allowed to warm to room temperature over 30 minutes. The chloroform layer was washed with distilled water until neutral and dried over magnesium sulfate. Proton nuclear magnetic resonance analysis indicated a 95% yield of 2-chloro-4-(n-butoxy)-6-glycidoxy-1,3,5-triazine (BGCC).

:

Rl:)-l 9372 CIP of RD-18777 Example 3 To a mechanically stirred solution of 50 g. ~0.175 mole) 2, 4,6-trimethylphenyl dichlorocyanurate (prepared by 5 the reaction of equimolar amounts of mesitol and cyanuric chloride) in 170 ml. methylene chloride, cooled to 0-lO C, was added 26.38 g. (0.356 mole) glycidol in one portion.
Aqueous sodium hydroxide (50% solution; 14.26 g.) was added to the mixture dropwise with stirring over about 25 minutes maintaining the reaction temperature between 0 and lO C and - preferably around 0-5 C. After stirring an additional 30 minutes, the reaction mixture was allowed to warm to room temperature. The methylene chloride layer was washed with -distilled ~ater until neutral and dried over magnesium sul-15 fate. The reaction product was found by proton nuclear mag-netic resonance to be 2-chloro-4-(2,4,6-trimethylphenoxy)-6-glycidoxy-1,3,5-triazine (MGCC).
Various options are available for the reaction of the polyphenylene ether with the epoxychlorotriazine. In one method, the reaction is conducted in solution in a non-polar organic liquid, typically at a temperature in the range of about 80-150 C and preferably about 100-125 C. The basic reagent employed in this method should be soluble in the or-ganic li~uid and is generally a tertiary amine. Its identity is not otherwise critical, provided it is sufficiently non-volatile to remain in the reaction mixture at the tempera-tures employed. Pyridine is often preferred.
The amount of epoxychlorotriazine employed in this option is generally in the range of about 1-20% by weigh~, based on polyphenylene ether. The amount of basic reagent is an effective amount to promote the reaction; in general, about 1.0-1.1 equivalent thereof per mole of chloroepoxytri-azine is adequate.

:
- ~ . .
.

- 15 Z~n~
-CIP of RD 18777 The epoxytriazine-capped polyphenylene ethers made in solution by the above-described process are generally found to contain rather high propoctions (e.g., at least about 0.4~ by weight) of chemically combined chlorine, prin-cipally covalently bound. It is believed that the covalen~lybound chlorine is the result of epoxy groups competing with the organic base as a hydrogen chloride acceptor, with the formation of chlorohydrin moieties. This may be followed by condensation of said chlorohyd~in moieties with additional epoxy groups tO produce such molecular species as polypheny-lene ether-epoxytriazine block copolymers and homopolymeric epoxytriazine oligomers.
Upon molding, compositions containing polyphenylene ether copolymers prepared from products containing such species form articles which are ductile but have impact strengths somewhat lower than desired under certain condi-tions. This is particularly true of copolymers with polyesters.
A second, preferred method of preparation produces epoxytriazine-capped polyphenylene ethers with little or no covalently bound chlorine. In this method, the reaction is conducted interfacially in a medium comprisin~ water and an organic liquid as previously described. The basic reagent is a water-soluble base, typically an alkali metal hydroxide and preferably sodium hydroxide. It may added to the mixture of epoxychlorotriazine and polyphenylene ether, or may initially react with the polyphenylene ether to form a salt which is then contacted with the epoxychlorotriazine. There is also employed a phase transfer catalyst. Any of such catalysts which are stable and effective under the prevailing reaction conditions may be used, those skilled in the art will readily perceive which ones are suitable. Particularly preferred are the tetraalkyla~onium chlorides wherein at least two alkyl . . : ~- , , - :
.

