CA2082735A1 - Polyphenylene ether-polyester copolymers and compatibilized molding compositions thereof - Google Patents

Abstract

POLYPHENYLENE ETHER-POLYESTER COPOLYMERS
AND COMPATIBILZED MOLDING COMPOSITIONS THEREOF
Abstract of the Disclosure Copolymers of epoxytriazine-functionalized polyphenylene ethers with segmented, linear copolyesters having carboxy end groups exhibit useful properties and fluid utility as molding compositions and as compatibilizers for blends of the component polymers. Representative epoxytriazine-capped polyphenylene ethers may be prepared by reaction of a polyphenylene ether with an epoxychlorotriazine such as diglycidyl chlorocyanurate, n-butyl glycidyl cholorcyanurate or mesityl gltcidyl chlorocyanurate.
Representative copolyesters are those characterized by recurring intralinear long chain ester units of formula:

(I) wherein G represents a divalent organic moiety remaining after removal of terminal hydroxy groups from a poly (alkylene ether) glycol; and R represents a divalent organic moiety remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than 300;
interrupted by short chain ester chain units of the formula:-

Description

2~273~
1 08CNo8534 , POLYPHENYLENE ETWER-POLYESTER COPOLYMERS
AND CO~P~IBILIZED ~Q~ING COMPOSI~IONS THEREOF
~ACR~QUNp QE ~ l9 Field o~ t~e Invent~n This invention relates to the preparation of polyphenylene ether-copolyester copolymers and their UB~ in compatib~lizing blends of the polyphenylene ethers and copolyesters.
Brie pesç~iption of the Pxio~
Polyphenylene ether~ are a wid~ly used cl~sfi of -thermoplastic engineering resins ~haracterized by excell~nt hydrolytic stability, di~ensional ~ta~ y/ toughness, heat resistanc~ and dielectric properties. However, they ~ay be deficient in cer~ain other desired properties ~uch as workability and non-polar solvent resi~tance. There~ore, there is a cont~nuing need for means of modi~ying polyphenylene ethers ~o i~prov~ certain properties.
For increased solvent resistan~e, ik would be : desirable to form molding compositions in which polyphenylene ethers are co~bined with polymeric resin~ h~ving a high degree of crystallinity and therefore high resistance to non-polar solvents.
Illu~trative o~ such re~ins are the thermopIastic ; polyesters.
However, polyphenylen@ ether-polyester blends frequently are incompatible and articles molded from them undergo phase separ~tion and dela~ination.
They typically contain large, incompletely dispersed :: polyphenylene e~her particles and lack phasa interaction betwee~ the two resin phases. Mol~ed ' ' ,:

2~273~
08CNo8534 parts made from such blends are typically characterized by extremely low impact strength, brittleness, delamination and the llke, particularly at low temperatures.
Numerous methods for compatibilizing polyphenylene ether-polyester blend compositions have been considered. For example, PCT published .; application 87/850 describes blends of these resins compatibilized by the addition of an aromatic polycarbonate. Such blends are useful in numerous applications such as the ~brication of automobile body parts. However, the presence of polycarbsnate may result in loss o~ certain other properties such as heat distortion properties.
; 15 In addition, a problem sometimes arises by virtue of the presence of aminoalkyl-substituted end : groups on certain commercially available polyphenylene ethers, as described in more detail hereinafter. For optimum impact strength, it is .~` 20 frequently necessary to remove such ~: aminoalkyl-substituted end groups and other amine constituents frequently pre~ent as impurities in the polyphenylene ether. Such expedients as the use of amine quenchers and/or vacuum ven~ing o~ the polyphenylene ether are effective in decreasing amino nitrogen content, but add a step to the processing operation which may be undesirable or uneconomical in certain circu~stances.
Various methods are al50 known for preparing copolymers of polyphenylene ethers with polyesters.
Some such copolymers are said tv be effective as compatibilizers for blends of the component resins.
To facilitate the copolymer ~or~ation, one frequently employs a polyphenylene sther containing . , ~ , .

~n~273S

: 3 , function~l groups. For example, epoxy groups can react with nucleophilic groups in polye~ters leading to copolymer ~ormation.
The copolymers oP the present invention comprise polyphenylene ether segments joined with : randomized block copolym~rs o~ crystalline hard polyester segments and with ~morphous glycol soft segments. Families of resins can be produced by varying the ratio of hard ~o soft ~egments.
Although the copolymers of the invention per se are useful as molding compositions, they are particularly use~ul as co~patibilizers in thermoplastic molding blends o~ the polyphenylene ethers and th2 copolyesters used in their preparation.
SUMMARY OF THE INVENTION
The invention comprises the copolymer of an epoxy-~unctionalized polyphenylene ~ther and a carboxy-terminated, segmented, lin~ar copolyester having recurring intralinear long chain ester units o~ formula:
., . _ _ ~ 25 _ - 9 - G - O - C - R - C - _ .
. _ _ , (I3 wherein G represents a divalent organic moiety remaining after removal of terminal hydroxy groups from a poly (alkylene ether) glycol; and R
represents a divalant organic moiety remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than 300:
interrupted by recurring short ch~in ester . chain uni~s of the ~ormula:-2~273$

_ O ~

_-- O -- D-- o-- c-- R-- c --_ ~
(II) wh~r-ln R h~ anln~ pr~v~oul~ly 8-oribQ~ to lt ~nd D r6l~prR~n~- ~ dlval~nt organl~ ~o~oty ~mainin~
A~tsr ro~4~rd~ o~ t~ l hy~r~q,l group~
diol havin~ ~ ~014~ wt~ lo~ th~n 2~0.
nv~n~ sn ~l~o ~o~pr$~a t~ o~ l¢
co~ t~on ~oldln~ blen~ls o;~ ~oly~ nyl~ th~sr ~n~ aopolyost~r~ colapat$~ilizod vl~ ~ ect~
A~oun~ ~or ao~lbillz~lon o~ ~o co~oly~ a~
v~ntion ~ h~ ho~ o~ th~lr ~ar-~ar~ion.
~n gono~al, ~n o~ ei~ oun~: ~or ~o~p~tiblll~-tion 1~ thln tb8 ~ llgll~ Og ~ a~out 0.5 t~ 99 p~ y ~oigh~ Or ~ Gopoly~ o~ lnv~n'e~on ~: 20 for sa~h 100 ~ ot th~ ~ond ~o~ eo~ lbil~z-~t~on~
~o~ ~r~ y, ~h~ copoly~or~ o~
polyph~nylon~ ~tltor~ o t:opo~y~cor- ~d~ up oP
~ ln ~nlS~ ot ~ho ~ormul~ ) and ~S~) ~r~
~as~rr d to h-roln ~ ti~ 3D l:h~ ~opoly~x~ o~
th~ lnv~rt~on~., Tho q:8r~ hl~ng d~ to~ un~ u~
h~r~in ~p~l~d leo unlt~ ln ~ ~oly~r ~ln r~rl~ to ~ ~owt~on produ~t o ~ lln-ar long c~hkin glyc~l 3~ w~ dl~r~wsylio ~ uc~ Wlong o~in un~t~ wh~h ~ a ~ocllrrin~ t ir~ tla~
~o~ly~sr~ im~ o~, ~o~o~ d to Po~l~ ho 1ong ~balR ~y~ ar~
pOay~ lyool~ 18V1n~ ln~l ~or ~ n~arly j5 t3rD1n~1 a~ po~ ) hyd~oxy g~p~l ~nd a aol~cular ~1gtl~; ~aVq3 ~OO lmd P~UC~Y ~ o~t; 4CO--~OOD.
mB l~n-a e:haln glyool~ d to p~a~p~rq~ t~

