CA2049297A1 - Thermoplastic copolyetherimide ester elastomer-acrylate rubber compositions - Google Patents

Abstract

2049297 9110708 PCTABS00006 Thermoplastic elastomer compositions are disclosed which comprise a thermoplastic copolyetherimide ester blended with a crosslinkable alkylacrylate rubber component. The rubber is subject to crosslinking during melt mixing resulting in a thermoplastic processable material.

Description

WO 91/107l~X PCI`/US91/00'l30 2v~29~

THERMOPLASTIC COPOLYET~ERIMIDE ESTER ~ -EI,ASTOMER-ACJ~Y~ATE RlJBBE}:t COMPOS TTION5 CROSS REFERENCE TO RELATEI:~ APPI.ICATI0N -.
The present application is a continuation-in-part of copending United States Patent Application Serial No.
07/467,677, filed January 19, 1990.
FIELD OF THE INVENTIt:~N :
The present invention relates to blends of a copolyetherimide ester elastomer and a rubbery ~rosslinkable alkylacrylate elastomer.
BACXGROUND OF THF INVENTION
: ':
Thermoplastic elastomers of ~he type known as . .
polyetherimide esters provide a variety of uniyue and excellen~ properties and are particularly useful in extru~ion and molding applications.
Polyetherim~de esters prepared from diols, dicarboxylic aclds and polyoxyalkylene dlimide dlacids are thermoplastic e}astomer~ havlng an excellent comb~nation of - stress-s~rain propertles, low tensile ~et, high melting temperaturec and excellent strength, toughne~s and flexibility properties~ All of the~e proper~les are variou-~ly useful in many elasto~er applications. Copoiyetherimide ester elastomers also process well, due to their rapid crystallization rate and excellent moldability characteristics. Elastomer~ with the low flexural modulus of polyetherimide ester~ in combina~ion with any of the afor~mentioned advantageous propertie3 have gained wide acceptance in the field of elastomers.
Nonetheless, it has now b~en found that polyetherimide esters can ~e improved or enhanced for certain application~, especially with re~pect to improving the "softne~s~ (lower durometer) of the el~s~omer, while retaining satisfactory tensile properties. The improvements are aecomplished by blendlng a rubbery ~ro~linkable alkylacrylate elastomer wi~h the polyetherimide ester and dynamically cros~linking ~he former.
Wor~ has been patented ~n which a rubber is mixed ~, :~ ' . . ., . .,. ,, . ,-~ . ,;, : .. . ..

wo 91/10708 2 ~ '~ 9 ~. ~ 7 PCT/US91/00430 with a ~hermoplastic re~in and su~equently cro~slinked while the ingredients are bein~ mixed. Thls is known in the art as "dynamic curing" or "dynamic vulcanization". Ge~sler et al., United States Patent No. 3,037,954 demons~rated "dynamic S curing~ of a butyl rubber/polypropylene blend. Fischex, Unlted States Patent No. 3,758,643, partially cu:red EPDM rubber in the presence of a polyolefin. Other polyolefin/rubber vulcanizates in which the rubber is polybutadiene, natural rubber, isoprene and EPDM are disclo~ed in United States Patent Nos. 4,104,210; 4,130,535; a~d 4,311,628. In United States Patent No. 4,594,390, a continuous proce~s ~or preparing EPDM/polypropylene dynamic vulcanizates is reported.
The Monsanto Co~pany commercially produces an EPDM/polypropylene dynamic vulcanizate under the rade name "SANTOPRENE", and a nitrile rubb~r/polyole~in dynamic -: .
vulcanizate ~n~er the trad~ nam~ "GEOLAS~". Further, United States Patent No. 4,801,647 disclo~e~ an EPDM/crystalline polyolefin dynamic vulcanizato.
Dyna~lc vulcanization has also been disclosed employing copolye~ters. Europ~ n patent, ~P O 293 821 A2, discloses a ~ultiblock copolye~tar melt mLxed with polychloroprene rubb~r wh~ch i~ then cro~311nked during mixing. In Unlted State~ P~tent No. 4,739,012, a segmented thermoplastic copolyQstar is bl~nd~d with a ~cond composition 2S which is`a blond of two partially cros~link~d polymers, such as PVC or PVDC and a copolymer of ethylen~ and one or more ethylenically unsaturated co~onom~r3 prepared by dynamic vulcanlzatlon.
Acryllc rubber~ are al30 ~nown to bQ employed in thermoplastic dynamic vulcanizat~ Coran ot al., Ru~ber Chem.
and Tech., 55, 116 (1982), disclo~e a m~trlx of polymers and rubhers u~ed in the prep~ration of dyna~ic vulcanizate compo it$on~ in which polyacrylate ru~ber w~ us~; however, not with copolyetherlmide e~ters. Wolf~, Unlted 5tates Patent :
~5 No. 4,782,110 di3close~ dyn~mlcally vulcanizing ethyle~e-al~ylacrylate copolymer r~bber~ wl~h crystalline polyolefln3.

