CA2010140A1 - Epoxytriazine-capped polyphenylene ethers and method of preparation - Google Patents
Epoxytriazine-capped polyphenylene ethers and method of preparationInfo
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Abstract
CIP of RD-18199 EPOXYTRIAZINE-CAPPED POLYPHENYLENE ETHERS
AND METHOD OF PREPARATION
Abstract Epoxytriazine-capped polyphenylene ethers are prepared by reaction of a polyphenylene ether with an epoxychlorotriazine such as diglycidyl chlorocyanurate, n-butyl glycidyl chlorocyanurate or mesityl glycidyl chlorocyanurate. The products undergo reaction with nucleophilic polymers such as polyamides and polyesters, to form copolymer-containing compositions which have excellent properties and which find utility as molding compositions and as compatibilizers for blends of similar polymers.
AND METHOD OF PREPARATION
Abstract Epoxytriazine-capped polyphenylene ethers are prepared by reaction of a polyphenylene ether with an epoxychlorotriazine such as diglycidyl chlorocyanurate, n-butyl glycidyl chlorocyanurate or mesityl glycidyl chlorocyanurate. The products undergo reaction with nucleophilic polymers such as polyamides and polyesters, to form copolymer-containing compositions which have excellent properties and which find utility as molding compositions and as compatibilizers for blends of similar polymers.
Description
- 1 - 2~ '10 CIP of RD-18199 EPOXYTRIAZINE-C~pPED POLYPHENyL~ ETHERS
AND METHOD OF PREPA~ATIQN
This application is a continuation-in-part of copending application Serial No. 210,547, filed June 23, 1988.
This invention relates to the preparation of polyphenylene ethers containing epoxy groups, and to the use of such polyphenylene ethers in the preparation of copolymer-containing compositions.
The polyphenylene ethers are a widely used class of thermoplastic engineering resins characterized by excellent hydrolytic stability, dimensional stability, toughness, heat resi~tance and dielectric properties. However, they are de-flcient in certain other properties such as workability and solvent resistance. Therefore, there is a continuing search for means for modifying polyphenylene ethers to improve these other propertles.
Among the means being studied are blending of polyphenylene ethers with certain other resinous materials such as polyesters, polyamides or olefin polymers. Blends of these other materials with polyphenylene ethers are, however, usually incompatible. Molded parts fabricated from such blends are generally brittle and may undergo catastrophic delamination upon impact.
Numerous methods for compatibilizing polyphenylene ether-polyester compositions have been developed. For exam-ple, PCT published application 87/850 describes blends com-patibilized by the addition of an aromatic polycarbonate.
Said blends are extremely versatlle in numerous critical ap-plications such as the fabrication of automobile body parts.
However, the presence of polycarbonate may result in degra-Zl[~10~40 CIP of RD-18199 dation of certain other properties such as heat distortion temperature.
In addition, a problem sometimes arises by virtue of the presence of aminoalkyl-substituted end groups on S 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 reslns. 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 polyamides as amino, hydroxy and carboxy groups, leading to copolymer formatlon.
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 dissolutlon of the polyphenylene ether in a large excess of epichlorohydrin, a relatively expensive reagent which is also a strong skin irritant and can cause kidney injury.
i _ 3 _ 2~ 0 CIP of RD-18199 PCT published application 87/7279 describes the reaction of polyphenylene ethers with terephthaloyl chloride and glycidol to form an epoxy-functionalized polyphenylene 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 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 methacrylate, are toxic. Moreover, the reactlon is generally accompanied by homopolymerization of the epoxy-functlonalized monomer, and it is then necessary to remove the homopolymer by such compllcated operations as dlssolution of the crude polymeric product followed by forma-tlon and decomposltlon of a polyphenylene ether-methylene chlorlde complex. Thus, these materials may not be readiiy adaptable to copolymer preparatlon on an industrial scale.
The present invention provides a simple method for introducing epoxy functionality into a polyphenylene ether, employing simple solution or interfacial conditions and relatively lnexpensive reagents. The products are hi.ghly reactive and readily convertlble under both solution and melt conditions to compositions comprislng copolymers of polyphenylene ethers with a wide variety of strongly and weakly nucleophilic polymers, notably polyesters and _ 4 ~ L40 CIP of RD-18199 polyamides. Said compositions have excellent physical properties, particularly when blended with conventional impact modifiers for polyphenylene ethers. They also compatibilize blends containing unfunctionalized polyphenylene ethers.
In one of its aspects, the invention includes epoxytria7ine-capped polyphenylene ether compositions which comprise polymer molecules having end groups of the formula Q2 Ql OX
(I) - ~ N ~
10 Q2~Ql \ O-Rl-CH-CH2 wherein:
each Ql is independently halogen, primary or sec-ondary lower alkyl (i.e., alkyl containing up to 7 carbon . 15 atoms), phenyl, haloalkyl, aminoalkyl, 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 1 ~~
(II) -R -CH-CH2 ; and 25Rl is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatlc hydrocarbon radical.
The compositions of this invention may be prepared as described hereinafter from the polyphenylene ethers known in the art. The latter encompass numerous variations and _ 5 _ 2(~ 0 CIP of RD-18199 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 Ql (III) -0 Q2 Ql and in each of said units independently, each Ql and Q2 is as 10 previously defined. Examples of primary lower alkyl groups suitable as Ql and Q2 are methyl, ethyl, n-propyl, n-butyl, 1sobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-f dlmothylbutyl, 2-, 3- or 4-methylpentyl and the corresponding heptyl groups. Examples of secondary lower alkyl groups are 15 lsopropyl, sec-butyl and 3-pentyl. Preferably, any alkyl ~ radlcals are stralght chaln rather than branched. Most of-ten, each Ql is alkyl or phenyl, especially Cl_4 alkyl, and , each Q2 ls hydrogen. Sultable polyphenylene ethers are dis-closed ln a large number of patents.
~oth homopolymer and copolymer polyphenylene ethers are lncluded. Suitable homopolymers are those contalning, for example, 2,6-dlmethyl-1,4-phenylene ether unlts.
5' Suitable copolymers lnclude random copolymers containing such un1ts ln combinatlon w1th ~for example) 2,3,6-trlmethyl-1,4-phenylene ether units. Many suitable random copolymers, as well as homopolymers, are dlsclosed ln the patent llterature.
Also lncluded are polyphenylene ethers contalning mo1et1eq which modlfy propertleq such as molecular welght, melt viscosity and/or lmpact strength. Such polymers are de-- 6- 2~
RD-l 94 90 CIP of RD-18199 scribed in 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 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 about 20,000-80,000, as determined by gel permeation chromatography. Its intrinsic vlscosity 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 oxldatlve coupling of at least one correspondlng monohy-droxyaromatlc compound. Partlcularly useful and readily avallable monohydroxyaromatlc compounds are 2,6-xylenol (wherein each Ql is methyl and each Q2 ls hydrogen), whereupon the polymer may be characterized as a poly~2,6-dlmethyl-1,4-phenylene ether), and 2,3,6-trimethylphenol (wherein each Ql and one Q2 ls methyl and the other Q2 is hydrogen).
A variety of catalyst systems are known for the preparation of polyphenylene ethers by oxidative coupllng.
There is no particular limitation as to cataly-st choice and any of the known catalysts can be used. For the most part, - 7 - Z ~
CIP of RD-18199 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 compound. Such catalystsare disclosed, for example, in U.S. Patents 3,~06,874, 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 (monomeric and poly-meric), o-hydroxyaryl oxlmes and ~-diketones. Also useful are known cobalt-containing catalyst systems. Suitable man-ganese and cobalt-containing catalyst system-~ for polypheny-lene 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 purposeC of this invention include those which comprise moleculeq having at least one of the end groups of the formulas - 8 - ZQ~0~40 RD-l 94 90 CIP of RD-18199 N (R3 ) 2 Q ~C(R )2 ( IV) -O~OH and Qj Q2 Q2 Ql (V) -O~ OH
Ql Q2 Q Ql wherein Ql and Q2 are as previously defined; each R2 is inde-pendently hydrogen or alkyl, with the proviso that the total number 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-substltuted end groups of formula IV are typically obtained by incorporating an appropriate prlmary 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 ~-hydrogen atoms on one or more Ql radicals. The principal site of reaction i~ the Ql radical ad~acent 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--_ 9_ 2(~
CIP of RD-18199 tions, probably involving a quinone methide-type intermediate of the formula Q ~,C (R2) 2 (VI) -O ~ > o 2 ~ 1 Q Q
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~ ~2 Q~ Ql (VI I ) 0~=
Ql--\Q2 Q~\Ql is present, especially in a copper-halide-secondary or ter-tiary amine system. In this regard, the disclo ure of U.S.