~0~273~

. S
copolyesters used as components of the copolymers of this invention are advantageously poly(alkylene ether) glycols having a carbon-to-oxygen ratio of about l.9 to 4.1. Representativs long chain glycols are poly(ethyl~ne ether) glycol, poly(tetramethylene oxide) glycol, random or block copolymers of ethylene oxide and 1,2-propylene oxide, and random or block copolymers o~ tetrahydrofuran with minor `~ a~ounts o~ a second monomer such as 3-methyl-tetraAydrofuran (used in proportions such that the carbon-to oxygen mole ratio in the glycol does not . exceed about 4.1). ~
~he term "short chain ester units" as used : herein applied to units in a polymer chain refers to ` 15 low molecular weight compounds or polymer chain - units having molecular weights les~ th~n about S50.
They are made by reactiny a low molecular weight diol (below about 250) with a dicarboxylic acid to ~: form ester units represented by Formula (II~
: 20 above.
DETAITI~D DESCRIPTION OY THE PREFER~ED
.. EMBODIMENTS OF THE INVENTION
., Epoxy-functionalized polyphenylene ethers are - known and disclosed in variou~ patents and public-25 ations. For example, U.S. Patent 4,460,743, inc-orporated herein by reference khereto, d~scribes the reaction of a polyphenylene ether with epichloro-hydrin, to produce an epoxy-functionalized polymer.
In addition, PCT published application 87/7279 describes the reaction of polyphenylene ethers with terephthaloyl chloride and glycidol to form an ~poxy-~unctionalized polyphenylene ether.
~ poxytriazin~-capped polyphenylene ethers for us8 in the preparation of the copolymers and ~08~3~

compositions of this invention are also well known as are methods of their preparation. They comprise polyphenylene ether polymer molecules having end groups of the formula:-~~

2 1 N ~ /O\

(III) wherein each Ql is independently halogen, primary or secondary lower alkyl (i.e., alkyl containing up to 7 carbon atoms), phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at ; l5 least two carbon atoms separat~ the halogen and oxygen atoms;
: each Q2 is independently hydrogen, halogen, primary or secondary lower alXyl, phe~yl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defi~ed for Q1 :
X is an alkyl, cycloalkyl or aromatic radical, or the monoYalent moiety of ~ormula:-; O
-R -CH-CE~
(IV) ; and R~ is a divalen~ aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radic~l. Examples of primary lower alkyl groups suitable as Q1 and Q2 are methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, ~-hexyl, 2,3-dimethylbutyl, 2-, 3 or 4-methylpentyl 2~73~
08CNo8534 and the corresponding heptyl groups. Examples of secondary lower alkyl groups are isopropyl, sec-butyl, 3-pentyl and the like. Preferably, the alkyl radicals are straight chain rather than branched. Most preferably, sach Ql is alkyl or phenyl, especially C~,4 alkyl, and each Q2 i5 hydrogen.
The epoxytriazine-capped polyphenylene ethsrs may be prepared as described in detail hereinafter from polyphenylene ethers known in the art. The latter encompass numerou~ variations and modifications all of which~-are applicable to the present invention, including but not limited to those described hereinafter.
The polyphenylene ethers comprise a plurality of structural units having ~he formula--Q~ Q1 X
.' ~0~o_ .

Q2 Q~ (V) and in each of said unit~ independently, each Q1 and Q2 i5 a~ previously defined.
;Both homopolymer and copolymer polyphenylene ethers are included. Representative homopolymers are those containing, for example, 2,6-dimethyl-1,4-phenylene ether units. Representative copolymers include random copolymers containing such units in combination with (~or example) 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable random copolymers, as well as homopolymer~, are di~closed P~3~ in the patent literature, see for example Hay, U.S.
~Patents 3,306,874 ~nd 3,306,875; Van Dort, U.S.

2~827~5 r Patent 3,365,422, Bennett and Cooper, U.S. Patents 3,639,656, 3,64~,699, 3,733,299, 3,838,102, 3,661,848 and 4,092,294, and Olander, U.S. Patent 4,083,828. All of these patents are incorporated herein by reference.
Also included are polyphenylene ethers containing moieties which modify properties such as molecular weight, ~elt viscosity and/or impact strength. Such polymers are d~scribed in the patent literature and may be prepared by grafting onto the polyphenylene ether in known ~anner such vinyl monomers as acrylonitrile~nd vinylaromatic compounds (e.g., styrene), or such polymers as polystyrenes and elastomers. The product typically contains both grafted and ungrafted moieties. Other suitable polymers are the couplad polyphenylene ether~ in which the coupling agent is reacted in ,-~ known manner with the hydroxy groups of two polyphenylene ether chains to produoe a higher 2C molecular weiqht polymer containing the reaction product of the hydroxy group~ and the coupling agent, provided substantial proportions of free hydroxy groups remain present~ Illustrative coupliny agents are low molecular weight polycarbonates, :~ 25 quinones, heterocycles and formals.
The polyphenylene ether generally has a number average molecular weight (M~ within the range of about 3,000-40,000 and a weight average molecular wei~ht ~) within the range of about 20,000-80,000, , 30 as determined by gel permeation chromatography.
Their intrinsic viscosity is mos~ o~ten in the range of about 0.15-0.~ dl./~., as mea~ured in chloroform at 25-C.
'; ' . .
~.
.

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The polyphenylene ethers are typically prepared by the oxidative couplins of at least one corres-ponding monohydroxyaromatic compound. Particularly useful and readily available monohydroxyaromatic compounds are 2,6-xylenol (wherein each Q1 is methyl : and ~ach Q2 is hydrogen), whereupon the polymer may be characterized as a poly(2,6-dimethyl-1,4-phenylene ~ ether), and 2,3,6-trimethylphenol (wherein each Q1 - and one Q2 is methyl and the other Q~ is hydrogen).
~0 A variety of catalyst systems are known for the preparation of polyphenylene ethers by oxidative coupling. There is no par~cular limitation as to catalyst choice and any of the known catalysts can be used. For the most part, they contain at least one heavy metal compound such as a copper, manganese or cobalt compound, usually in combination with : various other materials~
A first class of preferred catalyst systems consists of those containing a copper compound. Such catalysts are disclosed, for example, in U.S.
Patents 3,306,874, 3,306,875, 3,914,266 and 4,028,341, all of which are incorporated herein by reference thereto. They are usually combinations of ~uprous or cupric ion~, halide (i.e., chloride, bromide or iodide~ ions and at least one amine.
Catalyst systems containing manganese compounds sonstitute a second preferred class. They are generally alkaline systems in which divalent manganese is combined with such anions as halide, alkoxide or phenoxide. Most often, the manganese is present as a complex with one or mor~ ~omplexing and/or chelating agents such as dialkylamines, alkanolamines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds, W-hydroxyoximes - 20~735 08CN0~534 ~ono~r~c and poly~lc), o-hy~roxyaryl oxi~
~ik-tone~ lao u~erul ~r~ ~cnown coballt-~:ont~llning c~taly~t l~y~t~. suit~ble ~angan~ and oo~lt-cont~lnlnq c~ ly~t ~Iy~ or ~ nylene .~ 5 lat~er ~r~paration ~ l~o~n i~ ~hQ art by reason o~
d~¢losur~ in ~ 0us ~t~nts ~m!l publications, ~ poly~honyl~o oth~-r~ ~4~ ~y be ~l?
*or the~ ~U~3~S o~ thle~ $nve~10n ~lud~ tho~
s~h~¢h co~ri~ ol~aaule~ havin~ at l~a~t one o~ the n~ groups o~ ~3 3~o~mulao ~
. ~R3) 2 4 ~1 ~R~
-~0~
. ~
c~2 Ql ~Vl) ~n~
Ql Q2 Q Ql - 20 - o-<O>--~O~--~
~` Q~ 2 Q~Q~' ~VIT~
rein Ql an~ Q~ ~ro a~ ~r~Ylou~ly ~ r~n~dJ ~ach ~2 25 1~ indQp~nd~n~ly a~y~roy~ or al~l, ~rlth t~e ~o~ o t ~ total numb~ o~! c2rbon ato~s in l:lo~h R2 . . r~ cals ~ C or l~ ~oh R3 i~ ~pQndea~t:ly y gen ~ 6 p~ axy alk~l rzldlc~
Pr~ra~ly, oae~ hydxog~ R~
lX~l, e~p~c3ial~y ~3thyl or n-butyl.