CIP of RD-18777 groups per molecule, typica1ly 2 or 3, contain about 5-~0 carbon atoms.
In this method, reaction temperatures in the range of about 20-lOO C may be employed. The amount of epoxychlorotriazine is frequently lower than in the previ-ously described method, typically in the range of about 1-6 and preferably about 2-6% by weight based on polyphenylene ether, since the reaction of the epoxychlorotriazine with the polyphenylene ether apparently proceeds more nearly to com-pletion. Most often, the ratio of equivalents of base tomoles of epoxychlorotriazine is about 0.5-1.5:1, and the weight ratio of phase transfer catalyst to base is about 0.01-5.0:1.
Still another method utilizes an organic liquid and a solid base, typically a solid alkali metal hydroxide or an anion exchange resin in the free base form. Chloride salts may be removed by methods known in the art, including water washing when a hydroxide is employed and filtration when an anion exchange resin is employed.
Regardless of which method of preparation is used, the epoxytriazine-capped polyphenylene ether may be isolated by conventional methods, typically by precipitation with a non-solvent. Among the non-solvents which may be employed are methanol, l-propanol, acetone, acetonitrile and mixtures thereof.
When the non-solvent is an alcohol, and especially methanol, it may undergo base-promoted reaction with the ;
epoxytriazine moieties on the capped polyphenylene ether, usually resulting in a loss of epoxide groups. Either or both of two operations may be employed to suppress this reac-tion. The first is to neutralize the reaction mixture with any convenient acidic compound; carbon dioxide, in gaseous, liquid or solid form, is often preferred. The second is to , . : : :. . ~ . : .

- 17 - 2~

CIP of RD-18777 remove alcohol from contact with the product as rapldly and completely as possible by conventional means, typically in-cluding a subsequent drying step.
In the following examples which illustrate the preparation of epoxytriazine-capped polyphenylene ethers, proportions of epoxychlorotriazine are expressed as a per-centage of polyphenylene ether. The following polyphenylene ethers were employed:
PPE - a poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity in chloroform at 25 C of 0.40 dl./g.
W - PPE which had been extruded on a twin screw extruder within the temperature range of about 260-320 C, with vacuum venting to a max-imum pressure of about 20 torr.
LN - a poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.57 dl./g., having a low proportion of nitrogen as a result of preparation with a catalyst contain-ing no primary or secondary amine.

Percentages of epoxytriazine in the capped polymer were de-termined from the relative areas of peaks in the nuclear mag-netic resonance spectrum attributable to hydrogen atoms in the epoxy and aromatic moieties. Chlorine percentages were determined by quantitative X-ray fluorescence.
Exampl~s 4-14 To solutions of 400 grams of polyphenylene ether in 2500 ml. of toluene were added, with stirring, various quan-3S tities of pyridine followed by various quantities of epoxy-chlorotriazines, added in portions. The ratio or equivalents of pyridine to moles of epoxychlorotriazine was 1.04:1. The ~'' ' ~' . ~ : . .- . . - . - .

18 ~
-CIP of RD-18777 solutions were heated under reflux for various periods of time, after which the products were precipitated with methanol in a blender, filtered, washed with methanol and vacuum dried. The relevant parameters and analytical results are given in Table I.
TABLE I

Poly- Epoxy- %
phenylene chlorotriazine Reaction epoxy- ~ -~ampl~ ether Ident,~y ~ tims~ hr~. c~iazi~ chlorine 4 P~E DGCC 5 2 0.52 ---PPE DGCC 5 3 0.62 ---6 W DGCC 5 1 0.43 0.42 7 W DGCC 5 2 0.65 ---8 W DGCC 5 3 0.63 0.47 9 W DGCC 2.53.5 0.24 ---W DGCC lS 3 2.1 1.8 11 w DGCC 15 3 1.9 ---12 W BGCC S 3 O.S0 ---13 W BGCC 5 3 0.40 ---14 W ~GCC lS 3 1.79 ---ExamDles 15-25 To solutions of 400 grams of polyphenylene ether in 2500 ml. of ~oluene were added various quantities of epoxy-chlorotriazines dissolved in a small amount of methylene chloride. There were then added 48 grams of a 10% solution in toluene of a commercially available methyltrialkylammonium chloride in which the alkyl groups contained 8-10 carbon atoms, and 10% aqueous sodium hydroxide solution in the amount of 1.3 equivalents of sodium hydroxide per mole of epoxychlorotriazine. The mixtures were stirred vigorously for various periods at 25-40 C, after which the products were precipitated with methanol in a blender and rapidly filtered, washed with methanol and vacuum dried.