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wosl/l0708 2 0 d 9 2 ~ 7 PCT/US91/~

Coran et al., United States Patent No.
4,3~7,199, disclose employing an ethylene-acrylic type copolymer rubber containing free carboxylic moieties in blends with polyesters such as PBT. A metal oxide is used as a source of metal ions to neutralize the pendant acid groups, forming an ionomeric network structure as distinguished from eo~alent bond formation. In Coran et al., United States Patent Nos.
4,310,638 and 4,473,683 the ethylene ac:rylic copolymer is blended with a nylon resin and a metal oxide; and amorphous styrene ~ased resins and a metal oxide, re~pectively.
~ lso to be mentioned are United States Patent Nos. 4,116,914 (ethylene vinyl acetate rubber dynamical1y vulcaniz~d with polyolefins); 4,480,074 (two step process for dynamically vulcanizing an EPDM/PP vulcanizate with additional EPDM); 4,226,953 (nitrile rubber dynamically vulcanized with styrene-acrylonitrile re~ins); 4,207,407 ~chlorinated polye~hylene dynamically vulcanized with nylon resins);
4,287,324 (ep ,nlorohydrin rubber dynamically vulcanized with polye~ter~ such a~ P3T); and 4,593,062 (mixture of halogenated butyl rubber and polychloroprene dynamically vulcanized with polyolefins such a~ PP and PE). Special mention is made of EP0 327 010 A2, ~EP '010") which d~scloses blends of polyether ester copoly~er with polyacrylate elastomers.
None of these howe~er di close a polyacrylate rubber which ha3 been dynamically vulcanized with a thermopla~tic copolyethorimide e~ter. It has now been discovered and is shown in the examples hereinafter that dynamically vulcanizlng a polyacrylate rubber with a ther~opl~tlc copolyetherimide est~r provides an elastomer compo~ition with improved softness whlle retaining excellent tensile prop~rties. This is unexp~ctad because the copolyether e~ters employed in EP '010 suffer from the loss of tens1le properties to a much greater extent when mixed with cros~}lnkable polyacryla~e rubbers and dynam1cally vuleanized.

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. ' ' .

WO 91/10708 ~ 2 ~ ~ PCT/U891/00430 SUMMARY OF THE INVENTION
According to the pre~ent invention, there is provided a ~hermoplastic elastomer composition comprising:
(A) a poly~therimide ~ster copolymer;
(B) a crosslinkable rubbery alkylacrylate, and (C) a crosslinklng agent.
The polyetherimide ester copolymer can comprlse the reaction product o~ (a) one or more low molecular weight diols; (b) one or more dicarboxylic acids; and (c) one or more polyoxyalkylene diimide diaclds. Preferably the dlol component (a) comprises from about 60 to about 100 mole p~rcent 1,4-butanediol, th~ dicarboxylic acid component (b) comprises from abou~ 60 to about 100 m~le percent dimethyl terephthalate, and the polyoxyalkylene diimide diacid component (c) is derived from tr~mellitic anhydride and a polyoxyalkyl diamlne selec~ed from the group con~lsting of polypropylene oxide dlamln0 and a copoly(ethylena oxlde-propylene oxlde ) diamine h~ving pr~dominantly polyethylene oxlde ln the backbone.
The pre~erred rubbery al~yl acrylate i9 based on repeating u~its co~prising the ~ormula:

(CH2-CH) ; :
C-O
1 :
OC2~5 The pre~erred cros~linklng a~ent i~ sodlum stQarate. Also contemplated are thermopla~tic elastoMer compo~l~ions further comprising a f~ller such as a s~llca and a plasticizer. The preferred compositions comprise component (A) ln an amount : ranging from about 20 to about 99 par~s by weight and : component (B) in an amoun~ ranging f rom abou~ 80 to abou~ l part by welgh~ based upon 100 parts by weigh of (A) and (B) together. ~ :
Al~o according to th~ pr~ent invent~on, there is `~ provlded a proca~ for produc1ng a thermoplastlc elastomer .

~ Pcr/ussl/ooq30 -

2~2~7 -5- :
composition somprising:
(Il mixing (i) a polyetherimide ester copolymer, and (ii) a crosslinXable rubbery alkylacrylate; and (II) curing the mixture obtained in step (I) by addiny a crosslinXing agent.
Preferably, step (II) of the procsss further comprises adding an accelerator such as sulfur, sulfur donors, magnesium oxide, tertiary amines and mixtures of any cf the foregoing. Most preferred are quaternary ammonium compounds.

DETAILED DESCRIPTION OF THE INVENTION
The polyetherimide esters useful in the practice of the present invention may be prepared from one 01- more dlols, one or more dicarboxylic acids and one or more high molecular weight polyoxyalkylene dlimide diac~ds.
They are generally comprised of recurring polyether imide ester 3tructural units having the general formula:
O O
t ~ / N- G -N R - C-O-R2~0 Jx ;
,t il O O

wherein G i3 a divalent radical remaining a~er removal of the amlno ~roups o~ a h~gh molecular we~ght polyalkylene ether diamine; R i~ a trlvalent organic ra~ical; R2 is the divalent radical r~m~ining ater the removal of the hydroxyl grou~s of a diol; and x is a whole number having a value of from 2 to about 40.
Pr~paration of such ma~eriAl~ is described in dotail in U.S. Paten~ No. 4,556,705 of R.J. McCready, issued Deca~ber 3, 1985 and hereby incorporated by reference.
The poly(etherimide e~ er3) u~ed herein may be prep red by ~onv~ntional proces~e~, ~uch ~ e~terifica~lon and con~nsation re~ctions far the prs~uction of poly~t;ers, to '` ~
.~.