:, , , ,1 ~ - .
, . . , ~ .

~273~
08CNo8534 Polymers containing the aminoalkyl-substituted end groups of formula (VI) are typically obtained by incorporating an appropriate primary or ~econdary monoamine as one o~ the constituents of the oxidative coupling reaction mixture, especially when a copper-~ or ~anganese-containing catalyst i~ 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 Q1 radicals. The principal site of reaction is the Ql radical_adjacent to the hydroxy ~ ~roup on the terminal unit of the polymer chain.
During further processing and/or blending, the aminoalkyl-substituted end groups may undergo various reactions, probably involving a quinon0 methide-type intermediate of the formula:-Q ~ (R )2 '~ ~
~ 20 - o ~ o Y >=~
Q2 Ql (VIII~

with numerous beneficial e~fects o~ten including an increase in imp~ct strength and compatibilization with other blend components. Reference is made to U.S. Patents 4,054,553, 4,092,29~, ~,477,649, 4,477,651 and 4,517,341, the disclosure~ of which are incorporated herein by re~eren¢e thereto.
~: Polymers with 4-hydroxybiphenyl end groups of formula (VII) are o~ten especially use~ul in the present invention. They ar~ typically obtained from reac~ion mixtures in which a by-product diphenoquinone of the formula:-, :

"~, .
,' . , :
, , 20827~
08CN0~534 O- ~ --o Q1 Q2 Q2 Ql (IX) ; i~ present, especially in a copper-halide-secondary or tertiary amine sy~tem. In this regard, the disclosure of U.S. Patent 4,477,649 ~s again lo pertinent as are those of U.S. 4,234,706 and 4,482,697, which are also ~ncorporated by reference herein. ~n mixtures o~ this type, the diphenoquinone is ultimately incorporated into the polymer in substantial proportions, largely as an end group.
In many polyphenylene ethers obtained under the above-described conditions, a substantial proportion of the polymer molecules, typically constituting as much as about 90% by weight cf the polymer, contain end groups having one or frequently both of ~ormulae (VI) and (VII). It should be understood, however, that oth~r end groups may be present and that the in~ention in its broadest sense may not be dependent on the molecular struc~ures o~ the polyphenylene ether end groups. It is, however, reguired that a : 25 substantial proportion of free, non-hydrogen bonded hydroxy groups be present: th~t is, that a substantial proportion o~ hydroxyterminated end groups have ~tructures other than that of Formula (VI), for example a structure as shown in Formula VII, above.
As ~ention~d above, the use o~ polyphenylene ethers containiny ~ubstantial amounts of unneutralized amino nitrogen may a~ord composi~ions ' :
, , , -': :
1 ;, ' ~ :

" .

--- 208~73~

.~

with undesirably low impact strengths. The possible :, reasons ~or this are explained hereinafter. The : ~mino compounds include, in addition to the aforementioned aminoalkyl end group~, traces of S amine (particularly ~econdary amine) in the catalyst u~ed to form the polyphenylene ether.
Th~ present inYention therefore also includes ~he u~e of polyphenylene etherc in which ~
"~ ~ubstantial proportion of ~mino compounds have been removed or inactivated. Polymers ~o treated contain unneutralized amino nitrogen, i~ ~ny, in amounts no greater than ~bout 800 pp~
A pref~rred ~ethod of inactivation is by P extrusion of the polyphenylene ether at a temperature within the range of about 230-350'C, with vacuum venting. This may be achieved in a preliminary extrusion step, by connecting the vent o~ the extruder to a YacUUm pump capable of reducing the pressur~ to about 200 torr or le~. Ther~ may also be advantage~ in employing vacuu~ venting during extrusion of the composition of this inv~ntion.
It is believed that this inactivation ~ethod aids in ~he r~moval by ~vaporation o~ any traces ~
free amines (predominantly ~econdary am~nes) in the poly~er, including amine~ generated by conversion of aminoalkyl end groups to quinone ~ethide~ of ~he type represented by formula (YI).
. It will be apparent to those skilled in the art from the foregoing that the polyphenylene e~hers ~ conte~plated for u~e in the pre~ent inventlon ; include all those presently ~nown, ~rrespective of ;:: variations in structural un~ts or ancillary che~ical featureR.

, ,' ' ; ~ :
:.~ '. , , ,, .

8273~
08CNo8534 The end groups on the epoxytriazine-capped polyphenylene ethers have formula (III), in which Q
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 aro~atic radical, typically monocyclic and containing 6-10 carbon atoms and especially an : aromatic hydrocarbon radical; or a radical of ~ormula (rV). In for~ulae (III) and (IV), R1 may be ~0 aliphatic, alicyclic, aromatic (including aroma~ic : radical~ containing art-recognized substituents~ or heterocyclic. It is u~ual~y lower ~lkylene and ~ especially methylene.
: The above-described epoxytriazine-capped polyphenylene ether compositions may be prepared by contacting under reactive conditions, ~n the pres~nce of a basic reagent, at least one polyphenylene ether with an epoxychlorotriazine of the ~ormula:-Cl O
~ /\
X~ ~R~ C Hz .,.
. (X) wherein Rl ~nd X are ag previou ly defined.
Typical ~poxychlorstriazines o~ formula (X) include 2-chloro-4,6-diglycidoxy-1,3,5-triazine (hereinafter "DGCCn), 2-chloro 4-~ethoxy-6-glycidoxy-1,3,5-triazine, 2-chloro-4-(n-butoxy) 6-glycidoxy-1,3,5-triazine Shereinafter ~B~,~C") and 2-chloro-4-52,4,6-trimethylphenoxy) , .:

' ' '' ' .

, 8273~
08CNo8534 -6-glycidoxy-1,3,5-triazine (hereinafter ~MGCC"3.
These compounds may also be named ~ though deri~ed from cyanuric acid and designated diglycidyl chlorocyanurate, n-butyl glycidyl chlorocyanurate and 2,4,6-trim~thylphenyl glycidyl chlorocyanurate, ; resp~ctively. Ihey may be prepared, ~or example, by the reaction of 2j4,6-tri~hlorotriazine (cyanuric chloride) with glycidol or combination thereof witb ~-buta~ol or mesitol. Cyanuric ~hlorid~ and n butyl dichlorocyanurate are both commercially available.
Intermediates ~uch ~s DGCC, BGCC and ~GCC and the method for their prep~r~tion ~re known. ~heir preparation i8 illustrated by the following procedures.
PREPARAT10~ 1 : To a mechanically stirred 601ution of 220.~ g.
(1.2 moles) cyanuric chlorid~ in 1500 ml.
chloroform, cooled to 0-10C, was added 266.4 g.
(3.6 moles) glycidol in one portion. Aqueous sodium hydroxide (50% ~olution; 192 g.) was add~d to the mixture dropwi~e wi~h stirring over abou~ 3 hours maintai~ing the reaction temperatur~ below ~O-C and pre~erably ~round 0-S-C. ~he reaction ~xture was allowed to warm 810wly to room temperature. The chloroform layer wa~ washed with di~tilled water until neutral and dried over magnesiu~ sulfate. The reaction pro~uct w~ ~ound by carbon-13 nuclear ~agnetic re~onan~e to be 2-chloro-4,6-: diglycidoxy-1,3,5-triazin~ (DGCC). Analysis by ~ 30 liquid chro~atography ~howed about 95% (by weight) ,~ chlorodiglycidoxytriazine. The reaction mixture also .` was ~ound to contain small amount~ o~
i trigly~idoxytriazin~ and dichlorsglycidoxytriazine.
.~
,, 7~