:: -'' ' :

-19- ~n~

CIP of RD-18777 The results are given in Table II. Chlorine pro-portions were less than 200 ppm., the minimum detec~able b~
quantitative X-ray fluorescence.
~a~
Polyphenylene Epoxychlorotria~ine Reaction Exam~ls _ ethe~, _ Iden~i~Y - ~ t.im~. m; n ~
PPE DGCC 1.5 30 0.52 16 PPE DGCC 2.0 30 1.03 17 PPE DGCC 2.5 30 0.95 18 PPE DGCC 3.0 30 0.96 19 PPE* DGCC 3.0 30 1.01 20~* PPE DGCC 3.0 30 1.24 21 ~N DGCC 3.0 30 0.48 22 PPE DGCC 5.0 30 1.40 23 W DGCC S.0 10 0.68 24 PPE 8GCC 3.0 30 1.25 PPE MGCC 3.0 30 1.50***
~16% qlurry of crude PPE in toluene.
~R~action muxture neutralized with gaqeouq carbon dioxide.
*~*Average of 3 run~.

Any condensation polymer containing carboxy end groups may be employed in the present invention. Polyesters are particularly preferred. Howe~er, carboxy-terminated polymers containing linkages other than ester linkages, either alone or in combination with ester linkages, are included.
Such polymers are illustrated by various elastomeric polyesteramides, including block polyetheresteramides prepared by the reaction of a carboxy-terminated polyamide with a polyoxyalkylene glycol such aspolyethylene glycol, polypropylene glycol or polytetramethylene glycol. Typical carboxy-terminated -polyamides are prepared by the polymerization of amino acids or lactams such as e-caprolactam, ll-aminoundecanoic acid and 12-aminododecanoic acid in the presence of a dicarboxylic -''` ` ' ~ ~ ~ ' - 20 ;~ 3~fl~
.

CIP of RD-18777 acid such as adipic acid. A class of suitable block polyetheramides is sold by Atochem Inc. under the trade name PEB~X.
Also included are polyesteramides such as the S material sold by Dow Chemical under the designation xuS-63115. It is typically prepared by first forming a carboxy-terminated polyester and subsequently effecting reaction of said polyester with an aromatic diisocyanate.
The polyesters, which are preferred~ generally comprise structural units of the formula (IX) -0-Rq-O-C-A -C-wherein each R4 is independently a divalent aliphatic, lS alicyclic or aromatic hydrocarbon or polyoxyalkylene radical and Al is a divalent aromatic radical. They include thermoplastic polyesters illustrated by poly(alkylene dicarboxylates~, elastomeric polyesters, polyarylates, and polyester copolymers such as copolyestercarbonates. Because the principal reaction which occurs with the epoxy groups in the capped polyphenylene ether involves a carboxylic acid group of the polyester, it is highly preferred that said polyester have a relatively high carboxylic end group concentration. Concentrations in the range of about 5-250 microequivalents per gram are generally suitable, with lO-lO0 microequivalents per gram being preferable, 30-lO0 being more preferable and 40-80 being particularly desirable.
The polyester may include structural units of the formula - 21 ~

CIP of RD-18777 R R

( X ) -O -R4 -o-ll _A2 \ N s C \C
a 1~

wherein R4 is as previously definedr R5 is a polyoxyalkylene radical and A2 is a trivalent aromatic radical. The Al radical in formula IX is most often p- or m-phenylene or a mixture thereof, and A2 in formula X is usually derived from trimellitic acid and has the structure ~ ~ , ' The R4 radical may be, for example, a C2_l0 aLkylene radical, a C6_l0 alicyclic radical, a C6_20 aromatic radical or a polyoxyalkylene radical in which tne alkylene groups contain about 2-6 and most often 4 carbon atoms. As 15 previously noted, this class of polyesters includes the -poly(alkylene terephthalates) and the polyarylates.
~oly(alkylene terephthalates) are frequently preferred, with poly(ethylene terephthalate) and poly(butylene terephthalate) being most preferred.
The polyester generally has a number average molecular weight in the range of about 20,000-70,000, as determined by intrinsic viscosity (IV) at 30 C in a mixture of 60% (by weight) phenol and 40% l,1,2,2-tetrachloroethane.
Either solution or melt blending procedures may be employed for the preparation of the copolymer compositions of this invention. Typical reaction temperatures are in the - 22 - ~ &~ 41.