WO 91/10708 2 0 4 9 ~ ~ 7 PCT/US91/00430 --6 ~
provide random or block copolymers. Thus, polyetherimide esters may be generally characterized as the reaction produc~
of the aforementioned diols and acids.
Preferred composition~ encompas~ed by the present lnvention may be prepared from (a) one orrnore C2-C ; aliphatic or cycloaliphatic diols, (b) one or more C4-C,6 aliphatic, cycloaliphatic or aromatic dicarboxylic acids o-- ester derivatives thereof and (c~ one or more polyoxyalkylene diimide diacids. The amount of polyoxyalkylene diimide diacid employed is generally dependent upon the deGiired properties of the resultant polyetherimide ester. In general, the weight ratio of polyoxyalkylene dilmide diacld (c~ to dicarboxylic acid ~b) is from about 0.25 to 2.0, preferably from about 0.4 to about 1.4.
Suitable diols (a) for u~a in preparing the compo~itions of the present inYention include saturated and un~aturated aliphatic and cycloaliph~tlc dih~droxy compound~
as w~ll as aromat~c dihydroxy compound~ . These d~ ols are prefer~bly of a low molecular weight, i.e. having a molecular welght of about 250 or le~. When u~d herei~, the term "d~ols" and "low molecular welght dlols" Yhould be const~ued to include equivalent e8ter for~lng d~irlva~l~es thereof, provi~ed, however, that the moLecul~r weight requirement pertains to the diol only and not to i~ derivatives.
~5 Exemplary of est~r ~orming der1v~tive3 the~e m~y be given the acstate~ of ~he dlol~ a well a~ for exampl~ ~thylene oxide or ethylene c~bon~te for ethylene glycol.
Pre~erred satur~ted and unsaturated al~phatic and cycloaliphatic dlol~ are tho~e havlng from 2 to 19 carbon atoms. Exemplary of these diols thursi m~y ba glven ethylene glycol; propane diol; butane dLol; pentan~ dlol; 2-methyl propane diol; 2, 2-di~ethyl propan~ diol; hexaine diol; decane diol; 2-octyl undecane diol; l, 2-, l, 3-, and 1, 4-~yclohexane dlmethanol; 1,2-, 1,3-, and 1,4-dlhydroxy cycloh~xane; but2ne dlol; and h~xene d~ol. E pecialiy pr~erred ar0 1,4-bu~ane diol and mixture~ thereo~- wil:h hex~ne dlol or bu~ene diol, mo~t p~Q~sr~bly l, 4-butanedio~l .

.

:' .. .~: ~

2 ~ 7 PCTtUS91/~30 _ 7 _ Aromatic diols suitable for use in the practice of the present invention are generally those having from 6 to a~out 19 carbon atoms. Included among the aromatic dihydroxy compounds are resorcinol; hydroquinone; 1,5-dihydroxy naphthalene; 4,4'-dihydroxy diphenyl bis(p-hydroxy phenyl)methane and 2,2-bis(p-hydroxy phenyl)propane.
Especially preferred diols are the saturated aliphatic diols, mixtures thereof and mixtures of a saturated diol~s) with an unsaturated diolts), wherein each diol contains from 2 to about 8 carbon atom~. Where more ~han one diol is employed, it is preferred that at least about 60 mole %, based on the total diol content, be the same diol) most preferably at least 80 mole %. As mentioned above, the preferred compositions are those in which 1,4-butanediol is present in a predominant amount, mo~t preferably when 1,4-butanediol is the only diol.
Dicarboxylic acidsl(b) which are suitable for use in the practice of the preqent ~nvent1on are aliphatic, cycloaliphatic, and/or aromatic dicarboxyllc acids. These aclds are preferably of a low molecular weight, i.e., having a molecular weight of less than about 300; however, higher molecular weigh~ dicarboxylic acids, especially dimer acids, which are fully de~cribed in K~r~-Othmer,Encyclo~edia of Chemical Technolo~y, 3rd Edition, vol. 7, John Wiley & Sons, N.Y., pp. 768-782, m~y also be used. The term "di-arboxylic aclds" as;used herein, includes equivalents of dicarboxylic acldsi hav~ng two functional carboxyl groups which perform subst~ntlally like dicarboxylic acids in reaction with glycols and dlols in forming polyester polymers. These equivalents include e~ters and ester-farmlng derivatives, such as acid halides and anhydrides. The molecular weigh preference, mentlo~ed abo , pertains to the acid and nc~ to its equivalent e ter or es~er-~orming deriva~lve.
; Al~phatic dicarboxyl~c aclds, a ~he term is used herein, re~ers to carboxylic acids havi~g two car~oxyl groups each of whlch is attached ~o a satu~ted carbon atom. If the carbon atom to whlch the carboxyl group is attached is WO 91/10708 2 9 4 9 2 9 7 PCT~US91/00430 saturated and is in a ring, the acid is cy~loaliphatic.
Aromatic dicarboxylic acids, as the term is used herein, are dicarboxylic acids having two carboxyl groups each of which is a~tached to a carbon atom in an isolated or fused benzene ring system. It ls no~ necessary that both earboxyl groups be attached to the sa~e aromatic ring and where more than one ring is present they can be joi.ned by aliphatic or aromatic divalent radicals such as -O- or -SO2-.
Representative aliphatic and cycloalipha~ic acids which can be used for this invention include se~acic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyolohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, gLutaric acid, succinic acid, oxalic acid, azelaic acid, diethylmalonic acid, allylmalonic ac~d, 4-cyclohexane-1,2-dicarboxylic acid, 2-e~hylsuberic acid, tatramethylsuccinic :
acid, cyclopentanedlcarboxylic acid, decahydro-1,5-naphthalene dlcarboxylic acid, 4,4'-bicyclohexyl dicarboxylic acid, decahydro-2,6-naphthalen~ dicarboxylic acid, 4,4-methylenebis(cyclohsxane carboxyllc acid), 3,4-furan dicarboxyl~c acid, and l,l-cy~lobutane dlc~rboxyl$c acid.
Preferred aliphatic acid~ are cyclohexane dicarboxylic acids, glutaric a~id, azelaic acid and adlplc ac~d.
R~presentative aromati~ dicarboxyl~c acid~ which can be u~ed include terephth~lic acid, isoph~halic acid, phthal~c acld, bi-benzoic acid, ~ub~tituted dicarboxy compounds wlth two benzene nuclei such a2 bis(p- :
ca~boxyphenyl)me~hane~ oxybi3~benzoic ~cld), ethylena 1,2-bis-(p-oxybenzolc acld), l,S-naphthylene dlca~oxyllc acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, phananthr~ne dic~rboxylic acid, anthracene dicarboxylic acid, 4,4'-sulfonyl dlbenzoic acid, and halo and C1-C,2 alkyl, alkoxy, and aryl ring substitution deri~tiv~ thereof.
Hydroxy acids such ~ p-(beta-hydroxy0thoxy~banzoic acid can al~o b~ u~ed provided an arcmatlc dicarboxy1ic acid is also .:
pre~ent. .-Preferred dicarboxylic ~cid~ for the prep~ration ~. .
of the polyetherimlde e3ters of the pre~e~t lnvention ase the . . .