R~PARATION ~
To A magnetically ~itirred 601ution of 250 g.
(1.125 moles) n-butyl dichlorocyanurate in 757 ~1.
chloroform, ~ooled to 0-10-~, was ~dded 250 g.
(3~375 moles) glycidol in one port~on. Aqueous ~odium hydroxide (50% 601ut$0n; 90 g.) wa~ added to the mixture dropwi~ie withi stirring over about 2 hour~, maintaining the reaction temperature below lO-C and prererably i~round O-~-C. The reaction mixture was allowed to war~ to roo~ temperature over - 30 ~inutesi. Th2 chloroform layer was wash~d with .~ diGtill~d ~ater until neu~2al ~nd dried over magnesium sulfateO Proton nucle~r magnetic resonance analysis indicat~d a 95~i yield o 2-chloro-4-. 15 (n-butoxy)-6-glycidoxy-1,3,5-triazine (BGCC).
PREPARATION ~
To a mechanically stirr~d solution of 50 g.
.` (0.175 mole) 2,4, 6-trimethylphenyl dichlorocyanurate (prepared by the raaction of equimolar amounts of ~esitol ~nd cyanuric chloride) in 170 ml. ~ethylene chlor~de, cooled to O-lO~C, was added 26.38 g. (~.356 mole) glycidol in one portion.
~:; Aqueous sodium hydroxide ~50% ~iolution; 14.26 g~) was added to the mixture dropwise with stirring over about 25 ~inutes ~aintaining th~ reacti4n temperature between 0- and lO-C and pre~erably round 0-5C. After ~itirring an additional 30 . minutes, the re~ction mixture wa~i allowed to warm to i.~ room tQ~pexature. The ~ethylene ~hloride layer wa~
waRhed with distill~ wa~er until neutral ~nd dried :' over m~gnesiu~ sul~ate. Th~ rea~tion product wa~
;: found by proton nucle~r mag~etic rçsonance to be 2-chloro-4-(~,4,6-trimethylphenoxy)-6-glycidoxy-1,3,5-triazine (MGCC~.
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~ ~) 8 2 7 3 ~
08CNo8534 Yarious options are available for the reaction of the polyphenylene ~ther with the epoxychlorotriazine, ~ preferred method of preparation produces S epoxytriazine-capped polyphenylene ~ther6 by a reaction conducted interfacially in a ~edium ~o~pri~ing water ~n~ ~ non-polar organic liquid.
The basi~ reagent i6 a water-soluble base, typically an alkali ~etal hydroxide ~nd preferably ~odium ~0 hydroxide. It may added to the mixture of ~poxychlorotriazine and polyphenylene ether, or may initially react with the pol~phenylen~ ether to form ~ 6alt which is then contacted w~th the epoxychlorotriazine. There is al~o employed a phase transfer catalyst. ~ny of ~uch catalysts which are stable and effective under the prevailing reaction conditions ~ay be used; those 6killed in the art will readily perceive which ones are ~uitable.
Particularly preferred are the tetraalkylammo~ium chlorides wherein at lea~ two alkyl groups per molecule, typically 2 or 3, contain about 5-~0 carbon atom~.
I~ this ~ethod, reaction temperature~ in the ; range of about 20-llO-C m~y be employed. The amount of epoxychlorotriazin~ is ~requently lower than in the previou~ly d~.cribed method, typically in the i~ rang~ of about 1-6~ ~nd preferably about 2-6% by weight based on polyphenylene ether, ~lnce th~
reacti~n of th~ epoxychlorotriazin~ with the polyphenylena ether ~pparently proceed~ ~ore naarly ~ to co~pl2tion. ~ost often, the ratio of ~quivalent~
of base to mol~s of epoxychlorotriazine is about 0.5-1.5:1, and the weight ratio of phase transfer c~taly~t to ba~e is about 0.01-5.0:1.

,, , 2~8273~
08CNOg534 Still another method util~zes an organic liquid : and a solid ba~e, ~ypically a %olid ~lkali metal . hydroxide or an anion exchange resin in the ~ree ,~ base ~orm. Chloride salt~ m~y be removed by methods known in the ar~, including water washing when a : hydroxide is employad and filtration when an anion ~xchange resin i8 e~ployed.
Regardless of which ~ethod of preparation i~
u~ed, the epoxytriazine-capped polyph~nylene ether may be isolated by conventional ~ethods, typically by precipitation with a non-solvent. Among the non--solvents which may be~mployed are methanol, l-propanol, acetone, ~cetonitr~le, mixtures thereof ~- and the l~.ke.
When the non-~olvent i8 an alcohol, and e~pecially ~ethanol, it may undergo base-promoted reaction with the epoxytriazine moieties on the ~ capped polyphenylene ether, u~ually resulting in a : loss o~ epoxide groups~ Either or both of two ~0 op~rations may be employed to suppress thi~
reaction. The ~ir~t i8 to neutralize the reaction mixture with any ~onvenient acidic compound; carbon dioxide, in gaseous, liquid or ~olid ~orm, is oft~n ; preferred. The ~eoond is to reDove alcohol from 2~ contact with the product as rapidly and completely po sible ~y conventional means~ typic~lly ; including a ~ub6equ~nt drying ~tep.
In the ~ollowing ~rep~rations 4-1~ which : illu~trate the preparation of epo~ytriazine-capped polyphenylene ethers, proportions of epoxychlorotriazine are expressed a~ a percentage of : polyphenylene ether. T~e rollowing polyphenyl~ne ~ ether~ were e~ployed:

:.

, :
.'1 ~
, 20~273~
;~ 08CNo8534 .~

PPE - a poly~2,6-dimethyl-1,4-phenylene ether) having an ~ntrinsic vi~cosity in chloroform at 25-C of 0.40 dl.~g.
YV - PPE w~ich had been extruded on a twin screw extruder within the temperature range of About 260-320-C, with vacuum venting ~o ~ maxi~um pre~sure o~ about 20 torr.
LN - a poly(2,6-dimethyl~1,4-phenylene ether) having an intrin~lc v~scosity of 0.57 dl./g., having a low proportion of nitrogen as ~ result o~ preparation with a cataly~t cont~ining no primary or ~econdary a~ine.
~:~ Percentages of epoxytriazin~ in the capped poly~er were determined fr~ the r~lativ~ areas o~ peaks in the nuclear magnetic re~onance ~p~etrum attr~butable to hydrogen ato~s in the epoxy and aromatic ; moieties. C~lorine percentages w~re determined by guantitative X-ray ~luorescence.
pREPARATIONS ~4 To ~olutions o~ 400 gra~s o~ polyphenylene ether in 2500 ~1. o toluene were Added, ~ith fitirring, various quantities of pyridine ~ollowed by various quant~tie~ of ~po~ychlorotriazin~s, added in portions. The ratio of equiv~lents o~ pyri~ine to mol2~ of epoxychlorotr~azine was ~oO4 1~ The ~olution~ were h~ated under re~lux for variou~
per~ods o~ time, ~fter which the product~ w re pr~cip~tat.d with methanol ln ~ blender9 ~iltered, wa~ed with ~thanol and vacuu~ dried. ~he relevant : p~rameters an~ analytical results ~re giv~n ln ~3~ i below.