CIP of RD-18777 range of about 175-350 C. Thus, relatively high boiling solvents such as o-dichlorobenzene, nitrobenzene or 1,2,4-trichlorobenzene are preferred for solution reactions.
Melt reaction procedures are frequently preferred because of the availability of melt blending equipment in commercial polymer processing facilities. Conventional equipment of this type is suitable, with the use of extrusion equipment generally being convenient and therefore often preferred.
The principal reaction which takes place between the epoxytriazine-capped polyphenylene ether and a polyester generally involves the carboxylic acid end groups of the latter, which open the epoxide rings to form hydroxy ester groups. Thus, a preferred embodiment of the invention is polyphenylene ether-polyester copolymers comprising molecules containing at least one polyphenylene ether-polyester linkage of the formula Q~ Ql ozl ~XI) - ~ ~ O ~ ~ CH2-Z2 ~ N ~ 1 1 3 Q2 Ql O-R -CH-Z

wherein Ql, Q2 and Rl are as previously defined; zl is an alkyl, cycloalkyl or aromatic radical (most often lower alkyl fH2_z2 or aromatic hydrocarbon) or -R -CH-Z ; and z2 is OH and Z3 is -O-C-, or z2 is -O-C- and Z3 is OH.
Another possible reaction is between hydroxy end groups of the polyester and the epoxy groups of the capped polyphenylene ether. Thus, the compositions of the invention .
. -. .

:: :

- 23 - ~ 41 ~D-19372 CIP of RD-18777 are not limited to compounds containing linkages of formula XI but may include compounds with linkages of similar structures containing ether moieties replacing the carboxylate moieties of z2 or Z3.
The proportions of polyphenylene ether and other polymer employed for the preparation of the compositions of this invention are not critical; they may be widely varied to provide compositions having the desired properties. Most often, each polymer is employed in an amount in the range of about 5-95-~, preferably about 30-70%, of the composition by weight.
In addition to polyphenylene ether-polyester copolymer, the compositions of this invention also contain unreacted polyphenylene ether. This will include any polyphenylene ether molecules having only hydrogen bonded end groups (i.e., the aminoalkyl-substituted end groups of formula Iv), as well as other polyphenylene ether which is unfunctionalized as a result of incomplete capping or which is functionalized but fails to react with polyester. Said compositions may also contain unreacted polyester. In any event, molded parts produced from said compositions are generally duc~ile and ha~e higher impact strengths than those produced from simple polyphenylene ether-polyester blends, which are incompatible and often exhibit brittleness or delamination as previously described.
Experimental data suggest that certain other factors are of importance in preparing compositions of maximum impact strength. One of these is the proportion of chlorine in the epoxytriazine-capped polyphenylene ether.
Compositions of this invention prepared from high chlorine capped polyphenylene ethers, obtained by the solution method previously described, often have lower impact strengths ~han , - . ~ .~ . , .

.
.

CIP of RD-18777 those prepared from the low chlorine materials obtalned by the interfacial method.
Another factor is the proportion of unneutralized amino nitrogen in the polyphenylene ether. ~igh proportions may cause side reactions, including opening of epoxide rings, displacement of epoxide groups from the cyanurate moiety and cleavage of ester linkages. Such side reactions can be minimized by vacuum venting the polyphenylene ether and/or the composition of this invention as previously described. A
third factor is the molecular structure of the copolymer, which may vary with the molecular structure of the capping agent used ~BGCC or MGCC as contrasted with DGCC) and i.s proportion.
It also appears that compositions containing "high chlorine" capped polyphenylene ethers have a greater tendency toward ductili~y and high impact strength when a polyphenylene ether containing a low proportion of unneutralized amino nitrogen is employed, while the opposite is true for "low chlorine" materials. The reason for this is ~0 not presently understood.
The compositions of this invention may contain other constituents in addition to the polyphenylene ether, other polymer and copolymer. Examples are impact modifiers compatible with either or both of the polyphenylene ether and the other polymer.
Suitable impact modifiers include various elastomeric copolymers, of which examples are ethylene-propylene-diene polymers (EPDM's~, both unfunctionalized and functionalized with (for example) sulfonate or phosphonate groups; carboxylated ethylene-propylene rubbers; polymerized cycloalkenes; and block copolymers of alkenylaromatic compounds such as styrene with polymerizable olefins or dienes, including butadiene, isoprene, chloroprene, ethylene, ~ .
- -, :
-: . .
~ . .