WO9l/10708 2 0 ~ 3 ~ ~ 7 P~TtUS9l/~30 _g_ aromatic dicarboxylic acids, mixtures thereof and mixtures of one or more dicarboxylic acids with an allphatic or cycloaliphatic dicarboxylic acid, mos~ preferably the aromatlc dicarboxylic acids. Among the aromatic acLds, those with 8-16 S carbon atoms are preferred, partic~].arly the benzene dicarboxylic acids, i.e., phthalic, terephthalic and isophthalic acids and their dimethyl derivatives. Especially preferred is dimethyl terephthalate.
Finally, where mixtures of dicarboxylic acids are employed in the practice of the present inven~ion, it is preferred that at least about 60 mole %, preferably at least about 80 mole %, based on 100 mole ~ of dicarboxylic acid (b) be of the same dicarboxylic acid or ester derivative thereof.
A5 mentioned above, the preferred compositions are those in lS which dimethyl terephthalate is the predominant dicarboxylic a~id, most preferably when dimethyl terephthalate is the only dicarboxylic acid.
Polyoxyalkylene dlimide dlacids (c) suitable for u~e h~reln are high molecular weight diim1de diacids wherein the average molecular weight i~ greater than about 700, most preferably greater than about gO0. They may be prep~red by the imidization reaction of one or more tricarboxyllc acid compounds containing two vicinal carboxyl groups or an anhydrlde group and an additional carboxyl group which must be es~erifiable and preferably is nonimidizable with a high molecular weight polyox~alkylene diamine. The polyoxyalkylene diimide diacid~ and proces3es for their preparatisn are more fully dt~closed in McCready, European Patent No. 180,149, published May 7, 1986, and entltled "~lgh Molecular Weight Dilmide-Diacid Compounds Ucieful in the Preparation of Polyether Imide E~ter(s) and Amide~s)~, incorporated herein ~y ~ :
reference.

WO 91~10708 ~ 7 PCT/US91/00430 -la-.
In general, the polyoxyalkylene dlimide diacids useful herein may be characterized by the following formula:
' .

O O
~C~ ~C~ ;
}~ ' OOC R N-G-N R-COOR ' C \ C

O Q :.

wherein each R is independently a ~rivalen~ organic radical, preferably a C2 to C20 aliphatic~ aro~ati~ or.cycloa;Liphatic trivalent organic radical; each R' is lndapandently hydrogen or a monovalent organic radical pre~erably s~lected ~rom the group con~lsting of Cl to C6 aliphatic and cycloaliphatic radicalq and C6 to C12 aromatlc radlcals, e.g. phenyl, mo~t p~eferably hydrogen; and G is the r~dic~l re~ining aft~r the r~moval of tho terminal (or as nearly teEmlnal as po~sible) hydroxy groups of a long chaln ether glyco~ having an average :.
molecular weigh~ of ~rom about 600 to about 12000, prefer~bly from abou~ 900 to abou~ 4000, and a carbon-to-oxygan ratlo of about l.8 to about 4.3. .
Represen~a~ive long chAin ether glycols from which the polyoxyal~ylsne diam~n~ i~ prep~red include poly(ethylene ether)glycol; poly(propylene e~her) glycol;
poly(tetramethylene ether)glycol; rando~ o~ block copolymers of ethylene oxide and propylene ox~do, lncludlng propylene oxide termlnated poly(ethylene ether)glycol; and random or : ~0 block copolymer~ of tetrahydrofuran wlth ~inor amoun~ of a . --second monomer such as methyl tetrahydrofuran (u~ed in propor~ion such that the carbon-to-oxyg~n mol~ ratio in ~he glycol does not ~x~eed a~out 4.3)~ Especially preferred poly(alkylene ether)qlycols are poly(propylene ether)glycol : .-35 and poly(ethylene ether)glycoLs en~ c~pped with paly(propylene ether)~lycol or propylene oxide.
In general, the polyoxyalkyl~C~C6~ne dla~ne . "' .