~2~

C
?L I lolo Q
N n u) ~r o C> ~
~: oooooo~,ioo,i ~a_ I

U U V U V U U V

_l ~
L

E ~ 1~ 0 q-~ N ,~ ~r `.

;

2~8~735 PREP~RATIONS lS~
To solutions of 400 grams of polyphenylene ether in 2500 ~l.of toluene were ~dded various quantities of epoxychlorotri~zines dissolved in a small a~ount of methylene chloride. There were then ~dded 48 gra~ of ~ 10~ solu~ion in toluene of a com~ercially a~ilable methyltri~lkyla~monium chloxide in ~hiGh the alkyl groups contained 8-10 carbon atom~, and 10~ ~queou~ sodiu~ hydroxide solution in the amount o~ 1.3 equivalents o* sodium . hydroxide per ~ole of epoxychlorotriazine. The mixtures were stirred vigo~ously ~or various periods ~t ~5-40-C, ~ter which the product~ were precipitated with methanol in a blender and rapidly filtered, washed with ~ethanol and vacuu~ dried.
The result~ ~re given in ~bl- 2, below.

, "
,' r to o co In o . ~ ~ u)oo~cno~r~m 0~i00~i0~0~

.` .
O E
~, ~ C~ o o o o o o o Cl C~ o o ;
_ 0 _ U
N~l InOt~OOO~OOO~ :~
.j ~ 0~ .
:: ~ o ~ ~ u ~ v u ~ 3 ~
8 ~ æ æ
~,.
.
i D I

s. a ~ 9 .. ~ O
,.-. ~ e~
.;

C ~I r~l ~1 ~ ~1 ~1 N t'~

:;
.~ .

2~8273~

Carb~xy group end-terminated linear copolyesters having chain unita of the Formulae (I) ~nd (II) as described above are generally well known as are methods of their preparation; see for : 5 example the descriptions given in the U.S. Patents 3,763,109 and 3,7~4,520, both of which ~re : ~nc~rporat~d her~ifi by ref~rence th~reto. In ge~eral, these copolyest2rs may b2 prepared by transesteri~ication of the alkyl e~ter of ~
dicarboxylic acid having a ~olecular weight of less than about 300 with a mixture of long chain and short chain diols. :~ -Transest~xification may be ~f~ected by heating to a temperature of ~rom about 150-260 C. in the presence o~ a trans~sterification ~atalyst; see U.S.
Patent 3,763,109.
The dicarboxylic acids, the alkyl esters of which are employed in the transe~terification are generally well known as ar2 me~hods o~ their preparat~on. Representative of such dicarboxyl ic acids are the aliphatic and cycloaliphatic compounds ~uch as sebacic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, glutaric acid, ~uccinic acid, carbonic acid, oxalic ac~d, diethyl-malonic acid, allyl~alonic aci~, 4-cyclohexane-1,2 dic~rboxylic ~cid, 2- -ethylsuberic a~id, 3,3,3,3-tetramethyl~uccinic acid, cyclopentanedicarboxylic acid, decahydro-1,5-nap~thalene dicar~oxylic aci~, 4,4'-cyclohexyl dicar~oxylic acid, decahydro-2,6-naphthalene dicarboxylic ~cid, 4,4'-methylenebi~-(cyclohexan~
c~rboxylic acid), 3,4-~uran dicarboxylic acid, and 1,l-cyclobutane dicarboxyl~c acid. Preferred .

: 2~8273~
. 08CNo8534 ''~

;; aliphatic acids are cyclohexane-dicarboxylic acid and adipic acid.
: Representative aro~atic d~carboxylic acids ; which can be used include phth~lic, terephthalic and isophthalic acids, 6ubst~tutQd dicarboxy compounds with two benzene nuclei ~uch a8 b~s(p-carboxyphenyl)me~hanOE, p-oxy(p-carboxyphe~yl) ` benzoic acid, et~ylene-bis(p-oxybenzoic acid), 1,5-naphthalene dicarboxylic acid, 2,6-naphthalen2 dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid, anthr~cen2 ; dicarboxylic acid, 4,4'-su~fonyl dibenzoic acid, and : Cl-C10 alkyl and ring ~ubstitution derivative~
~hereof, ~uch as halo, alkoxy and aryl derivatives.
Hydroxyl acid~ such as p(N-hydro~yethoxy) benzoic ~'~ acid can also be used providing ~n aromatic dicarboxylic acid iB al80 pre~ent~
Aromati~ dicarboxylic acid~ are ~ preferred ~ clac~ ~or preparing the copolye6ter polymer6 used in !` 20 thi8 inven~ion. Among the aromatic acids, tho~e wi~h 8-16 carbon ~to~s ~re preferred, particul~rly the phenylene di~arboxylic acids, i.e,, phthalic, ~ ter~phthalic and isophthalic acids and ~ixtures ;~ thereog.
Advantageously, at le~st about 70 mole percent o~ th~ diGarboxylic a~ids incorporated into the polymer ~ill bQ terephthalic acid and at least about 30 to 40 ~ole perc~nt o~ the low ~olecular ~eight diol incorpor~ted into the polymer will be a mixture of 1,4-butanediol wi~ 1,6-hexanediol, optionally ::~ ~ith l,~-butenediol. This me~ns th~t 70% o~ the :: total ~ group~ in Formula (I) plu8 Pormu~a (II).
- above are phenylene radical~. Thus, fewer than 70%
, ~f the R group~ ln eith-r Or ~oraul~ cr For=ula ~', :, , ,. ~
, .,.

:
, .

20g2~3~

(II) can be 1,4-phenylene radical~ provided that at least 70% of the total R radicals in both formulae are 1,4-phenylene radicAls. At least about 70% of the D groups in For~ul~ (II) above ~re 1,4-butylene and 1,6-hexylene radical~ tderived from 1,4 butanediol or 1~6-hexan~diol~O
The term "dicarboxylic ~cidsN ~ used herein, includes eguivalent~ o~ dicarboxyl$c acids having two functional c~rboxyl groups which perform ~bstantially like dicarboxylic acid~ in-reaction with glycol~ ~nd diols in forming ¢opolyester polymers. These equivalents include esters and aster-forming derivatives, ~uch as acid halides and anhydrides. The molecular weight reguir~ment pertains to the acid a~d not to itC equivalent ester or ester-forming derivative. Thus, an ester Or a dicarboxylic acid having a molecular weight greater than 300 or an a id aquivalent of a dicarboxylic : acid having a molecular weight greater than 300 are included~
Included among the low molecular weight diols ~other than 1,4-butanediol) which react to ~orm ~hort chain estex unit~ (~I) ar~ ~cycl~c, alicyclic, ; and arom~tic dihydroxy co~pounds. Preferred ~re diol~ with 2 1~ c~rbon a~oms such a~ ethylene, propylene, tetra~ethylene, pentamethylen~, 2,2-dim~thyltrimethylene, hexamethylene, and decame~hylene glycols, ~ihydroxy cyclohexane~
cyclohexan~ dimethano~, reaorcinol, hydro~uinone, ; 30 l,~-dihydroxy naphthalene, the like and ~ix*ur~s thereo~. E~pecially preferred ~re aliphatic diol~
containing 2-8 carbon atom~. Includ~d a~ong the ~i~phenols which can be used are bi~p-hydroxy) diphenyl, bis(p-hydroxyphenyl) ~ethane and bis~p~

20~2~
;