Patént 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 hereln. In mixtures of this type, the diphenoquinone i9 ultimately incorporated into the polymer in substantial proportion~, largely as an end group.
In many polyphenylene ethers obtained under the above-described conditions, a substantial proportion of the - 10 - 2~ o CIP of RD-18199 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 not 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 of formula 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 amlne) ln the catalyst used to form the polyphenylene ether.
The present invention therefore includes the use of polyphenylene ethers ln whlch a substantial proportlon of amlno compounds has been removed or lnactivated. Polymers so treated contain unneutralized amino nitrogen, if any, in amounts no greater than 800 ppm. and more preferably in the 25 range of about 100-800 ppm.
A preferred method of inactlvation is by extrusion of the polyphenylene ether at a temperature wlthln the range of about 230-350'C, with vacuum ventlng. Thls ls preferably achleved ln a prellmlnary extrusion step, by connecting the vent of 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.
- 11 - 2~10~40 CIP of RD-18199 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 known, irrespective of variations in structural units or an-cillary chemical featureq.
The end groups on the epoxytriazine-capped polyphenylene ethers in the compositions of this invention 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 primary or secondary lower alkyl; an aromatic radlcal, typically monocyclic and containing 6-10 carbon atoms and especially an aromatic hydrocarbon radical;
or a radlcal of formula II. In formulas I and II, R~ may be aliphatlc, allcyclic, aromatlc ~lncluding aromatlc radicals contalning art-recognized sub~tituents~ or heterocyclic. It is usually lower alkylene and especially methylene.
Another aspect of the invention is a method for preparing the above-described epoxytriazine-capped polypheny-lene ether compositions. Said method comprises contacting under reactive conditions, in the presence of a basic reagent, at least one polyphenylene ether wlth an epoxychlorotrlazine of the formula Cl N ~ N
(VIII) XO/ \O-Rl-CH-CH2 - 12 - ~ ~ ~Q~40 CIP of RD-18199 wherein Rl 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 2,4,6-trimethylphenyl glycidyl chlorocya-nurate, respectively. They may be prepared, for example, by the reaction of 2,4,6-trichlorotriazine (cyanuric chloride) j 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 prepara'ion are disclosed and claimed in , copendlng, commonly owned application Serial No. 144,901, j 20 filed January 19, 1988. Thelr preparation is illustrated by the followlng examples.
To a mechanically stirred solution of 220.8 g. ~1.2 moles) cyanuric chloride in 1500 ml. chloroform, cooled to 0-lO C, wa~ added 266.4 g. ~3.6 moles) glycidol in one portion.
Aqueous sodium hydroxide (50~ solution; 192 g.) was added to the mixture dropwlse with stirrlng 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 - 13 - 2~ 4~) RD-l 94 90 CIP of RD-18199 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) chlorodiglycidoxytriazine. The reaction mix-ture also was found to contain small amounts of triglycidoxy-triazine and dichloroglycidoxytriazine.
Ex~le 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 f 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 untll 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 ~8GCC).
~m~
To a mechanically stirred solution of 50 g. (0.175 mole) 2,4,6-trimethylphenyl dichlorocyanurate (prepared by 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.
30 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 addltional 30 - 14 - Z~ 10 CIP of RD-18199 minutes, the reaction mixture was allowed to warm to room temperature. The methylene chloride layer was washed with distilled water until neutral and dried over magnesium sul-fate. The reaction product was found by proton nuclear mag-S 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 according to this invention. In one embodiment, the reaction is conducted in solution in a non-polar organic liquid, typically at a temperature in the range of about 80-lSO C and preferably about 100-12S-C. The basic reagent employed in this method should be soluble in the organic liquid and is generally a tertiary amine. Its identity is not otherwise lS critical, provided it is sufficiently non-volatile to remain ln the reaction mixture at the temperatures employed.
Pyridlne i9 often preferred.
The amount of epoxychlorotriazine employed in this optlon 19 generally in the range of about 1-20~ by weight, based on polyphenylene ether. The amount of baslc reagent is an effectlve amount to promote the reaction; in general, about 1.0-1.1 equlvalent thereof per mole of chloroepoxytri-azine is adequate.
The epoxytriazine-capped polyphenylene ethers made in solution by the above-described process are generally found to contain rather high proportions ~e.g., at least about 0.4~ by wolght) of chemlcally comblned chlorine, prin-clpally covalently bound. It i3 belleved that the covalently bound chlorlne is the re~ult of epoxy groups competing with the organlc base as a hydrogen chlorlde acceptor, with the formation of chlorohydrin moieties. Thls may be followed by condensation of said chlorohydrin moietles with additional epoxy groups to produce such molecular species as polypheny-Z~
CIP of RD-18199 lene ether-epoxytriazine block copolymers and homopolymeric epoxytriazine oligomers.
Upon molding, compositions containing polyphenylene ether copolymers prepared from products cor~aining such species form articles -.ich 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 embodiment of the method of this invention produces epoxytriazine-capped polyphenylene ethers with little or no covalently bound chlorine. In this method, the reaction is conducted interfacially in a medium comprising 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 epoxychlorotri-azine and polyphenylene ether, or may initially react with the polyphenylene ether to form a salt which is then contacted with the~ epoxychlorotrlazlne. There is also employed a phase transfer catalyst. Any of such catalysts whlch are stable and effective under the prevailing reaction condltions may be used; those skllled in the art will readily perceive which ones are suitable. Particularly preferred are the tetraalkylammonium chlorides wherein at least two alkyl groups per molecule, typi~ally 2 or 3, contain about 5-20 carbon atom~.
In this embodiment, reaction temperatures in the range of about 20-lOO'C may be employed. The amount of epoxy-chlorotriazine is frequently lower than in the previ-ously described method, typically in the range of about 1-6%
and preferably about 2-6% by welght based on polyphenylene ether, slnce the reaction of the epoxychlorotriazlne with the polyphenylene ether apparently proceeds more nearly to com-CIP of RD-18199 pletion. Most often, the ratio of equivalents of base to moles of epoxychlorotriazine is about 0.5-1.5:1, and the weight ratio of phase transfer catalyst to ~ase 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 epoxytrlazine moietles on the capped polyphenylene ether, uqually resultlng in a los-q of epoxide groups. Either or both of two operatlons may be employed to suppress thls reac-tion. The first is to neutralize the reactlon mixture with any convenient acidlc compound; carbon dioxide, in gaseous, liquld or solld form, is often preferred. The second is to remove alcohol from contact with the product as rapidly and completely as possible by conventional means, typically in-cludlng a subsequent drylng step.
In the following examples which illustrate the preparation of the epoxytriazine-capped polyphenylene ethers of thls lnventlon, proportions of epoxychlorotriazine are expressed as a percentage of polyphenylene ether. The following polyphenylene ethers were employed:
- 17 - 2~
CIP of RD-18199 -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.
Fxampleg 4-14 To solutions of 400 grams of polyphenylene ether in 2500 ml of tolùene were added, with stirrlng, varlous quan-tltles of pyrldine followed by varlous quantities of epoxy-chlorotrlazlnes, added in portions. The ratio of equlvalents of pyrldine to moles of epoxychlorotriazine was 1.04:1. The 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.
2~0~a - 18 ~
CIP Of RD-18199 TABLE I
Poly- Epoxy-phenylene chlorotriazine Reaction epoxy-Exa~le ether ~de~tity % t;~e. hr.~. tr;az;ne chlorine 4 PPS DGCC 5 2 0.52 ---PPE DGCC 5 3 0.62 ---6 W DGCC 5 1 0.430.42 7 W DGCC 5 2 0.65 ---8 W DGCC 5 3 0.630.47 9 W DGCC 2.5 3.5 0.24 ---W DGCC 15 3 2.1 1.8 11 W DGCC 15 3 1.9 ---15 12 W ~GCC 5 3 0.50 ---13 W 8GCC 5 3 0.40 ---14 W ~GCC 15 3 1.79 ---E~a~ple.c 15-25 To solutions of 400 grams of polyphenylene ether in 2500 ml. of toluene 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 methyltrlalkylammonium chlorlde ln whlch the alkyl groups contAined 8-10 carbon atoms, and 10~ aqueous sodlum hydroxide solutlon ln the amount of 1.3 equivalents of sodium hydroxide per mole of epoxychlorotrlazine. The mixtures were stirred vigorously for various periods at 25-40'C, after which the products were preclpitated with methanol in a blender and rapidly filtered, washed with methanol and vacuum dried.
The results are glven ln Table II. Chlorine pro-portions were less than 200 ppm., the mlnlmum detectable by quantltatlve X-ray fluorescence.