2~

CIP of RD-18777 propylene and butylene. Also included are core-shell polymers, includin~ those containing a poly(alkyl acrylate) core a~tached to a polystyrene shell via interpenetrating network, and more fully disclosed in U.S. Pa~ent 4,681,915.
The preferred impact modifiers are block (typically diblock, triblock or radial teleblock) copolymers of alkenylaromatic compounds and dienes. Most often, at least one block is derived from styrene and at least one other block from at least one of butadiene and isoprene.
Especially preferred are the triblock copolymers with polystyrene end blocks and diene-derived midblocks. It is frequently advantageous to remove (preferably) or decrease 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 and G1702.
The presence of such polymers as polycarbonates, copolyestercarbonates or polyarylates may have the effect of improving the impact strengths of molded articles under severe molding conditions, such as high molding temperatures and/or prolonged molding cycle times. The same purpose is frequently served by incorporating in the composition at least one other compound containing a plurality of epoxide moieties (hereinafter "polyepoxide"), generally in the amount of about 0.1-3.0 and preferably about 0.25-3.0% of the composition. Illustrative compounds of this type are homopolymers of such compounds as glycidyl acrylate and glycidyl methacrylate, as well as copolymers thereof, ^ preferred comonomers being lower alkyl acrylates, methyl methacrylate, acrylonitrile and styrene. Also useful are - 26 - 26~

CIP of RD-18777 epoxy-substituted cyanurates and isocyanurates such as triglycidyl isocyanurate.
The other polyepoxide may be introduced by blending with the other components in a single operation. ~owever, its effectiveness may be maximized by preblending with the polyester, typically by dry mixing followed by extrusion.
Such preblending frequently increases the impact strength of the composition. While the reason for the effectivene$s of the other polyepoxide is not entirely understood, it is believed to increase molecular weight, melt viscosity and degree of branching of the polyester by reaction with carboxylic acid end groups of a portion of the polyester molecules.
Finally, there may be present conventional ingredients such as fillers, flame retardants, pigments, dyes, stabilizers, anti-static agents, crystallization aids, mold release agents and the like, as well as resinous components not previously discussed.
In the following examples illustrating the preparation and properties of copolymer compositions of this invention, the polyesters and impact modifiers employed are identified as follows:
PET - various poly(ethylene terephthalates~. - 5 PBT - a poly(butylene terephthalate) having a number average molecular weight of about 50,000, as determined by gel permeation chromatography. 0 PATME - a commercially available elastomeric polyterephthalate from a mixture of tetramethylene glycol, hexamethylene glycol and poly(tetramethylene ether) glycol. 5 PTME(50,000) and PTME(54,000) - a commercially available elastomeric polyterephthalates from mixtures of tetramethylene glycol and .

- 2-~ - 2~

CIP of RD-18777 poly(tetrame~hylene ether) glycol, having the designated number average molecular weights and about 20% and 50% by weight, respectively, of poly(tetramethylene ether) glycol units.
PIE ~ a copolyester prepared from 1,4-butanediol and a 0.91:1 (by weight) mixture of dimethyl terephthalate and the diimide-diacid reaction product of trimellitic acid and a polyoxypropylenediamine having an average molecular weight of about 2000.
SEBS - a commercially available triblock copolymer with polystyrene end blocks having weight average molecular weights of 29,000 and a hydrogenated butadiene midblock having a weight average molecular weight of 116,000.
CS - a core-shell material containing 75% of a crosslinked poly(butyl acrylate) core and 25%
of a crosslinked polystyrene shell, prepared in accordance with U.S. Patent 4,684,696.
PO - a polyoctenylene with a cis-trans ra~io of 20 80~ having a weight average molecular weight of about 55~000~
The resinous blends described were prepared by dry mixing and extruded on a twin-screw extruder at 400 rpm. and 30 190-255-C (unless otherwise stated). The extrudates were quenched in water, pelletized, oven dried and molded at 280~C
in~o test specimens which were tested for notched Izod impact strength and tensile properties (ASTM procedures D256 and D638, respectively) and heat distortion temperature at 0. 455 MPa. (ASTM procedure D648)o All parts and percentages in the following examples are by weight. The proportion of bound polyphenylene ether, where listed, was determined by extracting uncopolymerized polyphenylene ether with toluene and determining the proportion of polyphenylene ether in the residue by nuclear magnetic resonance spectroscopy; it is a general indication of the amount of copolymer in the composition.

.. .- , . . . . . : , ~ . .