; 08CN08534 hydroxyphenyl) propane. ~quivalent ester-forming : derivatives of diol~ are al60 useful (e.g. ethylene oxide or ethylene carbonate ~an be used in place of ethylene glycol). The term ~low molecular weight diol~ as used herein should ~e construed to includ~
~uch e~uivalent ~ster-for~ing deriv t~ves; provided, ' however, ~hat th~ ~olecular weight requ~rement : pertains to ~he diol only and not to it~
derlv~tives.
Pr~ferred lin~ar copolyesters used in preparing copolymers of the invention are tho~e prepared ~rom di~ethyl terephthalat~ butanediol, 1,6- -hexanediol, poly(t~tra~ethylene ether) glycol and : the like having a molecular weight of at l~ast about 1000-2000 or poly(ethylene oxide) glycol having a ~olecular weight of at least about 1500-2500.
Optionally, up to ~bout 30 mole perc~n~ ~nd pr~ferably 5-20 mole percent o~ the dimethyl terephthalate in these polymers can be replaced by dimethyl phthalate or di~ethyl isophthalate.
The dicarboxylic acids or their derivatives and the polymeric glycol are incorporated into the final ; product in ~he same ~olar proportions as are present in the reactlon ~ixture. Th~ amount o~ low ~olecular weight diol ~ctually incorporatod correspond~ to the dif~erence between the ~oles of diacid and polymer~c glycol present in the reaction : ~ixture. Wben mixtures of low ~olecular weight d~ol~ ~re employed, the a~ount of each diol incorporated 1~ lar~ely a function of the amounts of the diols present, th~ir boiling points, and relative reactivities. The to~al ~mount of glycol incorporat~d i~ 8till the d~fference between mol~s of diacid and p~lym~ric glycol.

, 2082~3~
: 08CNOZ534 : 27 Because the principal reaction which occurs with the epoxy group~ in the endcapped polyphenylene ~ sther involve~ a car~oxylic acid group of the .'~ copolyester, it i8 highly preferred that the copolyester used have a relatively high carboxylic end group ~oncentratlon. Concentration3 in the range of about 5-250 microequiv~lent~ per gra~ are generally advantageous, wi~h lO-lO0 microeguivalents per gram being prefQrable, 20-lO0 being ~ore preferable and 20-50 being partlcularly desirable.
The polyphenylene ether-copolyester copolymers of the invention generally~have a weight aver~ge molecular weighk ~) in the range of about 50,000 to 270,000, as determined by size exolusion chromatography versu~ a polystyrene calibration u6ing a chloroform mobile phase containing 7 percent ; ~,1,1,3,3,3~hexafluoro-2-propanol. Both the architecture and the moleoular weight of the copolye~ter are i~portant to achieve th~ opti~um compatibilization and desirad physical properties in produc~s of the invention. As ~ convenient means of selection, ~he preferred copolymers of ~he invention will have ~ melt visoosity above abou~ lO00 poise ~nd ge~er~lly within the range o~ fro~ 1200 to 6000 pol~e measured by te~t method ASTM-D123~ at a temperaturQ o~ 250 C. under a 21.6 gg lo~d ~nd with 0.042 inch diameter, L/D 16/1 orifioe.
Either ~olution or melt blending procedure~ ~ay be employed ~ox the preparation of the copolymers of 30 ~hi8 invention. Typical r~action te~peratures are in th2 ranqe of ~bout 175-350-C. Thu~, relatively high boiling ~olvents ~u~h ~8 o-dichlorobenzene, nitrobenzene or 1,2,4-trichlorobenzen~ are preferred for aolution reac~ions.
' , ' , ' . ~

2~7~
08CNo8534 ~ ~elt reaction procedures are frequently preferred becau~e of the avail~bility of melt blending egu~p~ent in co~merc~al polymer proces~ing facilitia~. Conventional equip~ent of th~ 8 type i8 univer~ally av~ilabl~, ~ith tn~ ~s~ of extrusion eguipment generally being co~v ni~ntt for example, a vacuu~ ~ented, co-ro~ating twin scr~w 28 or 30 mm, Werner and P~leiderer extruder.
Although ~he in~entors are not to be bound by any par~icular theory, it is belie~ed that a principal reaction which take~ place between the pre~rred epoxytri~zine-capped polyphenylene ether and the copoly~ster generally involv~s the carboxylic acid end gro~ps of the latter. Another pos~ible reaction is ~etween hydroxy end groups of thQ polyester and the epoxy groupQ of the functionalized polyphenylene ether.
'rhose skilled in the art will appreciate that copolymers of the invention possess a variety of specific ~tructur~l formulae. The product of the - copolymeriza~ion reaction i8 in fact a mixture of copoly~ers, diffsring in ~pecific ~ruct~re~
one ~tructure may be ~ pol~phenylene eth~r-copolye~t~r copolymer ~lecule cont~ining at least one polyphenylene eth~r-copolyester linkage of the formula:-QZ Q~ OZ~

_~ 0--~
~ N ~ CH _z2 Q2 Ql ~-Rl-CH-Z3 2~8~3~
08CNOg534 wherein each Q1 i~ independently halogen, primary or secondary lower ~lXyl, phenyl, haloalkyl, aminoalXyl, hydrocarbonoxy, or h~lohydrocarbonoxy wherein at least two carbon atoms separate the halogen ~nd oxyg~n atoms: ~nd each Q2 i8 independently hydrogen, halog~n, primary or secondary lower ~lkyl, phenyl, haloalkyl, : hydrocarbonoxy or h~lohydrocarbonoxy as defined for Ql;
0 R1 i8 a divalent aliphatic, ~licyclic, heterocycli~ or unsubstituted or substituted aromatic hydrocarbon radio~l;
Zl iS an alkyl, cycloalkyl or ~romatic radical, or -Rl-cH_z3 O O
Z2 i~ 0~ and Z3 ~S -O-C-, or Z2 is ~O-C- and Z3 is OH;
~aid linkage ~eing interrupt2d by recurring ; intraline~r long chain ester units of the formula ~I) given above and which are interrupt~d by 6hort chain ester chain uni~s o~ the formula ~II) given above.
The crude product mixtures are use~ul ~ithout sep~ration into compositions o~ homogeneous Gopolymer structure as molding compositions or zs compa~ibilizers.
The proportions of epoxy-~unctionalized polyphenylene ether nd the copolyester e~ployed for th2 preparation of the copoly~er~ of the invention are not critic~l ~nd ~ay be widely varied to provide ~ompcs~t~ons havlng the desired propertie~. Most o~ten, each react~nt poly~er ig employed in an amount in the rang~ of about 5-95%, pre~erably abou~ ~0-70%, , 35 of the copolymer product by weight~

3 ~

In a preferred method of prepAring the copolymers o~ the invention, the ~poxy-functionalized polyphenylene ether is reacted with an excess ~guivalent proportion of the linear copolyester react~nt BO that ~he r~action product o~ the :~ copolymerization i~ sbtained dispersed in ~ continuous pha~e o~ unxeact~d copolyester r~s~n. ~he latter phase protects the copolymer reaction produ~t ~giving ~: che~ical resistance).
In addition to polyphenylene ether-copolye~ter . copolymer o~ the invention, the co~position6 of thi~
invention may al~o contai~Funreacted polyphenylene ether. This will include any polyphenylene ether ~olecules having only hydrogen bonded end groups (i.e., the aminoalkyl-su~stituted end groups of formula VI), as well a8 other polyphenyl~ne ether which is unfunctionalized as a result of incomplete capping or which is functionalized but fails to react wi~h th2 copolye~ter. The~e compositiGn~ ~ay also contain unreacted copolye~ter. In ny ~vent, molded part~ produced ~rom such co~positions ~re generally ductile a~d have highex impact ~tr~ngth~ than those produced ~r~ ~i~ple polyphenylene ether-copolyester ~ blen~, which are usually inco~patibls and often '. 25 exhibit brittlene~ or delamination ~s pr~viously , :~ dQscrlbed.
Exp~rim~ntal data ~ugges~ that certain o~her ~ctor~ ~re o~ i~portance in prepar~ng ~olding compo~i~ions of ~axi~um i~p~ct ~trength. One of these is the proportion o~ unneutralized amino nitrogen in the polyphenylene ether; high proportions ~y cause ~ide reactions~ including opening o~ epoxide rings, displace~en~ of epoxide group~ ~ro~ the cyanurate ~oiety and cleavage of ~ster linkages. Such sid~