wo 91/10708 2 3 4 ;~ 2 ~ 7 PC~/US91/00430 useful within the scope of the present inventlon will have an average molecular weight of from about 600 to 12000, pre~erabiy from about 900 to 4000. These may be characterized by the following general formula:

wherein G is the radical remaining after the removal of the amino groups of a lony chain alkylene et:her diamine. These polyether diprimary diamines are availab.le commercially from Texaco Chemical Company under the trademl3rk "JEFFAMINE". In general they are prepared by known procesC~es for the amination of glycols. For example, they may be prepared by aminating the glycol in the presence of ammonia, Raney nlckel catalyst t and hydrogen as set forth in Be~ium Patent No. 634,741.
Alternatively, they may be prepared by treating the glycol 1~ with a~monia and hydrogen over a nlckel-copper-chromium catalyst as taught by United Statec Patent No. 3,654,370.
Oth~r method~ for the productlon thereof lnclude those taught in Unlt~d Stat9~ patQnt No~. 3,155,728 and 3,236,~95 and French Patent No~. 1,551,605 and 1,446,708. A11 of the foregoing patent~ ar~ incorpor~ted her~in by reference.
Th~ tricar~oxylic co~ponent mAy be almost any car~oxylic acid anhydr~de conta~ning an additional carboxylic group or the corra~ponding acid ~h~reof containing ~wo imide-forming vicinal car~oxyl groups ln Lieu of the anhydride . -.
group. Mlxture~ thereof are al~o suita~le. The addi~ional carboxylic groùp must be esterlfiable and pr~ferably is sub~tantlally nonlmidlzable.
~he tricarboxylic acid material~ can be characterazed by the followlng formula:
O
Il /C\ ~ .
R ' OOC-R 0 ~ \ C / .
Iï .
O
where R i3 a triv~len~ oryanic radical, prefarably a C2 to C~0 aliphatlc, aro~'c~c, or cycloaliphatic trlvAlent organic Wo 91/10708 2 ~ 4 ~ PCT/US91/0043 radical and R' is preferably hydrogen or a monovalent organic radical prefexably selected from the group consisting of C to C6 aliphatic or cyc)oaliphatic radicals and C6 to C12 aromatic radicals, e.g. phenyl; most preferably hydrogen. A preferred tricarboxylic component is trimellitic anhydrlde.
~ riefly, these polyoxyalkylene diimide dlacids may be prepared by known imidiz~ation react1ons including melt synthesis or by synthesizing in a solvent system. Such reactions will generally occur at temperatures of from 100 degrees C to 300 degrees C, preferably at fro~ about 150 degrees C to about 250 degrees C while drawing off water or in a solvent system at the reflux te~perature of the solvent or azeetropic ~solvent) mixture.
Although the weight ratlo of the above in~redients is not crit1cal, it is preferred that the diol be present in at lea~ a molar equivalent amount, preferably a molar exc~Ys, most preferably at lea~t 150 mole % b~ed on the mole~ of dicarboxylic acid (b) and polyoxyalkylene diimide diacld (c) comblned. Such molar exce3~ of diol will allow for optim~l yLeld~, based on the amount of acld~, while accounting for the los~ of diol during e3~eri~icatlon~0ndensation.
Further, while the welght ratio of dicaEboxylic acid (b) to polyoxy~lkylenQ dlimide di~cid (c~ i~ not critical to form the polye~herimide e~ters used in the present invention, preferred compesitions are tho~e in which the weight ratio of the polyoxyalkylene diimide dlac~d (c) to dlcarboxylic acld (b) is ~ro~ about 0.25 to about 2, pre~erably from about 0.4 to about 1.4. ~he actual weight r2tio e~ployed will be dependent upon the specific polyoxyalkylene diimide diacld used and more importantly, the desired physical and chemic~l propertie~ o~ the resultant polyetherimide e ter. In general, the low~r the ratio of polyoxyalkylene diimlde diester to d~car~oxylic acid the better strength, crystallization and he2~ dlstortion propertie~ o~ the polymer. Alternatively, the higher the r~tio, the bet~er the ~lexibllity, ten~ile se~ and low temperature lmpact ~hAracteristicS.

, . ,:

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

wosl/10708 2 ~ PCT/US91/~30 In preferred embodiments, the poly~therimide ester product will comprise the reaction product of dimethyl terephthalaset most preferably, with up to 40 mole % of another dicarboxylic acid; 1,4-butanediol, optionally with up 5 to 40 mole % of another saturated or unsaturated aliphatic or cycloaliphatic dioli and a polyoxyalkylE!ne diimide dihcid prepared from a polyoxyalkylene diimine of ~olecular wei~ht of from about 600 to about 12000, preferably from about 900 to ~:
4000, and trimellitic anhydride. In its most preferred embodiments, the diol will be 100 mole ~ 1,4-butanediol and the dicarboxylic acid 100 mole ~ dimethyl terephthalate.
The polyetherimide esters described herein may be prepared by conventional esterification/condensation reac~ions for the production of polyes~ers. Exemplary of the proce~ses that may be practiced are as set forth in, for examp~e, U.S.
Pat. Nos. 3,023,192, 3,763,109, 3,651,014, 3,663,653 and

3,801,547, herein incorporated by reference. Additionally, the~e compositions may be prepared by such processe~ and other known proces~es to effect random copclymers, block copolymers or hybrids thereof wherein bo~h random and block unit~ are present.
It is customary and preferred to utilize a catalyst in the process for the prsduction of the polyetherimide esters of the present invention~ In general, any of the known e~ter-interchange and polycondenc~tion cataly~ts may be used. Although two sep~rate catalya~s or cataly~t sy~tem~ may bo used, one for e3ter interchange and one for polycon~ensatlon, it ls preferred, where appropriate, to u~e one catalyst or catalyst system for both. In those in~tances where two separate catalysts are used, it is preferred and advantageous to render the ester-interchange ~atalyst inaffective followin~ the completion of the precondensation reaction ~y means of known catalyst inhibitors or quenchers, in particular, phosphorus compounds such as phosphoric acid, phosphenic acit, phosphonic acld and the a}kyl or aryl e~ers of salts thereof, in order ~o increase the thermal stability of the resultant polymer.
, ," "
~ .