CIP of RD-18199 'r~RT~E I T
Polyphenylene ~poxychlorotriazine Reaction %
Examn~_ et~er Ide~t; ty % time. mln epoxytriazine 15 PPE DGCC 1.5 30 0.52 16 epE DGCC 2.0 30 1.03 17 PPE DGCC 2.5 30 0.95 18 PPS DGCC 3.0 30 0.96 19PPE* DGCC 3.0 30 1.01 20~PPE DGCC 3.0 30 1.24 21 LN DGCC 3.0 30 0.48 22 PPE DGCC 5.0 30 1.40 23 W DGCC 5.0 10 0. 6~
24 PPE 3GCC 3.0 30 1.25 25 PPE MGCC 3.0 30 1.50***
*16% slurry of crude PPE in toluene.
*~Reaction mlxture neutralized with ga~eouq carbon dioxide.
*~Average of 3 run3.
The epoxytriazine-capped polyphenylene ethers of thls lnvention react with other polymers containing nucleophilic groups, typlcally amine, lsocyanate, hydroxy or thlol groups or carboxy groups or functlonal derivatives thereof, to form copolymer-contalning composltlons. Sald composltlons may be molded into artlcles havlng hlgh lmpact strengths and other excellent physlcal propertles. They are al~o useful for compatiblllzlng polymer blends to form moldlng composltlons having similar excellent properties.
Composltions comprlslng copolymers of sald epoxytriazine-capped polyphenylene ethers with polyesters and polyamides are disclosed and clalmed ln copendlng, commonly owned applications Serlal No. ~RD-19372] and Serlal No. ~RD-19371], respectlvely.
Polyesters sultable for preparlng such copolymer composltlons generally ccmprise structural units of the formula ~n-~4~
CIP of RD-18199 ,.0 (IX) -o-R4-o-c-Al-c-wherein each R4 is independently a divalent aliphatic, 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 R
~X) -o-R4-o-C-A2 \ N 5 / \
C \C
O
wherein R4 is as previously defined, R5 is a polyoxyalkylene radical and A2 i~ a trivalent aromatic radical. The Al radical in formula IX ls 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 - 21 - Z~
CIP of RD-18199 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 the alkylene groups contain about 2-6 and most often 4 carbon atoms. As previously noted, this class of polyesters includes the poly(alkylene terephthalates) and the polyarylates.
Poly(alkylene terephthalates) are frequently preferred, with poly(ethylene terephthalate) and poly(butylene terephthalate) being most preferred.
The polyester generally has a number average molecular welght in the range of about 20,000-70,000, as determined by intrinsic viscosity (IV) at 30 C in a mixture lS of 60% (by weight) phenol and 40% 1,1,2,2-tetrachloroethane.
Either solution or melt blendlng procedures may be employed for the preparation of the copolymer compositions of thls invention. Typical reactlon temperatures are ln the range of about 175-350 C. Thus, relatlvely hlgh boiling solvents such as o-dichlorobenzene, nitrobenzene or 1,2,4-trlchlorobenzene are preferred for solution reactions.
Melt reaction procedures are frequently preferred because of the availability of melt blending equipment in commercial polymer processing facilitieq. Conventional equipment of this type is suitable, with the use of extrusion equipment generally being convenient and therefore often preferred.
The principal reactlon which takeq place between the epoxytriazine-capped polyphenylene ether and a polyester generally lnvolveq the carboxylic acid end groups of the latter, which open the epoxide rings to form hydroxy ester - 22 - X~Ol~
CIP of RD-18199 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 ~ QL oZ
(XI) - ~ ~ ~ fH2_Z
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 ~H2-Z2 or aromatic hydrocarbon) or -R -CH-Z ; and z2 is OH and Z3 is I~
-O-C-, or z2 ls -O-C- and Z3 is OH.
Another possible reactlon ls between hydroxy end group~ of the polyester and the epoxy groups of the capped polyphenylene ether. Thus, the composltlons of the invention are not llmlted to compound~ containlng llnkages of formula XI but may lnclude compounds with linkages of similar structures contalnlng ether moletles replacing the carboxylate moletles of z2 or Z3.
The proportions of polyphenylene ether and other polymer are not critical; they may be widely varled to provide composltions having the desired properties. Most often, each polymer 19 employed in an amount in the range of about 5-95%, preferably about 30-70%, of the compo~ition by welght.
In addltlon to polyphenylene ether-polyester copolymer, such compositions also contain unreacted polyphenylene ether This will include any polyphenylene :
- 23 - X~ O
CIP of RD-18199 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 composi~ions may also contain unreacted polyester. In any event, molded parts produced from said compositions are generally ductile and have 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 than those prepared from the low chlorine materials obtained by the interfacial method.
Another factor ls the proportion of unneutralized amino nitrogen in the polyphenylene ether. High proportions may cause side reaction~, including opening of epoxide rings, displacement of epoxide groups from the cyanurate moiety and cleavage of ester linkages. Such side reactlons 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 its proportion.
It also appears that compositions containing "high chlorine" capped polyphenylene ethers have a greater tendency - 24 - ~:Q~L03~0 CIP of R~-18199 toward ductility and high impact strength when a poly-phenylene 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 not presently understood.
The copolymer-containing compositions 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 ~re ethylene-propylene-diene polymers ~EPDM's), both unfunctionalized and functlonalized 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 dlene~, including butadlene, isoprene, chloroprene, ethylene, propylene and butylene. Also included are core-shell polymers, including those containing a poly(alkyl acrylate) core attached to a polystyrene shell via interpenetrating network, and more fully discloqed in U.S. Patent g,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.
E-~pecially preferred are the triblock copolymers with polystyrene end blocks and diene-derived midblocks. It is frequently advantageous to remove (preferably) or decrease the aliphatic un~aturation therein by selective hydrogenation. The weight average molecular weights of the impact modifiers are typically in the range of about 2~ 41~
CIP of RD-18199 50,000-300,000. Blo^k copolymers of this type are commercially available from Shell Chemical Company under the trademark KRATON, and include KRATON Dl101, Gl650, Gl651, Gl652 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 epoxy-substituted cyanurates and isocyanurates such as trlglycldyl lsocyanurate.
The other polyepoxide may be introduced by blending wlth the other components in a slngle operation. However, lts effectlveness may be maximized by preblending with the polyester, typically by dry mixing followed by extrusion.
Such preblending frequently increases the impact strength of the compositlon. While the reason for the effectiveness of the other polyepoxide is not entirely understood, it is belleved to lncrease molecular welght, melt viscosity and degree of branchlng of the polyecter 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, - 26 - z(~ 4~
CIP of RD-18199 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 polyphenylene ether-polyester copolymer compositions, the polyesters and impact modifiers employed are identified as follows:
PET - various poly(ethylene terephthalates).
P3T - a poly(butylene terephthalate) having a number average molecular weight of about 50,000, as determined by gel permeation chromatography.
PATME - a commercially available elastomeric polyterephthalate from a mixture of tetramethylene glycol, hexamethylene glycol and poly(tetramethylene ether) glycol.
PTME(50,000) and PTME(54,000) - a commercially available elastomeric polyterephthalates from mixtures of tetramethylene glycol and poly~tetramethylene ether) glycol, having the designated number average molecular welghts and about 204 and 50~ by weight, reqpectively, of poly(tetramethylene ether) glycol units.
PIE - a copolyester prepared from 1,4-butanedlol 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 welght average molecular welghts of 29,000 and a hydrogenated butadlene mldblock having a weight average molecular weight of 116,000.
CS - a core-shell materlal containing 75% of a crosslinked poly(butyl acrylate) core and 25%
of a crosslinked polystyrene shell, prepared in accordance with U.S. Patent 4,6~4,696.
"
- 27 - XQl~l~O
CIP of RD-18199 PO - a polyoctenylene with a cis-trans ratio of 20: 80, having a weight average molecular weight of about 55,000.
The resinous blends described were prepared by dry mixing and extruded cn a twin-screw extruder at 400 rpm. and 190-255 C (unless otherwise stated). The extrudates were quenched in water, pelletized, oven dried and molded at 280-C
into test specimens which were tested for notched Izod impact strength and tensile properties (ASTM procedures D256 and D638, regpectively) and heat distortion temperature at 0. 455 Moea. (ASTM procedure D648).
All parts and percentages in the following examples 15 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 magnetlc resonance spectroscopy; it is a general indication of the amount of copolymer in the composition.
Exampl es 2 6-3 5 Compositions containing various proportions of epoxytriazine-capped polyphenylene ethers prepared as described in Examples 4-14, various polyesters and SEBS were prepared and molded. The relevant parameters and test results are given in Table III.