2082~3~
oscNo8534 re~ctions can be ~inimizQd by ~acuum venting the polyphenylene ether and/or the composition of thi~
invention as melt blending i~ carried out. Another factor is the ~olecular ~tructur~ of the copolymer, wh$ch ~ay vary wit~ the ~ol~cular ~tructure o~ the c~pping agent u~ed (BGCC or N5CC a~ contrasted with DGCC) and it~ proportion or the archit~cture of the copolyester; i.e.; the linear nature of the copolyester.
Th~ thermoplastic molding composition6 of this invention may contain other constitue~t~ in addition to the copoly~ers o~ the ~vention, the unreacted polyphenylene ether, othQr polymer an~ copolymers.
Advantageously an optional constituent i5 an impact modifier. Examples ~re i~p~ct modifiers compatible with ~ither or both of the polyphenylene ether and the copoly~ster polymer.
Representative impact ~odifiers include various elastomeric copolymers, of which examples ~re ethylenepropylene-diene ~oly~er~ (EPD~'s), both un~unctionalized and funotionalized with (for example) sul~onate or phosphonate groups: carboxylated ethylene-propylene rubber~; polymerized cy~loalkenes;
and block copolymer6 o~ alkenylaromatic compounds such as ~tyrene with polymerizable olefins or dienes, inclu~ing butadi~ne, isoprene, chloroprene, ethylene, propyl~n~ and butylene. A180 included are core-6hell polymers, $ncluding tho8e eontaining a poly(alkyl acrylate) core ~ttached ts ~ polystyrene sh~ll Yia interpenetr~ting network, and more ~ully disclo~ed in U.S. Patsnt~ 4,681,915 ~nd 4,684,696 incorporated herein ~y referenc~.
The pre~erre~ impact ~odifiers ~re block (typically diblock, triblock or radial teleblock) 2~827~
~. 08CN08534 ' ~opolymers o~ alkenylaromatic co~pounds and dienes.
Mo~t often, at least one block i8 derived from styrene and ~t least one other block from at least one of butadien~ and isoprene. Especially praferred are the triblock copolymers with poly~tyrene end blocks and diene-derived ~idblocks. ~t i8 frequently ~dvantageous to remove (prefer~bly) or d~crease the aliphatic unsatur~tion therein by ~elective hy~rogenation. The ; welght ~verage molecular weight~ of the impact ~odifier~ are t~pically in tAe r~nge of about : 50,000-300,000. Block copolymers of thi~ ~ype ar~
commercially available rrQ@ Shell Che~i~al Co~pany under the trademark gRATON , and include KRATON~ DllOl, G1650, G1651, Gl652 and G1702.
Finally, there ~ay be present in thermoplastic blend molding compositions of the invention conventional ingredients such a5 fillers, flame retardant~, pigment~, dyes, thermal stab~lizers, anti-static agents, anti-oxidants, W -stabilizers, .; 20 l~bricants, viscosity ~odifiers, crystallization aids, ~old relea~e agents and the like.
; The ~ollowing examples de~cribe the manner and the process o~ making and using the invention and ~et forth the beet mode contemplated by the inventors, but :'~ 25 ~r~ not to b2 con~tru~d as li~iting th~ invention.
All parts 2nd percentages in the ~ollowing example~ ara by weight.
The re~inouR blend~ described by the examples ; were prepared ~y ~ry ~i~ing and extruded on ~
twin-~crew extruder at ~00 rpm. and 190-255-C. The extrudates wer2 quenched in wat~r, pelletized, oven : dried and ~old~d at 280-C into test ~peci~ens which were testea according to the following tas~
procedures.

: .

8273~

~otched Izod impact ~t~enoth and ~ensile proper~ies:
ASTM procedure~ D25S and D638, respectively He~t Distor~iQn Te~peratur~:
ASTM Procedure D648 ~t 0.455 MPa.
~el~ F~
AS~M t~st ~ethod D-12320 .Blend com~atibility:
Determinad by ~icroscopy to observe thQ
polyphenylen~ e~her p~rticle ~ize in a copolyester matrix. In thi~ re~pect, we have found that the : linear copolye~ters can be made co~patible with polyphenylene ethexs to gi~e blends containing polyphenylene ether particles with a ~ize of less than 1 micron. The smaller, controlled particle 8iZ~
~5 results in i~proved physical property performance on injection molded articles. The small, controlled particle ~ize i5 key to obtaining and maintaining excellent physical properties in molded parts.

A copolymer oP the invention is prepared by copolymerizing 35 part~ of an epoxytriazine-capped polyphenylsn~ ether prepared according to the ~ethod of Preparation 25, 6upr~. with ~0 p~rts of a linear copolyester prepared by polyesterirication o~
~quivalent ~xces~ of dimethyl terephthal~ with a 2:1 weight ~xture o~ 1,4-butanediol and 1,6-: hexanediol co~bined with ~bout 36% by weight poly(tetr~ethylene ether) glyc~l h~ving a number a~erage ~olecular weight of 2000 (Lo~od~, General Electric Co~pany, Mount Vernon, Indiana; ~elting Point circ~ 160 C and an acid endgroup number Or ~ro~ 20 to 303. The esteri~icatisn i~ by melt extrusion following the general procedure o~ Exa~ple 1, U.S.
Patent 3,763,lOg in the presence o~ 5 part o~ ~n . . .

7 ~ ~

impact-modifier (~raton D-1102, Shell Chemical Company).
The resulting copolyDer blend was tested to determine properties of heat distortion temperature (~DT), notch~d Izod (NI), dynatup impact (Dyn), tensile yield (Ty), tensil~ ~longation and break (TE), flexural ~odulus tF~), melt vi~co~ity and the particle . ~iz~ of th~ polyphenylene e~her disper6ed in the - polye3ter matrix (PPE size). The test results are set ~ 10 ~orth in the ~kl~_~, below.
~1~
The general procedure~of Exa~ple 1, ~upra., i5 repeated except that ~he polyester reactant as u~ed therein wa~ replaced with an equal proportion o~
Hytrel 4056 tE.I. DuPont de Nemours and Company). The Hytrel resins are b~lieved to be linear copolyesters which consi~t of hard block~ m~de from the esterific-ation of a mixture of dimethyl terephthalate with dimethyl isophthalate and butanediol and soft blocks of polytl,4-butanediol), using the general method o~
: U.S. Patent 3,763,109. The copolye~ter ha~ a melting point of circa 148 C ~nd an ~cid ~nd group number of from 20 to 35. The test res~lt~ are ~et forth in the Tabl~ ~, below.
For purpos~ o~ co~pari~ion, copnlym~rs were prepared a~ de~ribed above, except that ~he carboxy-terminated, ~egmented, linear c:opolye~ter component ~providing chain unit~ o~ the ormula (I) ~escribed above] was r~placed with ~ br~nchQd copoly(etherimide) 30 ester component providing chain unit~ of the for~ula:
' 7 3 ~
scNo8534 3~
.;
O O
Il a ~ 5 r 1l 3~C~ ~C~
-- O -- C-- R N -- G -- N R4 -- C - _ .: . _ \ C/ \C/ - .
Il 11 : O O
(~I) ; wherein G i~ as defined abova and each R3 and R~ i~
indep~ndently ~elected ~ro~ hydrogen or ~ ~onovale~t organic radical pre~erabl~sele~ted fro~ tha group ~onæisti~g of C1 to C6 aliphatic and eycloaliphatic radical~ ~nd C~ to C12 ~romatic radical~, e.g. benzyl, '~ mo~t pre~erably hydrogen;
carboxy group end-terminat~d branched copolyeæter having chain units of the for~ulae (II) ~nd (XI) a~
described ~bov~ ~re al50 generally well ~nown as ar~
methods of their preparation; ~ee for example the ~escrlption giv~n in the ~.~. Patent 4,556,705 which i~ inco~porated hQr~in by referenc~ th~reto.
~A~LE 3 (Comp~r~tive ~ L
The gener~l procedure o~ Example l i~ repeated, ~: 25 ~xcept that the linear copolyester u~ed ther~in was replac~d wi~h an equal proportion of a branched - copolye~ter such a~ one de~cribe~ in U.S. Pat~nt ~,556,705, or example one con~sting of h~rd block~
mad~ ~ro~ the polyester~fication of dim~thyl terephthalate with but~nediol co~bined wi~h ~oft segm~nts o~ an am~ne endcapped polypropylene glycol ~ which has been i~idized with tri~llitic a id. The ;~ imide acid ~o~t block i~ the reaction product o~:
Je~a~in~ D-2000, (a polypropylene ether di~mine, 2verage molecular w~ght 2000, Texaco Chemical Co.