. . ~ - . , :

- 28 ~

CIP of RD-18777 ExampLes 26-35 Compositions containing various proportions of epoxytriazine-capped polyphenylene ethers prepared as described in Examples 4-14, various polyesters and sEss were prepared and molded. The relevant parameters and test results are given in Table III.

: - :, : .. . -:
- , : ~ - . .. ..

-29- E~D-19372 -- C ' . ~ C~ ~ '`
_ ~, o ,_".,__ ~ o >~ o--n~,O C' ~ ~> r~ 5 0 0 _ ~ o> . 5 t:: 5--C`J
~: ~ O ~ _ a ~ > O ~
>~ 50 1 0 --~C~-->~ ~n 50 iJ ~ > ~ ~ = o ~ )` 5 I > O ~ ~ ~ ~ - O l~
>5~ ¢ ~0`~

,, ~O Q
O C C~ ' 3 ~ N C ~, ~e ~-_c~
C _ ~ ~ >. u ~
-- C~ L -- ~ _ 3 3 L ~ ~ _ _ _ _ ,. "

-, '' ' ' ,~- , ' , . ' ' ': , :
'.-'.: ' ~ . '' ' ` ' '~ ' ' '' .
:

- 30 - ~

CIP of RD-18777 Exam~les 3~-47 Compositions were prepared and molded from the epoxytriazine-capped polyphenylene ethers of Examples 15-25, PBT and SEBS. The relevant parameters and test results are given in Table IV.

' . . : ~' -31- ;~
Rr)-19372 ~ O ~ O ;r~
_,, ,~ ,` , I
-- C~ _ N ~ N N C ~ n r ~ C~
~ ~ 7 3 _ Lo r--o--~7 c ^
.~ _~ n N i N ~ 7 N S
_= _ 5 ~ s _ E
'~1 ~ ~7 O ~7 _ Ql O -- 7 Cl--u~ U~ O 'q W 7 c~
~ -Ul C 0~0000000~000 0 ~7 ~o :S S _ _ 5 3 _ _ _ N _ 5 c 3 0~ 0 0 o~7 0N o o a ~ f ~ ~ ~q ~ ~ r ~c> , , c c_ ~,n~r-~o--Nr~7~ ~~
~7 _ ~ ~ ~U ~ tU N
O ~ X X X X X X X X X X X X
0~
471 ~ 7 ~7 r~7 Y7 5 _ _ 5 _ _ 5 5 `, ' :, :

:. '' ~
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32 2~ ~3~ ~

CIP of RD-18777 Examplçs_4~-42 Compositions similar to those of Examples 18 and 24 were prepared and molded, substituting 18 parts of PPE for an equal weight of the epoxytriazine-capped polyphenylene ether.
The relevant test results are given in Table V.
TABI.E V
Example 4~ 49 Capped polyphenylene ether Ex. 18 Ex. 24 Izod impact strength, joules/m.48 64 15 Tensile strength, MPa.:
At yield 44.7 44.2 At break 35.1 36.8 Tensile elongation, ~ 39 61 Examples 50-$7 Compositions containing epoxytriazine-capped polyphenylene ethers, PET and (in Examples 50-55) SEBS were prepared and molded. In certain instances, the PET was first preextruded at 271-C and dried in order to increase the proportion of carboxylic acid end groups. The following PET's were employed:
"Kodapak 7352" (Eastman Kodak Co.) "Vituf lOOlA" (Goodyear Chemical) "Rohm & Haas 5202A"
Recycled bottle scrap, number average molecular weight about 40,000.
The relevant parameters and test results are given in Table VI.

.. ,. , : ~ : .

o .
~r x o L
`C C 3O I I ~ ~O N
~` X g C~
.1 Y u~ ,n ~ ~ ~ C 5 ~
~O 1 L----~
X C~ ~ - S
_ ~ ~
_ ~1 E 111 _ O 31 N S _ X o-- r- N N
C ~ ~ 55 X
~- `O ~ --O _ ~O N N
X -- o~__ ., ~;¦ N C 5 o, ~ N `O
L~i X O ~ N
--I 1~ X S 5 ~Z:l Y
N ~ ~ Sor-- --~a~ .
U' I X O - 5~ ~
~D ' .
e ~O C 5 0 ~ 5~
~ X ~ ,t ",~ e . S, C C ~.
>, ~ C ~ ~ .
_ ~o C
>, ~ - ~ O
- >, >. ~ u e ~ - x C'-- -- A ~ = 31 Q~
~_,~ c .~ .n--1' ~ =-=''' .
:

:

- 34 - ~ 3 CIP of RD-18777 Examples 58-~1 Compositions containing the epoxytriazine-capped polyphenylene ether of Examples 18, PBT, bottle scrap PET and (in Examples 58-60) SEBS were prepared and molded. The relevant parameters and test results are given in Table VII.