2Q~
t~ ~ ~ r ~ 1-- _ O ~ O
¢--~ .~ e ~---- G -_ ~ C
_ C:l > o _ C 1~--N 1~ 1 1 1 1 ~ _ o-- G ~ ~ ~
> ; ~ ¢ ,n--N ~1 1 I I I
"., L Q
~; ~ > ~ `O ~ O S O O
O> ~ I .~--N1` . .
C O ~- O "~
"~ N N
Cl_ ~ >~ 1- ~S~ = I I
C C o = C =--N ~ , X
I.~Ct.~ ~ > ~ = Q C '~O I I I I
" a C cl IL _ ~ >~a ~- so I o --~c~--g > ~ C U~-- I 'O C `Cl _ ~ ~
a ~ _ o ~ ~ C > O~ C
¢: _ ~I ~ > `O ~ . ' _ O ~O ~ S
a ~ ~ - o ~
o ~ o > ~ c ~---- -- I I I, c c _ __ a c ~ S
cl ~_ ~ ~C 3 C :~ ~ C L ~ ~ C
C _ X ~
C C--C ~ L oC L
_ C - ~ o ~ --O
_ C - _ _ ~ C ~ ~ ~ t ~-~ ~ C ~ I CJ ~ o 0 ~--~ O ~---- ~11 L O _ ~ ~ 0 3 L . c~ _ _ _ _ C--eL '' _ IL ~ L ~1 0 ~ C ~ < C
~ O ~ C~ _ O
2~
CIP of RD-18199 Exam~1es_~6-47 Compositions were prepared and molded from the epoxytriazine-capped polyphenylene ethers of Examples 15-25, S PBT and SEBS. The relevant parameters and test results are given in Table IV.
X~
~cl `-"I . .
C C-- ----N-- ---- ----~_c,c, ., O~~o--~a I ~--,r~_ < 01 0~ ~ N u'l N C ~ ~ ~1~ N
_ _ . ~ ~===5 1 ~=~
U e c :1 I _ ~ o ~ C ~ O _ ~ < ol ~o ~ ~ N ~--~ N _ _ ,,~ .
_ ~ ~ Cl O _ ~ ~--~c.~
;~1 .~ .
c ~1 oeooooccc~ooo _ al --------__--_____ L
~C~ ~
C '~ ~ _ N--s C ~ ~ `.0 ~ ~ ~ ~ ~ ~0 ~0 N ~o ~0 c ~l G _ c :-l x x x x x x x x x x x x c ~ t--C ~ O--N ~ s Z~ 0 CIP of RD-18199 E~m~4 8-4 9 Compositions similar to those of Examples 18 and 24 were prepared and molded, substituting 18 parts of PPE for an S equal weight of the epoxytriazine-capped polyphenylene ether.
The relevant test results are given in Table v.
Example 48 ~q 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 Examz19s 50-57 Compositions contalning 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 o carboxylic acid end groups. The following PET's were employed:
"Kodapak 73S2" ~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.
AND METHOD OF PREPA~ATIQN
This application is a continuation-in-part of copending application Serial No. 210,547, filed June 23, 1988.
This invention relates to the preparation of polyphenylene ethers containing epoxy groups, and to the use of such polyphenylene ethers in the preparation of copolymer-containing compositions.
The polyphenylene ethers are a widely used class of thermoplastic engineering resins characterized by excellent hydrolytic stability, dimensional stability, toughness, heat resi~tance and dielectric properties. However, they are de-flcient in certain other properties such as workability and solvent resistance. Therefore, there is a continuing search for means for modifying polyphenylene ethers to improve these other propertles.
Among the means being studied are blending of polyphenylene ethers with certain other resinous materials such as polyesters, polyamides or olefin polymers. Blends of these other materials with polyphenylene ethers are, however, usually incompatible. Molded parts fabricated from such blends are generally brittle and may undergo catastrophic delamination upon impact.
Numerous methods for compatibilizing polyphenylene ether-polyester compositions have been developed. For exam-ple, PCT published application 87/850 describes blends com-patibilized by the addition of an aromatic polycarbonate.
Said blends are extremely versatlle in numerous critical ap-plications such as the fabrication of automobile body parts.
However, the presence of polycarbonate may result in degra-Zl[~10~40 CIP of RD-18199 dation of certain other properties such as heat distortion temperature.
In addition, a problem sometimes arises by virtue of the presence of aminoalkyl-substituted end groups on S 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 reslns. 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 polyamides as amino, hydroxy and carboxy groups, leading to copolymer formatlon.
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 dissolutlon of the polyphenylene ether in a large excess of epichlorohydrin, a relatively expensive reagent which is also a strong skin irritant and can cause kidney injury.
i _ 3 _ 2~ 0 CIP of RD-18199 PCT published application 87/7279 describes the reaction of polyphenylene ethers with terephthaloyl chloride and glycidol to form an epoxy-functionalized polyphenylene 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 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 methacrylate, are toxic. Moreover, the reactlon is generally accompanied by homopolymerization of the epoxy-functlonalized monomer, and it is then necessary to remove the homopolymer by such compllcated operations as dlssolution of the crude polymeric product followed by forma-tlon and decomposltlon of a polyphenylene ether-methylene chlorlde complex. Thus, these materials may not be readiiy adaptable to copolymer preparatlon on an industrial scale.
The present invention provides a simple method for introducing epoxy functionality into a polyphenylene ether, employing simple solution or interfacial conditions and relatively lnexpensive reagents. The products are hi.ghly reactive and readily convertlble under both solution and melt conditions to compositions comprislng copolymers of polyphenylene ethers with a wide variety of strongly and weakly nucleophilic polymers, notably polyesters and _ 4 ~ L40 CIP of RD-18199 polyamides. Said compositions have excellent physical properties, particularly when blended with conventional impact modifiers for polyphenylene ethers. They also compatibilize blends containing unfunctionalized polyphenylene ethers.
In one of its aspects, the invention includes epoxytria7ine-capped polyphenylene ether compositions which comprise polymer molecules having end groups of the formula Q2 Ql OX
(I) - ~ N ~
10 Q2~Ql \ O-Rl-CH-CH2 wherein:
each Ql is independently halogen, primary or sec-ondary lower alkyl (i.e., alkyl containing up to 7 carbon . 15 atoms), phenyl, haloalkyl, aminoalkyl, 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 1 ~~
(II) -R -CH-CH2 ; and 25Rl is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatlc hydrocarbon radical.
The compositions of this invention may be prepared as described hereinafter from the polyphenylene ethers known in the art. The latter encompass numerous variations and _ 5 _ 2(~ 0 CIP of RD-18199 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 Ql (III) -0 Q2 Ql and in each of said units independently, each Ql and Q2 is as 10 previously defined. Examples of primary lower alkyl groups suitable as Ql and Q2 are methyl, ethyl, n-propyl, n-butyl, 1sobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-f dlmothylbutyl, 2-, 3- or 4-methylpentyl and the corresponding heptyl groups. Examples of secondary lower alkyl groups are 15 lsopropyl, sec-butyl and 3-pentyl. Preferably, any alkyl ~ radlcals are stralght chaln rather than branched. Most of-ten, each Ql is alkyl or phenyl, especially Cl_4 alkyl, and , each Q2 ls hydrogen. Sultable polyphenylene ethers are dis-closed ln a large number of patents.
~oth homopolymer and copolymer polyphenylene ethers are lncluded. Suitable homopolymers are those contalning, for example, 2,6-dlmethyl-1,4-phenylene ether unlts.
5' Suitable copolymers lnclude random copolymers containing such un1ts ln combinatlon w1th ~for example) 2,3,6-trlmethyl-1,4-phenylene ether units. Many suitable random copolymers, as well as homopolymers, are dlsclosed ln the patent llterature.
Also lncluded are polyphenylene ethers contalning mo1et1eq which modlfy propertleq such as molecular welght, melt viscosity and/or lmpact strength. Such polymers are de-- 6- 2~
RD-l 94 90 CIP of RD-18199 scribed in 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 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 about 20,000-80,000, as determined by gel permeation chromatography. Its intrinsic vlscosity 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 oxldatlve coupling of at least one correspondlng monohy-droxyaromatlc compound. Partlcularly useful and readily avallable monohydroxyaromatlc compounds are 2,6-xylenol (wherein each Ql is methyl and each Q2 ls hydrogen), whereupon the polymer may be characterized as a poly~2,6-dlmethyl-1,4-phenylene ether), and 2,3,6-trimethylphenol (wherein each Ql and one Q2 ls methyl and the other Q2 is hydrogen).