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, ."; ',." ., ' ', , ;.' `', ' :" ,.' ' ". ' ~ . ".' '. . , ' " ' ' " ' ~ ' '" . '' . ' ., ' " .'' , ' ' WO 91/10708 2~ 9 7 PC~/US91/00430 Exemplary of the suitable known catalysts th~re may be given the acetates, carboxylates, hydroxides, oxides, alcoholates or organic complex compounds of zinc, manganese, antimony, cobalt, lead, calcium and the alkall metals insofar as these compounds are soluble in the reaction mixture.
Specific examples include, zinc acetate, c~Lcium acetate and combinations thereof with antimony tri-oxide and the like. ~-:
These catalysts as well as additional useful catalysts are described in U.S. Pat. Nos. 2,465,319; 2,534,023; 2,850,483;
2,892,871; 2,937,160; 2,998,412; 3,047,539; 3,110,693 and 3,385,830, among others, incorporated herein by re~erenc~. -.
Where the reactants and reactions allow, it is prefer.red to us~ the titanium catalysts including th~ inorganlc and organic titanium containing catalysts, such a tho~e descrlbed in, for lS example, U.S. Pat. Nos. 2,720,502; 2,727,8~1; 2,729,619;
2,822,34a; 2,906,737; 3,047,515; 3,056,817, 3,056,818; and ...
3,075,952 among others, incorporated herein by reference.
Especlally preferred are tha organic tltanate~ such as tetra-butyl titana~e, tetra-i~opropyl tltanata and tetra-octyl tltanate and the co~plex titan8t~3 derlvod rom alkali or alkaline earth metal alkoxides and titan~te esters, most preferably the organlc titan~tss. Thcse too may be used alone or in combin~tion wi~h other cat~ly~t~ such a3 for example, zinc acetate, mangano~e acetate or antimony rioxide, and/or with a ca~alyst quencher a~ d~scribed abov~.
Although the~e polyetherimide esters pos~e~s many de~l~abl~ propertie , it i5 often preferred to stabllize the compoRitlon~ tO h~at, oxldatlon, radiation by W light and the like, a8 de~cribed in the afore~ntioned U.S. Patent No.

4,556,705.
: The polyacrylate ela8~0m~r~ or rubbery a}kylacxylates are generally copolymer~ h~ving two major components: the b~ckbone, compri~ing from about 95 to about 99 ..
welght percent of tha polymer; and t~e react1ve cure site, compri3in~ fro~ abou~ 1 to abou~ 5 weight percent of the :poLymer. Preferably the copolym~rs have h~gh ~olecular weights, typ~cally arcund 100,000 MY (Yi~cos~ty average : , ' Wo 91/10708 2B4~ 7 PC~/US91/00430 molecular weight). The backbones are made from mo~omeric acid esters to form repeating units of primarily two types:

(CH2-CH) or (CH~-CHi C=~ C=0 O-CnH2n+l O-cnH2noc~H2tn+l where n is 2 or 4 and m is 1 or 2. The most common cure site monomers ar~ described in the below referenced Starmer et al.
ar~icle. Especially preferred are 2-chloroethyl vinyl ether and allyl gly~idyl ether. Physically, polyacrylate elastomexs are inherently sof and tacky. ~hey commonly have relatively low Mooney viscosities ~ML-1+4 @ 100 C) in the 2S to 60 ~ -ranqe. These elastomers are more fully de cribed in P.H.
Starmer and F.R. ~olf, Encyclopedia of Polymer Sci~nce and Engineering, 2d Ed., 306-325 (1985), incorporated herein by reference.
The mixing o~ the polyeth~rim~de e~ters and polyacrylate elastomer~ may be carried out ln any device known to those skilled in the art. Prefe~bly the components are melt mixed in a compoundlng device ~ueh a~ an internal mix~r : (Brabender or Banbury typ~) and extru~er~ ~twln screw or kneading). The polyetheri~ide ~ter~ and polyacrylate ~.
elasto~ers arQ typically combin~ble in proportlons ranging from ab~u~ 20 to about 99 parts by w~igh~ polyeth~rimide ester and ~ro~ about 80 to a~out 1 part by w~igh~ polya~rylate ela8tomer based upon lO0 parts by welght of the two reRins comblned. P~ferably, the polyetherimlde e~ter lS pres~nt in an amount xanginq from 20 to about 80 partS by weight, most pr~erably from abo~t 40 to about 60 p~r~s by wo~ght; and corre~pondingly the~polyacryla~e ela~tomer i9 pre~ent in an ~: amount~ranging fro~ about:80 to a~out 20 part~ by weight, most preferably f~om about 60 to abou~ 40 parts by weight. In another preferr~d e~bodiment the co~po~ltions of the present 35 ~ invention compri3e about 50~p r~ by welght polyetherimide ;~
e~ter and about 50 p~rts by we~gh~ poly~cryl~t~ elastomer.