.

. . :
" ~
! :

.

2u~ ~33 with tri~ellitic ~nhydride. a 2.08 mol ratio of trimellitic anhydride to Jeffamine D-2000 gives a branched resin with melt viscosities in the 1,000-2000 poise ran~e ~Test Method AST~ D-1238: 0.042 inch dia~eter, L/D 1~/1 orifice; 250 C, 21.6 kg). The ratio o~ hard blocks to o~t block~ iB about 1:1. The bran~hed copolyest~r has an ~.P. o~ ~irca 200 C and an ~cid end group numb~r of from 25 to 40. ~he te~t re~ults are ~hown in the Ta~le 3, below.
EXA~P~B ~ (Comparative~
The general procedure of Example 3 was repeated axcept that the copolye~ as used ~herein was replaced with an equal proportion of an ~nalog copolyester haYing a hard block to ~oft block ratio of about 1.6:1 (weight ratio).
The test result~ are ~et ~orth in Table 3, below.

2~273~

.~ 1 t ~~
~ ~ _ .
.'', ~
. ~

E~ ~ ~ N ~ 2 ~ ~

--~I u~ N

~ . .

~ U~ ~ ¢ O_ N ~ V ~ æ ~ u "~ ~ O ~ O
., ~ ~ ~
.

.
, ~ :

. :

2~273~

, 38 As ~een in the data, there i~ ~ dramatic differenca in the blends with the linear polymers when compared to the branched re3in. It i8 i~portant to note that all o~ the copolye6ters used had ~id end group nu~bers in th~ 20 to 35 range, ~o that ~he materials all hav~ ~q~al r~activity to the epoxy functionalized polyphenylena ether.

:

., , ,, , ~' , :

,i .

'i, .

Claims (24)

1. The copolymer of an epoxy-functionalized polyphenylene ether and a carboxy-terminated, segmented, linear copolyester having recurring intralinear long chain ester units of formula:

(I) wherein G represents a divalent organic moiety remaining after removal of terminal hydroxy groups from a poly (alkylene ether) glycol; and R
represents a divalent organic moiety remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than 300;
interrupted by short chain ester chain units of the formula:- (II) wherein R has the meaning previously ascribed to it and D represents a divalent organic moiety remaining after removal of terminal hydroxyl groups from a diol having a molecular weight of less than 250.

2. A copolymer according to claim 1 wherein the epoxy-functionalized polyphenylene ether has end groups of the formula:- (III) wherein each Q' 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 the monovalent moiety of formula:- (IV), and R1 is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical.

3. A copolymer according to claim 1 wherein the polyphenylene ether comprises a plurality of structural units having the formula:- 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.

4. A copolymer according to claim 3 wherein R
is p- or m-phenylene or a mixture thereof.

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

6. A copolymer according to claim 5 wherein D
is methylene and R is p-phenylene.

7. A copolymer according to claim 6 wherein D
is ethylene.

8. A copolymer according to claim 6 wherein D
is tetramethylene.

9. A copolymer according to claim 6 wherein G
is polyoxytetramethylene.

10. A copolymer according to claim 6 in admixture with an impact modifier.

11. A composition according to claim 10 wherein the impact modifier is a triblock copolymer wherein the end blocks are derived from styrene and the midblock is derived from at least one of isoprene and butadiene.

12. A composition according to claim 11 wherein the midblock has been hydrogenated.

13. A molding composition, which comprises;
polyphenylene ether-copolyester copolymer molecules containing at least one polyphenylene ether-copolyester linkage of the formula:- 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 scondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q1;
R1 is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical;
Zl is an alkyl, cycloalkyl or aromatic radical, or ;

Z2 is OH and Z3 is , or Z2 is and Z3 is OH;
said linking being interrupted by recurring intralinear long chain ester units of the formula:- (I) wherein G represents a divalent organic moiety remaining after removal of terminal hydroxy groups from a poly(alkylene ether) glycol; and R represents a divalent organic moiety remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than 300;
interrupted by short chain ester chain units of the formula:- (II) wherein R has the meaining previously ascribed to it and D represents a divalent organic moiety remaining after removal of terminal hydroxyl groups from a diol having a molecular weight of less than 250.

14. A composition according to claim 13 wherein D
is a lower alkylene radical.

15. A composition according to claim 14 wherein the polyphenylene ether is a poly(2,6-dimethyl-1,4-phenylene ether).

16. A composition according to claim 15 wherein D
is ethylene.

17. A composition according to claim 16 wherein D
is methylene and R is p-phenylene.

18. A composition according to claim 17 wherein Zl is a lower alkyl or aromatic hydrocarbon radical.

19. A composition according to claim 18 wherein Z1 is methyl, n-butyl or 2,4,6-trimethylphenyl.

20. A composition according to claim 17 wherein Z1 is .

21. A copolymer havinq repeating or recurring chain units of the formula:- 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;
said units being interrupted by recurring intralinear long chain ester units of the formula:- (I) wherein G represents a divalent organic moiety remaining after removal of terminal hydroxy groups from a poly(alkylene ether) glycol; and R represents a divalent organic moiety remaininq after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than 300;
interrupted by short chain ester chain units of the formula:- (II) wherein R has the meaning previously ascribed to it and D represents a divalent organic moiety remaining after removal of tenminal hydroxyl groups from a diol having a molecular weight of less than 250.

22. A molding composition which is the reaction product of an epoxy-functionalized polyphenylene ether and an equivalent excess of a carboxy-terminated, segmented, linear copolyester having recurring intralinear long chain ester units of formula:

(I) wherein G represents a divalent organic moiety renaining after removal of terminal hydroxy groups from a poly (alkylene ether) glycol; and R represents a divalent organic moiety remaining after removal of carboxyl groups from a dicarboxylic acid having molecular weight of less than 300;
interrupted by short chain ester chain units of the formula:- (II) wherein R has the meaning previously ascribed to it and D represents a divalent organic moiety remaining after removal of terminal hydroxyl groups from a diol having a molecular weight of less than 250.

23. The composition of claim 22 which further comprises an additive selected from the group consisting of impact modifiers, fillers, flame retardants, pigments, dyes, thermal stabilizers, anti-static agents, anti-oxidants, UV-stabilizers, lubricants, viscosity modifiers, crystallization aids and mold release agents.

24. The invention as defined in any of the preceding claims including any further features of novelty disclosed.