A variety of catalyst systems are known for the preparation of polyphenylene ethers by oxidative coupllng.
There is no particular limitation as to cataly-st choice and any of the known catalysts can be used. For the most part, - 7 - Z ~
CIP of RD-18199 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 compound. Such catalystsare disclosed, for example, in U.S. Patents 3,~06,874, 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 (monomeric and poly-meric), o-hydroxyaryl oxlmes and ~-diketones. Also useful are known cobalt-containing catalyst systems. Suitable man-ganese and cobalt-containing catalyst system-~ for polypheny-lene 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 purposeC of this invention include those which comprise moleculeq having at least one of the end groups of the formulas - 8 - ZQ~0~40 RD-l 94 90 CIP of RD-18199 N (R3 ) 2 Q ~C(R )2 ( IV) -O~OH and Qj Q2 Q2 Ql (V) -O~ OH
Ql Q2 Q Ql wherein Ql and Q2 are as previously defined; each R2 is inde-pendently hydrogen or alkyl, with the proviso that the total number 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-substltuted end groups of formula IV are typically obtained by incorporating an appropriate prlmary 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 ~-hydrogen atoms on one or more Ql radicals. The principal site of reaction i~ the Ql radical ad~acent 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--_ 9_ 2(~
CIP of RD-18199 tions, probably involving a quinone methide-type intermediate of the formula Q ~,C (R2) 2 (VI) -O ~ > o 2 ~ 1 Q Q
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~ ~2 Q~ Ql (VI I ) 0~=
Ql--\Q2 Q~\Ql is present, especially in a copper-halide-secondary or ter-tiary amine system. In this regard, the disclo ure of U.S.
Patént 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 hereln. In mixtures of this type, the diphenoquinone i9 ultimately incorporated into the polymer in substantial proportion~, largely as an end group.
In many polyphenylene ethers obtained under the above-described conditions, a substantial proportion of the - 10 - 2~ o CIP of RD-18199 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 not 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 of formula 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 amlne) ln the catalyst used to form the polyphenylene ether.
The present invention therefore includes the use of polyphenylene ethers ln whlch a substantial proportlon of amlno compounds has been removed or lnactivated. Polymers so treated contain unneutralized amino nitrogen, if any, in amounts no greater than 800 ppm. and more preferably in the 25 range of about 100-800 ppm.
A preferred method of inactlvation is by extrusion of the polyphenylene ether at a temperature wlthln the range of about 230-350'C, with vacuum ventlng. Thls ls preferably achleved ln a prellmlnary extrusion step, by connecting the vent of 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.
- 11 - 2~10~40 CIP of RD-18199 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 known, irrespective of variations in structural units or an-cillary chemical featureq.
The end groups on the epoxytriazine-capped polyphenylene ethers in the compositions of this invention 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 primary or secondary lower alkyl; an aromatic radlcal, typically monocyclic and containing 6-10 carbon atoms and especially an aromatic hydrocarbon radical;
or a radlcal of formula II. In formulas I and II, R~ may be aliphatlc, allcyclic, aromatlc ~lncluding aromatlc radicals contalning art-recognized sub~tituents~ or heterocyclic. It is usually lower alkylene and especially methylene.
Another aspect of the invention is a method for preparing the above-described epoxytriazine-capped polypheny-lene ether compositions. Said method comprises contacting under reactive conditions, in the presence of a basic reagent, at least one polyphenylene ether wlth an epoxychlorotrlazine of the formula Cl N ~ N
(VIII) XO/ \O-Rl-CH-CH2 - 12 - ~ ~ ~Q~40 CIP of RD-18199 wherein Rl 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 2,4,6-trimethylphenyl glycidyl chlorocya-nurate, respectively. They may be prepared, for example, by the reaction of 2,4,6-trichlorotriazine (cyanuric chloride) j 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 prepara'ion are disclosed and claimed in , copendlng, commonly owned application Serial No. 144,901, j 20 filed January 19, 1988. Thelr preparation is illustrated by the followlng examples.
To a mechanically stirred solution of 220.8 g. ~1.2 moles) cyanuric chloride in 1500 ml. chloroform, cooled to 0-lO C, wa~ added 266.4 g. ~3.6 moles) glycidol in one portion.
Aqueous sodium hydroxide (50~ solution; 192 g.) was added to the mixture dropwlse with stirrlng 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 - 13 - 2~ 4~) RD-l 94 90 CIP of RD-18199 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) chlorodiglycidoxytriazine. The reaction mix-ture also was found to contain small amounts of triglycidoxy-triazine and dichloroglycidoxytriazine.
Ex~le 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 f 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 untll 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 ~8GCC).
~m~
To a mechanically stirred solution of 50 g. (0.175 mole) 2,4,6-trimethylphenyl dichlorocyanurate (prepared by 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.
30 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 addltional 30 - 14 - Z~ 10 CIP of RD-18199 minutes, the reaction mixture was allowed to warm to room temperature. The methylene chloride layer was washed with distilled water until neutral and dried over magnesium sul-fate. The reaction product was found by proton nuclear mag-S 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 according to this invention. In one embodiment, the reaction is conducted in solution in a non-polar organic liquid, typically at a temperature in the range of about 80-lSO C and preferably about 100-12S-C. The basic reagent employed in this method should be soluble in the organic liquid and is generally a tertiary amine. Its identity is not otherwise lS critical, provided it is sufficiently non-volatile to remain ln the reaction mixture at the temperatures employed.
Pyridlne i9 often preferred.
The amount of epoxychlorotriazine employed in this optlon 19 generally in the range of about 1-20~ by weight, based on polyphenylene ether. The amount of baslc reagent is an effectlve amount to promote the reaction; in general, about 1.0-1.1 equlvalent thereof per mole of chloroepoxytri-azine is adequate.
The epoxytriazine-capped polyphenylene ethers made in solution by the above-described process are generally found to contain rather high proportions ~e.g., at least about 0.4~ by wolght) of chemlcally comblned chlorine, prin-clpally covalently bound. It i3 belleved that the covalently bound chlorlne is the re~ult of epoxy groups competing with the organlc base as a hydrogen chlorlde acceptor, with the formation of chlorohydrin moieties. Thls may be followed by condensation of said chlorohydrin moietles with additional epoxy groups to produce such molecular species as polypheny-Z~
CIP of RD-18199 lene ether-epoxytriazine block copolymers and homopolymeric epoxytriazine oligomers.
Upon molding, compositions containing polyphenylene ether copolymers prepared from products cor~aining such species form articles -.ich 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 embodiment of the method of this invention produces epoxytriazine-capped polyphenylene ethers with little or no covalently bound chlorine. In this method, the reaction is conducted interfacially in a medium comprising 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 epoxychlorotri-azine and polyphenylene ether, or may initially react with the polyphenylene ether to form a salt which is then contacted with the~ epoxychlorotrlazlne. There is also employed a phase transfer catalyst. Any of such catalysts whlch are stable and effective under the prevailing reaction condltions may be used; those skllled in the art will readily perceive which ones are suitable. Particularly preferred are the tetraalkylammonium chlorides wherein at least two alkyl groups per molecule, typi~ally 2 or 3, contain about 5-20 carbon atom~.
In this embodiment, reaction temperatures in the range of about 20-lOO'C may be employed. The amount of epoxy-chlorotriazine is frequently lower than in the previ-ously described method, typically in the range of about 1-6%
and preferably about 2-6% by welght based on polyphenylene ether, slnce the reaction of the epoxychlorotriazlne with the polyphenylene ether apparently proceeds more nearly to com-CIP of RD-18199 pletion. Most often, the ratio of equivalents of base to moles of epoxychlorotriazine is about 0.5-1.5:1, and the weight ratio of phase transfer catalyst to ~ase 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 epoxytrlazine moietles on the capped polyphenylene ether, uqually resultlng in a los-q of epoxide groups. Either or both of two operatlons may be employed to suppress thls reac-tion. The first is to neutralize the reactlon mixture with any convenient acidlc compound; carbon dioxide, in gaseous, liquld or solld form, is often preferred. The second is to remove alcohol from contact with the product as rapidly and completely as possible by conventional means, typically in-cludlng a subsequent drylng step.
In the following examples which illustrate the preparation of the epoxytriazine-capped polyphenylene ethers of thls lnventlon, proportions of epoxychlorotriazine are expressed as a percentage of polyphenylene ether. The following polyphenylene ethers were employed:
- 17 - 2~
CIP of RD-18199 -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.
Fxampleg 4-14 To solutions of 400 grams of polyphenylene ether in 2500 ml of tolùene were added, with stirrlng, varlous quan-tltles of pyrldine followed by varlous quantities of epoxy-chlorotrlazlnes, added in portions. The ratio of equlvalents of pyrldine to moles of epoxychlorotriazine was 1.04:1. The 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.