TA~LE VT I
Example ~8 5~ 60 61 Capped polyphenylene ether, parts36 36 36 40 Polyester, parts:

SEBS, parts 10 10 10 --Izod impact strength, joules/m. 753193 812 --Tensile strength, MPa.:
At yield 43.9 41.644.546.1 At break 42.3 40.839.640.6 Tensile elongation, ~ 151 220195 178 ExamRl~ 62-64 Compositions containing epoxytriazine-capped polyphenylene ethers similar to that of Example 18 but containing 0.75-0.8S% epoxytriazine, PBT and CS or PO were prepared and molded. The relevant parameters and test results are given in Table VIII.
.

CIP of RD-18777 62 ~ 64 Capped polyphenylene ether, parts 36 37 36 PBT, parts 54 55 54 Impact modifier, parts:

PO ~ 10 Izod impact strength, joules/m.561219 155 Tensile strength, MPa.:
At yield 46.744.741.9 At break 40.841.434.9 15 Tensile elongation, % 134135 70 Heat distortion temp.~ C -- 156 162 Exam~les 65-74 Compositions containing epoxytriazine-functionalized polyphenylene ethers, various elastomeric polyesters and (in Examples 65-71) SEBS as an impact modifier were prepared and molded. The relevant parameters and test results are given in Table IX.

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, , ~- . - :

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_ ~

_ ~ o C
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~ C o r-~o~oo00 C o --~ 5---- ~ N-- ~ N
1--_ Q
w N ~ ~ 5 0 ~ N ~O
3 ~ ~ O ~ 0 ~ IN~----5~-----~5 _ c Q
c ~ s i ~ ~ ~ I
t 3 5: E
C~ ~ * ~_~ ~ r N c3_ ~ -- i~
--6a ~1 ._ ~ L 111 0 0 0 0 0 0 0 1 Xi ~-- Ll _ _ _ ~
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L a. __. __ O

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3 ~ ~ ~ n S ~ j W~
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-- C' XXXXXXXXXX O
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El ll~`D~'10~0--N~S
xi ` ` ` ` ` )-- .

, , - . - .: - ~ , . . . , , :

91~.

CIP of RD-18777 Exam~les 7~- ao Compositions containing the epoxytriazine-capped polyphenylene ether of Example 18, mixtures of PBT with various elastomeric polyesters, and (in Examples 75-79) SEBS
as an impact modifier were prepared and molded. The relevant parameters and test results are given in Table X.

- - ~ .

.

- 3 8- ~ 4~

C~ 5 I t . .

~ o~ I I ~o- r-o~
rO ~

~o~ I ~ I ON ~O
31 r ~ 1 s C~
8~ ~o~ ~ oo OCls r ~ I N I ~ Os X

c ~I t 5 ~ u~ I O s C~ ~ ~
C:l N --CD--~ ~O 1` 1~ ~ I O ~
r~ ~ ~1 N I I ~ t CL ~
..

C ~ c ~ o C -- L~
O ^~
5:~ O ul c c~
,~ O O Ut ~ L ~ X ~ ' ~
O ~ ~_ O L ~O ~~ ~ ~ ,: , E ~-- a G
O L~
c~ ~ u~
CLI tJ Q. ~ C. ~ O - ~t " ~
c,~ n--r 1--' ' . : ` :

.
:: :

CIP of RD-18777 Exam~le~ 81-86 Compositions were prepared by extrusion at 120-290 C from various proportions of an MGCC-capped polyphenylene ether prepared using 5% MGCC, three different grades of PEBAX block copolyetheramides and (in certain examples) impact modifier. The relative proportions and test results are given in Table XI. No delamination was observed.
~
Example 81 82 a3 84 85 86 15Polyphenylene ether 40 36 40 36 40 36 (MGCC-capped), %
Block polyetheramide, %:

Impact modifier, % -- 10 -- 10 -- 10 Izod impact strength, -- 438 -- 689 - *
joules/m.
Tensile strength, Mæa.:
25At yield -- -- -- 26.3 -- --At break 21.921.3 31.9 35.913.9 14.1 Tensile elongation, % 240224 167 214 585 568 *~id not break; too flexible.
Examples 87-41 The epoxytriazine-capped polyphenylene ethers employed in these examples were MGCC-capped products similar to that of Examples 81-86, prepared employing 3.5% and 5%
MGCC. The other polymer was a polyesteramide prepared from azelaic acid, l,4-butanediol and methylene bis~p-isocyanato-benzene), commercially available from Dow Chemical under the ': -,~ .
, - 40 ~

CIP of RD-18777 grade designation XUS 63115. The blending procedure was that employed in Examples 81-86.
The proportions and test results are given in Table XII, in comparison with two controls employing uncapped polyphenylene ethers. No delamination was observed.

:., . .~

X ~ I ~ I ~ I O N ~ N--O O ~

X O I O I I O O ~ ~ I N q:l N ~_ .

~ t ~N I~U O o ~ ~
to ~u ~
\ I ~ O~ O I I I I N--r C~ ;P
X ~ O I II O ~ O
` O
X O ~ o S I S N
~s~ .
X r~ ~o I II :S I O I N ~
~ .
X

=
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C tJ~ :~ ~ c~ C .~
~ ~~ qJ c -- c t~ ~ --~ I_ o o 0 21 a~ ,~ J
> ~O O ~ 0 _ ~ O ~L o ~ ~ '~ ~ a ~
' ' . : : -i

Claims (22)

1. A composition comprising polyphenylene ether-polyester copolymers prepared by the reaction of an epoxytriazine-capped polyphenylene ether with at least one condensation polymer containing carboxy end groups.

2. A composition according to claim 1 wherein the condensation polymer is an elastomeric copolyesteramide.

3. A composition according to claim 1 wherein the condensation polymer is a polyester comprising structural units of the formula (IX) , wherein each R4 is independently a divalent aliphatic, alicyclic or aromatic hydrocarbon radical or polyoxyalkylene radical and Al is a divalent aromatic radical.

4. A composition according to claim 2 wherein the polyphenylene ether comprises a plurality of structural units having the formula (III) , herein each Q1 is independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Q2 is independently hydrogen, halogen, primary or secondary CIP of RD-18777 lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q1.

5. A composition according to claim 4 wherein Al is p- or m-phenylene or a mixture thereof.

6. A composition according to claim 5 wherein the polyphenylene ether is a poly(2,6-dimethyl-1,4-phenylene ether).

7. A composition according to claim 6 wherein R1 is methylene and Al is p-phenylene.

8. A composition according to claim 7 wherein R4 is ethylene.

9. A composition according to claim 7 wherein R4 is tetramethylene.

10. A composition according to claim 7 wherein R4 is polyoxytetramethylene.

11. A composition according to claim 7 which also contains an impact modifier.

12. A composition according to claim 11 wherein the impact modifier is a triblock copolymer wherein the end blocks are derived from styrene and the midblock is derived from at least one of isoprene and butadiene.

13. A composition according to claim 12 wherein the midblock has been hydrogenated.

14. A composition according to claim 7 wherein the polyester also contains units of the formula CIP of RD-18777 wherein R5 is a polyoxyalkylene radical and A2 is a trivalent aromatic radical.

15. A composition comprising polyphenylene ether-polyester copolymer molecules containing at least one polyphenylene ether-polyester linkage of the formula wherein R1 is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical;

Z1 is an alkyl, cycloalkyl or aromatic radical, or ;

and Z2 is OH and Z3 is , or Z2 is and Z3 is OH.

16. A composition according to claim 15 wherein R1 is a lower alkylene radical.

17. A composition according to claim 16 wherein the polyphenylene ether is a poly(2,6-dimethyl-1,4-phenylene ether).

18. A composition according to claim 17 wherein R4 is ethylene.

19. A composition according to claim 18 wherein R1 is methylene and A1 is p-phenylene.

20. A composition according to claim 19 wherein Z1 is a lower alkyl or aromatic hydrocarbon radical.

21. A composition according to claim 20 wherein Z1 is methyl, n-butyl or 2,4,6-trimethylphenyl.

CIP of RD-18777

22. A composition according to claim 19 wherein Z1 is .