., - .:

~ /107U~ 2 ~ ~ ~ 2 .3 ~ PCT/US91/~

The mixing compositions may also contain, Ln addition to resin and rubber, various additives known t.o those skilled in the art for use in compounding of thermoplastics, rubbers, and their blends, to modify the properties thereof, such as, - but not limited to fillers, stabilizers, antidegradents, processing aids, plastic:izers, pigments and the like. Typical fillers would include carbon blacks, silicas, clays, minerals or mixtures threof. Both low an~ high molecular weight plasticizers are contemplated.
In a typical composition, the thermoplastic copolyetherimide ester resin, rubber and additives are mixed in the appropriate device at a temperature high enough to soften and~or melt the materials such that an intimate mixture is obtained. Once an intimate mixture is obtained, the rubber material is cured by the add~tion of crosslinking agents, and optionally accelerators and heating, e.g., at from about 200 C to about 250 C, for from about 30 min. ~o about 30 sec., preferably from 5 min. to about 30 sec.
Crosslinking agents are any agents which promote vulcanization of the acrylic elastomer. The cure system employed varies with type of cure-site monomer present in the acrylic elastomer. Pref~rred crosslinkiny agents are soaps including metallic carboxylates such as sodium or potassium stearate. Optionally the cure system may also comprise an accelerator as well as a crosslin~ing agent. PreEerred accelerators include sulfur; sulfur donors such as tetrame~hylthiouram; or bases such as magnesium oxide or tertiary amines. Ammonium benzoate, ammonium adipate, and soap/quaternary amine systems are also known to be effective cure systems, as are red lead/ethylene ~hlourea and diamines and polyamines. ~ost preferred is a soap/quaternary ammonium system. These and others are more extensively discussed in the above-ref~renced Starmer et al. article.
Mixing ti~e is determined by ~he temperature and/or amounts of crosslinking agents added. The materials thus produced are processable by common thenmoplastic processing techniques, such as injection and oompression WO91/107~X 2 ~ 7 PCTlUSg~ 30 molding techniques and yield flexible, elastomeric parts.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples illustrate the present invention. They are not tO be construed to limit the claims in any manner whatsoever.
EXAMPLES ~ AND lA*
To a ~anbury mixer are added a crosslinXable polyacrylate elastomer comprisin~ alkyl halide vinyl ether cure sites ("H'--EMP" 4451CG, Zeon Chemical Co.), a polyetherimide esler resin ~"LO-MOD" J-1013, GE Plastics, Pittsfield, MA, MeCready, U.S. Patent No. 4,456,705), a hindered phenolic antioxidant stab~lizer ~ GANOX l0l0", CIBA-Geigy), a plasticizer ("PARAPLEX" G-62, C. P. Hall Co., Chicago, IL, U.S.A.), and a phosphite/thioes~er secondary stabilizer t"MARX" 5117, Argus Div., Witco Co., ~.Y., U.S.A.).
The mixture is mixed to form an intLmate blend. Once an intimate blend is obtained, a crosslinker (sodium stearate) and an acce}erator (quate~nary ammonium complex, "~PC-50", Zeon Chemical Co., Japan) are added. The m~xtu~e is then dynamically cured by mixing for 3 to 4 minutes a~ a temperature o~ 200 to 220 C. The composition is injection molded into test spe~imens and te~ted for tensile strength properties. For comparative purposes, a back-to-back sample is prepared, except that a copolyether ester resin simiLar to those described in EPO 0 327 0l0 A2 ("HYTREL" G-4078) is employed as the thermoplastic elastomerinstead of the polyetherimlde e~ter resin. The ~o~mulations used and the physical properties obtained are ~et forth in Table l.

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", WO 91/10708 2 a ~ ~ 2 ~ ~ PCT/US91/00430 1~

TABLE_ l ExamDle lA~ 1 In~redientstParts/wt) Polyetherimide ester resina _- 763.6 Polyether ester reslnb 76:3.6 --Polyacrylate elastomerC 763.6 763.6 Sodium stearate crosslinker 39.5 30.5 Quaternary ammonium acceleratord 15.3 . 15.3 Hindered phenol antioxidante 3.8 3. a Plasticizerf 7.6 7.6 Secondary antioxidant5 3.8 3.8 Processing aidh 7.6 7.6 Properties .
Tensile break strength, psi 889 1063 Elongation break, % 182 156 .
....................................... ..... ..... ........ ... ................ ... ... ..
_ _ _ _ _ a--''LOMODI~ J1013, GE Plastics, Pittsfield, MA 01201, U.S.A.
b--"HYTREL" G-4078, DuPont Company, Wilmington, DE, U.S.A.
c--"HYTE~P" 4451CG, Zeon Chemica} Co., Japan :
d--"NPC-50", Zeon Chemical Co., Japan ~ :
e--"IRGANOX"1010, CIB~-Geigy Co., Ardsley, NY, U.S.A. .
f--"PARAPLEX" G-62, C.P. HALL Co., Chicago, IL, U.S.A.
g--"MARX" 5117, Witco Chemical Co., N.Y. U.S.A. ~:
h--"STRUKTOL" ~S-280, Struktol Co., U.S.A.
The foregoing results demonstrate that a compocition prepared by dynamically vulcanizing a crosslinkab}e polyacrylate rubber with a thermoplastic copolyetherimlde ester resin unexpectedly provides better retention of tensile properties t-han a composition prepared by dynamically vulcanizing a polyacrylate rubber with a .
th~rmoplastic copolyether ester resin, as ~au~ht Ln the prior :~
art EPO 0 327 010.
This is especially surprising in light of the be~ter tensile.properties of the copolyether eqter alone when compared with the copolyetherimide ester alone, tensile . : : . . .. . , . ~ . ,: ..