2~0~a - 18 ~
CIP Of RD-18199 TABLE I
Poly- Epoxy-phenylene chlorotriazine Reaction epoxy-Exa~le ether ~de~tity % t;~e. hr.~. tr;az;ne chlorine 4 PPS DGCC 5 2 0.52 ---PPE DGCC 5 3 0.62 ---6 W DGCC 5 1 0.430.42 7 W DGCC 5 2 0.65 ---8 W DGCC 5 3 0.630.47 9 W DGCC 2.5 3.5 0.24 ---W DGCC 15 3 2.1 1.8 11 W DGCC 15 3 1.9 ---15 12 W ~GCC 5 3 0.50 ---13 W 8GCC 5 3 0.40 ---14 W ~GCC 15 3 1.79 ---E~a~ple.c 15-25 To solutions of 400 grams of polyphenylene ether in 2500 ml. of toluene 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 methyltrlalkylammonium chlorlde ln whlch the alkyl groups contAined 8-10 carbon atoms, and 10~ aqueous sodlum hydroxide solutlon ln the amount of 1.3 equivalents of sodium hydroxide per mole of epoxychlorotrlazine. The mixtures were stirred vigorously for various periods at 25-40'C, after which the products were preclpitated with methanol in a blender and rapidly filtered, washed with methanol and vacuum dried.
The results are glven ln Table II. Chlorine pro-portions were less than 200 ppm., the mlnlmum detectable by quantltatlve X-ray fluorescence.
CIP of RD-18199 'r~RT~E I T
Polyphenylene ~poxychlorotriazine Reaction %
Examn~_ et~er Ide~t; ty % time. mln epoxytriazine 15 PPE DGCC 1.5 30 0.52 16 epE DGCC 2.0 30 1.03 17 PPE DGCC 2.5 30 0.95 18 PPS DGCC 3.0 30 0.96 19PPE* DGCC 3.0 30 1.01 20~PPE DGCC 3.0 30 1.24 21 LN DGCC 3.0 30 0.48 22 PPE DGCC 5.0 30 1.40 23 W DGCC 5.0 10 0. 6~
24 PPE 3GCC 3.0 30 1.25 25 PPE MGCC 3.0 30 1.50***
*16% slurry of crude PPE in toluene.
*~Reaction mlxture neutralized with ga~eouq carbon dioxide.
*~Average of 3 run3.
The epoxytriazine-capped polyphenylene ethers of thls lnvention react with other polymers containing nucleophilic groups, typlcally amine, lsocyanate, hydroxy or thlol groups or carboxy groups or functlonal derivatives thereof, to form copolymer-contalning composltlons. Sald composltlons may be molded into artlcles havlng hlgh lmpact strengths and other excellent physlcal propertles. They are al~o useful for compatiblllzlng polymer blends to form moldlng composltlons having similar excellent properties.
Composltions comprlslng copolymers of sald epoxytriazine-capped polyphenylene ethers with polyesters and polyamides are disclosed and clalmed ln copendlng, commonly owned applications Serlal No. ~RD-19372] and Serlal No. ~RD-19371], respectlvely.
Polyesters sultable for preparlng such copolymer composltlons generally ccmprise structural units of the formula ~n-~4~
CIP of RD-18199 ,.0 (IX) -o-R4-o-c-Al-c-wherein each R4 is independently a divalent aliphatic, 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 R
~X) -o-R4-o-C-A2 \ N 5 / \
C \C
O
wherein R4 is as previously defined, R5 is a polyoxyalkylene radical and A2 i~ a trivalent aromatic radical. The Al radical in formula IX ls 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 - 21 - Z~
CIP of RD-18199 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 the alkylene groups contain about 2-6 and most often 4 carbon atoms. As previously noted, this class of polyesters includes the poly(alkylene terephthalates) and the polyarylates.
Poly(alkylene terephthalates) are frequently preferred, with poly(ethylene terephthalate) and poly(butylene terephthalate) being most preferred.
The polyester generally has a number average molecular welght in the range of about 20,000-70,000, as determined by intrinsic viscosity (IV) at 30 C in a mixture lS of 60% (by weight) phenol and 40% 1,1,2,2-tetrachloroethane.
Either solution or melt blendlng procedures may be employed for the preparation of the copolymer compositions of thls invention. Typical reactlon temperatures are ln the range of about 175-350 C. Thus, relatlvely hlgh boiling solvents such as o-dichlorobenzene, nitrobenzene or 1,2,4-trlchlorobenzene are preferred for solution reactions.
Melt reaction procedures are frequently preferred because of the availability of melt blending equipment in commercial polymer processing facilitieq. Conventional equipment of this type is suitable, with the use of extrusion equipment generally being convenient and therefore often preferred.
The principal reactlon which takeq place between the epoxytriazine-capped polyphenylene ether and a polyester generally lnvolveq the carboxylic acid end groups of the latter, which open the epoxide rings to form hydroxy ester - 22 - X~Ol~
CIP of RD-18199 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 ~ QL oZ
(XI) - ~ ~ ~ fH2_Z
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 ~H2-Z2 or aromatic hydrocarbon) or -R -CH-Z ; and z2 is OH and Z3 is I~
-O-C-, or z2 ls -O-C- and Z3 is OH.
Another possible reactlon ls between hydroxy end group~ of the polyester and the epoxy groups of the capped polyphenylene ether. Thus, the composltlons of the invention are not llmlted to compound~ containlng llnkages of formula XI but may lnclude compounds with linkages of similar structures contalnlng ether moletles replacing the carboxylate moletles of z2 or Z3.
The proportions of polyphenylene ether and other polymer are not critical; they may be widely varled to provide composltions having the desired properties. Most often, each polymer 19 employed in an amount in the range of about 5-95%, preferably about 30-70%, of the compo~ition by welght.
In addltlon to polyphenylene ether-polyester copolymer, such compositions also contain unreacted polyphenylene ether This will include any polyphenylene :
- 23 - X~ O
CIP of RD-18199 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 composi~ions may also contain unreacted polyester. In any event, molded parts produced from said compositions are generally ductile and have 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 than those prepared from the low chlorine materials obtained by the interfacial method.
Another factor ls the proportion of unneutralized amino nitrogen in the polyphenylene ether. High proportions may cause side reaction~, including opening of epoxide rings, displacement of epoxide groups from the cyanurate moiety and cleavage of ester linkages. Such side reactlons 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 its proportion.
It also appears that compositions containing "high chlorine" capped polyphenylene ethers have a greater tendency - 24 - ~:Q~L03~0 CIP of R~-18199 toward ductility and high impact strength when a poly-phenylene 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 not presently understood.
The copolymer-containing compositions 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 ~re ethylene-propylene-diene polymers ~EPDM's), both unfunctionalized and functlonalized 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 dlene~, including butadlene, isoprene, chloroprene, ethylene, propylene and butylene. Also included are core-shell polymers, including those containing a poly(alkyl acrylate) core attached to a polystyrene shell via interpenetrating network, and more fully discloqed in U.S. Patent g,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.
E-~pecially preferred are the triblock copolymers with polystyrene end blocks and diene-derived midblocks. It is frequently advantageous to remove (preferably) or decrease the aliphatic un~aturation therein by selective hydrogenation. The weight average molecular weights of the impact modifiers are typically in the range of about 2~ 41~
CIP of RD-18199 50,000-300,000. Blo^k copolymers of this type are commercially available from Shell Chemical Company under the trademark KRATON, and include KRATON Dl101, Gl650, Gl651, Gl652 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 epoxy-substituted cyanurates and isocyanurates such as trlglycldyl lsocyanurate.
The other polyepoxide may be introduced by blending wlth the other components in a slngle operation. However, lts effectlveness may be maximized by preblending with the polyester, typically by dry mixing followed by extrusion.
Such preblending frequently increases the impact strength of the compositlon. While the reason for the effectiveness of the other polyepoxide is not entirely understood, it is belleved to lncrease molecular welght, melt viscosity and degree of branchlng of the polyecter 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, - 26 - z(~ 4~
CIP of RD-18199 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 polyphenylene ether-polyester copolymer compositions, the polyesters and impact modifiers employed are identified as follows:
PET - various poly(ethylene terephthalates).
P3T - a poly(butylene terephthalate) having a number average molecular weight of about 50,000, as determined by gel permeation chromatography.
PATME - a commercially available elastomeric polyterephthalate from a mixture of tetramethylene glycol, hexamethylene glycol and poly(tetramethylene ether) glycol.
PTME(50,000) and PTME(54,000) - a commercially available elastomeric polyterephthalates from mixtures of tetramethylene glycol and poly~tetramethylene ether) glycol, having the designated number average molecular welghts and about 204 and 50~ by weight, reqpectively, of poly(tetramethylene ether) glycol units.
PIE - a copolyester prepared from 1,4-butanedlol 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 welght average molecular welghts of 29,000 and a hydrogenated butadlene mldblock having a weight average molecular weight of 116,000.
CS - a core-shell materlal containing 75% of a crosslinked poly(butyl acrylate) core and 25%
of a crosslinked polystyrene shell, prepared in accordance with U.S. Patent 4,6~4,696.
"
- 27 - XQl~l~O
CIP of RD-18199 PO - a polyoctenylene with a cis-trans ratio of 20: 80, having a weight average molecular weight of about 55,000.
The resinous blends described were prepared by dry mixing and extruded cn a twin-screw extruder at 400 rpm. and 190-255 C (unless otherwise stated). The extrudates were quenched in water, pelletized, oven dried and molded at 280-C
into test specimens which were tested for notched Izod impact strength and tensile properties (ASTM procedures D256 and D638, regpectively) and heat distortion temperature at 0. 455 Moea. (ASTM procedure D648).
All parts and percentages in the following examples 15 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 magnetlc resonance spectroscopy; it is a general indication of the amount of copolymer in the composition.
Exampl es 2 6-3 5 Compositions containing various proportions of epoxytriazine-capped polyphenylene ethers prepared as described in Examples 4-14, various polyesters and SEBS were prepared and molded. The relevant parameters and test results are given in Table III.
2Q~
t~ ~ ~ r ~ 1-- _ O ~ O
¢--~ .~ e ~---- G -_ ~ C
_ C:l > o _ C 1~--N 1~ 1 1 1 1 ~ _ o-- G ~ ~ ~
> ; ~ ¢ ,n--N ~1 1 I I I
"., L Q
~; ~ > ~ `O ~ O S O O
O> ~ I .~--N1` . .
C O ~- O "~
"~ N N
Cl_ ~ >~ 1- ~S~ = I I
C C o = C =--N ~ , X
I.~Ct.~ ~ > ~ = Q C '~O I I I I
" a C cl IL _ ~ >~a ~- so I o --~c~--g > ~ C U~-- I 'O C `Cl _ ~ ~
a ~ _ o ~ ~ C > O~ C
¢: _ ~I ~ > `O ~ . ' _ O ~O ~ S
a ~ ~ - o ~
o ~ o > ~ c ~---- -- I I I, c c _ __ a c ~ S
cl ~_ ~ ~C 3 C :~ ~ C L ~ ~ C
C _ X ~
C C--C ~ L oC L
_ C - ~ o ~ --O
_ C - _ _ ~ C ~ ~ ~ t ~-~ ~ C ~ I CJ ~ o 0 ~--~ O ~---- ~11 L O _ ~ ~ 0 3 L . c~ _ _ _ _ C--eL '' _ IL ~ L ~1 0 ~ C ~ < C
~ O ~ C~ _ O
2~
CIP of RD-18199 Exam~1es_~6-47 Compositions were prepared and molded from the epoxytriazine-capped polyphenylene ethers of Examples 15-25, S PBT and SEBS. The relevant parameters and test results are given in Table IV.
X~
~cl `-"I . .
C C-- ----N-- ---- ----~_c,c, ., O~~o--~a I ~--,r~_ < 01 0~ ~ N u'l N C ~ ~ ~1~ N
_ _ . ~ ~===5 1 ~=~
U e c :1 I _ ~ o ~ C ~ O _ ~ < ol ~o ~ ~ N ~--~ N _ _ ,,~ .
_ ~ ~ Cl O _ ~ ~--~c.~
;~1 .~ .
c ~1 oeooooccc~ooo _ al --------__--_____ L
~C~ ~
C '~ ~ _ N--s C ~ ~ `.0 ~ ~ ~ ~ ~ ~0 ~0 N ~o ~0 c ~l G _ c :-l x x x x x x x x x x x x c ~ t--C ~ O--N ~ s Z~ 0 CIP of RD-18199 E~m~4 8-4 9 Compositions similar to those of Examples 18 and 24 were prepared and molded, substituting 18 parts of PPE for an S equal weight of the epoxytriazine-capped polyphenylene ether.
The relevant test results are given in Table v.
Example 48 ~q 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 Examz19s 50-57 Compositions contalning 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 o carboxylic acid end groups. The following PET's were employed:
"Kodapak 73S2" ~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.
- 3 2 - 2~ 0 .
~ Cl CL
r o ~ o I I = = ~
x o ~ ~c~
. ~ c ~n ~
~c o t~ C I I u~ C m . =
X o ~ _ U~ ~ ~ C =~
~=C ~ ~
_ ~ ~"
_ ~ ~ 1 N = =
_ x c ~ r ~u N
C ~
X ~ ~_ r ~0 _ =C5 ~aNtU
Ir X -- o~__ Y
C~
co ~a o = z c~
~. u~ X g Y~
_l ~.~ ~ = _ c ~a ~o ~ z r. ~
x o _ ~ _ 2 ~ Y ==
c_ ~z ~
u~ X ~ ~ ~ ~ U~ r a y =~
. L
_ ..
o .
o c ~ C c ~i o _ ~ c o ~ - o o .~ 1 C~ ¢
1~ ~ c c~ ~ ~ ~c < <
.. o 2Q~ 40 CIP of RD-18199 Exam~les 58-61 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.
~LE~
Example Capped polyphenylene ether, parts36 36 36 40 Polyester, parts:
SEBS, parts lO 10 lO
Izod impact strength, joules/m. _753198 812 --Tensile strength, MPa.:
At yield 43.9 41.644.546.1 At break 42.3 40.839.640.6 Tensile elongatlon, % 151 220195 178 ~L~
Compositions contalning epoxytriazine-capped polyphenylene ether~ similar to that of Example 18 but containing 0.75-0.85~ epoxytriazine, PBT and CS or PO were prepared and molded. The relevant parameters and test results are given in Table VIII.
201~140 CIP of RD-18199 -TABLF~ VT I T
62 6~ 64 s Capped polyphenylene ether, parts 36 37 36 PBT, parts 54 55 54 Impact modifier, parts:
Izod impact strength, joules~m.561219 155 Tensile strength, MPa.:
At yield 46.7 44.7 41.9 At break 40.8 41.4 34.9 15 Tensile elongation, ~ 134 135 70 Heat distortion temp., C -- 156 162 Esl~plga 65-74 Compositions containing epoxytriazine-functionalized polyphenylene ethers, various elastomeric polyester~ and (in Examples 65-71) SEBS as an impact modifier were prepared and molded. The relevant parameters and test result~ are glven in Table IX.
2~
t~
e~
., I . i . . I 1, ~_ L ~ - ~ s =~ C El _ ~ .
0 e o r-~acs~u~ooeo e o--~ ~ ~ ~ nJ ~_ o .~: ~ _ ~ = O '7 N `O
--cn . ~ ~ ~s -- e C~ ~ " _ _ _ -- o I ~ ~
r O O _ I I I
O ~ e I J 1~
~ -- r _ .~ o . L ..
C~ ~ ~ ~ ooooooo I I I
X C~ O _ __ _ __ __, I I
e E--C
1~ _ C ~ ~SS-_ ~OCO
Cl O O O O C O
C~--SO SO SO
~ ~ z I ~ 1.,1~ S S ~
--o L ` ~ ~O ~ `O 'O ~o C C--c ~7~1.7r7~7S=_ L
~_ o. C~
I ~ ~ ~ ¢ S S S ~ ~ C~ --~" r .. _ ------N ~ ~J _ _ _ ~11 O '; . . . . . . . , . . L
-- C XXXXXXXXXX O
O ~1 ~I_L~b~L.I
O, ~
~D U~
_ u~ ~ ~ o--~ ~ s wl .
- 36 - 2 ~
CIP of RD-18199 E"x~_ples 75-80 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 7 - . ~
cl o c I I o I I ~
¢ N S I I _ I I . ."-~ C~
C Ou~ I I ~0_ ~0 I~ N '~ I t r7 o ~-¢ ~C~ I O~ I ON N~
C ~ I = I--~
X ~O~- I ~ I CO O¢S
I --O . S
r- ~`0--Xl ~
~ ~c ~ ~ I u~
_ ~ ~S I I __ . .--C~
r_ ~ N N I I --~ N ~--C 1' .
L L
C C
q~ L ' ~I~
' C ~ Z
_ o C. O
C g_ o g ~C o " L~ L Co O L_ i L ~
G--O~ll~ S C O O
1- ~- O ~ ~ --_ ~ _~ Z--~
a ~ ~ ~ -, C C _ < ~ C
~ Cl CL
r o ~ o I I = = ~
x o ~ ~c~
. ~ c ~n ~
~c o t~ C I I u~ C m . =
X o ~ _ U~ ~ ~ C =~
~=C ~ ~
_ ~ ~"
_ ~ ~ 1 N = =
_ x c ~ r ~u N
C ~
X ~ ~_ r ~0 _ =C5 ~aNtU
Ir X -- o~__ Y
C~
co ~a o = z c~
~. u~ X g Y~
_l ~.~ ~ = _ c ~a ~o ~ z r. ~
x o _ ~ _ 2 ~ Y ==
c_ ~z ~
u~ X ~ ~ ~ ~ U~ r a y =~
. L
_ ..
o .
o c ~ C c ~i o _ ~ c o ~ - o o .~ 1 C~ ¢
1~ ~ c c~ ~ ~ ~c < <
.. o 2Q~ 40 CIP of RD-18199 Exam~les 58-61 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.
~LE~
Example Capped polyphenylene ether, parts36 36 36 40 Polyester, parts:
SEBS, parts lO 10 lO
Izod impact strength, joules/m. _753198 812 --Tensile strength, MPa.:
At yield 43.9 41.644.546.1 At break 42.3 40.839.640.6 Tensile elongatlon, % 151 220195 178 ~L~
Compositions contalning epoxytriazine-capped polyphenylene ether~ similar to that of Example 18 but containing 0.75-0.85~ epoxytriazine, PBT and CS or PO were prepared and molded. The relevant parameters and test results are given in Table VIII.
201~140 CIP of RD-18199 -TABLF~ VT I T
62 6~ 64 s Capped polyphenylene ether, parts 36 37 36 PBT, parts 54 55 54 Impact modifier, parts:
Izod impact strength, joules~m.561219 155 Tensile strength, MPa.:
At yield 46.7 44.7 41.9 At break 40.8 41.4 34.9 15 Tensile elongation, ~ 134 135 70 Heat distortion temp., C -- 156 162 Esl~plga 65-74 Compositions containing epoxytriazine-functionalized polyphenylene ethers, various elastomeric polyester~ and (in Examples 65-71) SEBS as an impact modifier were prepared and molded. The relevant parameters and test result~ are glven in Table IX.
2~
t~
e~
., I . i . . I 1, ~_ L ~ - ~ s =~ C El _ ~ .
0 e o r-~acs~u~ooeo e o--~ ~ ~ ~ nJ ~_ o .~: ~ _ ~ = O '7 N `O
--cn . ~ ~ ~s -- e C~ ~ " _ _ _ -- o I ~ ~
r O O _ I I I
O ~ e I J 1~
~ -- r _ .~ o . L ..
C~ ~ ~ ~ ooooooo I I I
X C~ O _ __ _ __ __, I I
e E--C
1~ _ C ~ ~SS-_ ~OCO
Cl O O O O C O
C~--SO SO SO
~ ~ z I ~ 1.,1~ S S ~
--o L ` ~ ~O ~ `O 'O ~o C C--c ~7~1.7r7~7S=_ L
~_ o. C~
I ~ ~ ~ ¢ S S S ~ ~ C~ --~" r .. _ ------N ~ ~J _ _ _ ~11 O '; . . . . . . . , . . L
-- C XXXXXXXXXX O
O ~1 ~I_L~b~L.I
O, ~
~D U~
_ u~ ~ ~ o--~ ~ s wl .
- 36 - 2 ~
CIP of RD-18199 E"x~_ples 75-80 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 7 - . ~
cl o c I I o I I ~
¢ N S I I _ I I . ."-~ C~
C Ou~ I I ~0_ ~0 I~ N '~ I t r7 o ~-¢ ~C~ I O~ I ON N~
C ~ I = I--~
X ~O~- I ~ I CO O¢S
I --O . S
r- ~`0--Xl ~
~ ~c ~ ~ I u~
_ ~ ~S I I __ . .--C~
r_ ~ N N I I --~ N ~--C 1' .
L L
C C
q~ L ' ~I~
' C ~ Z
_ o C. O
C g_ o g ~C o " L~ L Co O L_ i L ~
G--O~ll~ S C O O
1- ~- O ~ ~ --_ ~ _~ Z--~
a ~ ~ ~ -, C C _ < ~ C
Claims (20)
1. An epoxytriazine-capped polyphenylene ether composition comprising polymer molecules having end groups of the formula (I) , wherein:
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;
each Q2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q1;
X Is an alkyl, cycloalkyl or aromatic radical or (II) ; and R1 is a divalent, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical.
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;
each Q2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q1;
X Is an alkyl, cycloalkyl or aromatic radical or (II) ; and R1 is a divalent, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical.
2. A composition according to claim 1 wherein the polyphenylene ether comprises a plurality of structural units having the formula CIP of RD-18777 (III) wherein 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 lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q1.
3. A composition according to claim 2 wherein R1 is a lower alkylene radical.
4. A composition according to claim 3 wherein the polyphenylene ether is a poly(2,6-dimethyl-1,4-phenylene ether).
5. A composition according to claim 4 wherein R1 is methylene.
6. A composition according to claim 5 wherein X is a lower alkyl or aromatic hydrocarbon radical.
7. A composition according to claim 6 wherein X is methyl, n-butyl or 2,4,6-trimethylphenyl.
8. A composition according to claim 5 wherein X
has formula II.
has formula II.
9. A method for preparing an epoxytriazine-capped polyphenylene ether composition which comprises contacting under reactive conditions, in the presence of a basic reagent, at least one polyphenylene ether with an epoxychlorotriazine of the formula CIP of RD-18199 (IX) , wherein:
X is an alkyl or aromatic radical or (II) ; and R1 is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical.
X is an alkyl or aromatic radical or (II) ; and R1 is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical.
10. A method according to claim 9 wherein the polyphenylene ether is a poly(2,6-dimethyl-1,4-phenylene ether)
11. A method according to claim 10 wherein the reaction is conducted in solution in a non-polar organic liquid at a temperature in the range of about 80-150-C, and the basic reagent is soluble in the organic liquid.
12. A method according to claim 11 wherein the basic reagent is pyridine and the organic liquid is toluene.
13. A method according to claim 12 wherein the amount of epoxychlorotriazine is in the range of about 1-20%
by weight, based on polyphenylene ether, and the amount of basic reagent is about 1.0-1.1 equivalent per mole of chloroepoxytriazine.
by weight, based on polyphenylene ether, and the amount of basic reagent is about 1.0-1.1 equivalent per mole of chloroepoxytriazine.
14. A method according to claim 10 wherein the reaction 19 conducted interfacially at a temperature in the range of about 20-100 C, in a medium comprising water and a non-polar organic liquid, the basic reagent is a water-soluble base, and a phase transfer catalyst is also employed.
CIP of RD-18199
CIP of RD-18199
15. A method according to claim 14 wherein the basic reagent is sodium hydroxide, the organic liquid is toluene and the phase transfer catalyst is a tetraalkyl-ammonium chloride wherein at least two alkyl groups per molecule contain about 5-20 carbon atoms.
16. A method according to claim 15 wherein the amount of epoxychlorotriazine is in the range of about 2-6%
by weight based on polyphenylene ether, the ratio of equivalents of base to moles of epoxychlorotriazine is about 0.5-1.5:1, and the weight ratio of phase transfer catalyst to base is about 0.01-5Ø
by weight based on polyphenylene ether, the ratio of equivalents of base to moles of epoxychlorotriazine is about 0.5-1.5:1, and the weight ratio of phase transfer catalyst to base is about 0.01-5Ø
17. A method according to claim 10 wherein the reaction mixture is subsequently neutralized with an acidic compound.
18. A method according to claim 17 wherein the acidic compound is carbon dioxide.
19. A composition prepared by the method of claim 9.
20. A composition prepared by the method of claim 11 .
WHP/tg
WHP/tg
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/351,905 US5096979A (en) | 1988-06-23 | 1989-05-15 | Epoxytriazine-capped polyphenylene ethers and method of preparation |
| US351,905 | 1994-12-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2010140A1 true CA2010140A1 (en) | 1990-11-15 |
Family
ID=23382925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2010140 Abandoned CA2010140A1 (en) | 1989-05-15 | 1990-02-15 | Epoxytriazine-capped polyphenylene ethers and method of preparation |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2010140A1 (en) |
-
1990
- 1990-02-15 CA CA 2010140 patent/CA2010140A1/en not_active Abandoned
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