WO91/1070h 2 ~ ~ v~ 2 ~ 7 PCT/US91/~30 breaking strengths being typically 2359 psi and 2159 psi, respectively, and elongations at break of 532 % and 215 %, respectively.
Thus, by employing a copolyetherimide ester as the thermoplastic resin dynamically vulcanized with a crosslinkable rubbery alkylacrylate there is observed a 49.2 percent retention in tensile break strength and a 72.6 percent retention in elongation at break, as compared to a 37.7 percent retention in tensile break strength and 34.2 percent retention in elongation at break with the copolyether ester of the prior art.

To a Brabender mixer are added 42.6 g of a polyacrylate elastomer (l00 phr), 28.4 g of a polyetherimide lS ester (66.7 phr) and 0.43 g (l phr) of an antioxidant ("IRGANOX" l0l0). The mixture is mlxed and heated at 220 C to form an intimate blend. Once an ~timate blend is obtained, 1.70 g (4 phr) of a crosslinker ~sodium 3tearate) and 0.85 (2 phr) of an accelerator ("NPC-50") are added. The mixture is dynamica~ly cured by mixing for 2 to 3 minutes at 220 C and the composition is compression molded into test specimens and tested ~or tensile strength properti~s according to ASTM
D-412. For comparative purposes, tests are run wLthout curing.
The results along with compositional data are set forth below in Table 2.

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wos1/1070x '~ 2 9 7 PCT/US9~ 30 It can be seen from. Table 2 above that dynamically curing the polyetherimide ester vastly improves the tensile break streng~h with a minimal decrease in .
elongation break. (Example 3 vs. 3A*). In the copolyetherimide ester examples, curing improved the tensile break strength.

EXAMPLES ~8 .
The procedure of Examples 2-4 is repeated except employing a Banbury mixer and various other addit~es and the concen~ration of a filler is variedO The compositions are then injection molded into ASTM D-412 Type } bars. The results along with compositional data are set forth in Table 3 below.

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wogl/10708 7.a49~7 PCT/US91/~30 EXAMPLES 9-l3 .
The procedure of Examples 5-8 is repeated except various other additives are employed and two different plasticizers are employed at two concentration levels (2.5 and 5.0 phr). The results are set forth in Table 4 below.

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WO9~10708 ~ 2 3 7 PCT/U~g~ 30 TABLE 4 (continued !
' = Polyacrylate elastomer (Zeon ChemicaLs Co., footnote a Table 2) = Polyetherimide ester (General Elec~ric Co., footnote b Table 23 A = Failed du~ing initial straining at 100 B = Failed during hold at 100% strain c = according to ASTM D395-B for 22 hours, avera~e values of four runs.

EXAMPLES_14-18 The procedure of Exa~ples 5-8 is repeated except various other additives are employed and the rubber/res in wei~ht ratio ~s varied at 20/80, 40/60, 50/50, 60/40 and 80/20. The re~ults along with compo81tlonal data are ~et forth below in Table 5.

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WO 91/10708 2 ~3 4 ~ ~ ~ 7 PCT/IJS91/00430 From the above Tables 1-5 it can be seen that the physical properties of a typical composition containing 60 parts by weight rubber and 40 parts by weight crystalline thermoplastic polyetherimide ester and a suitable additives package are: Tension Set (ASTM D412) typically 15 to 25 percent; Compression Set (ASTM D395 Method ~-plied sample) approximately 16 percent at 23 C/22 hours and 45 percent at 100 C/22 hours. Hardness values (Shor~ A durometer) of 55 to 80+ points can be achieved by suitable choice o~ components and additives.
The compositions of the present invention are placed under Dynamic Mechanical Thermal Analysis (DMTA) to produce DMTA curves. Typical thermoplastic materials, such as th~ thermoplastic elastomer~ u~ed herein, exhibit storage modulus versus temperature DMTA curves whLch can be described as posse~sing a glas3y plaiteau which ~g generally constant in magnitude, followed by a glass transition region which is characterized by a two to three order o~ magnituda drop in the storage modulus to the ~o-called rubb2ry plateau. The rubbery plateau-storage modulus va~ue is then u~ually ob~srved to decrease with increasing temperature in thermoplastics (i.e.
- viscous flow~. In semi-cry~alllne thermopla3tic~ the rubbery plateau is then followed by a large drop of~ at the crystallin~ melting point of the polymer.
In the compositions of the present invention, the drop o~f of modulus associated with the melting of the polyetherimide ester is observed to be followed by what may be termed a ~econd rubbery plateau which wa~ ~oundi to be of es~entially constant magnitude to the extent of the ~temperature tested ~250 C). The presence of this second rubbery plateau was ~ound ~o be dependent on ~he ratio of rubber to thermoplastic with compo~it$on~ having below 50 weight percen~ ~rubber not exh~bL~ing the ~econd rubbery plateau. In a thermoset rubber ma erial, the ~torage modulus would be essentially constant in the rubbery plateau region and would not drop of~ with ~increa~ing ta~perature (until . ~ . . , . , , . ~ . ~ , . . ..

WO Yl/1071J~ 2 ~ ~ ~ 7. 9 7 PCI/US91/0~430 degradation occurs), due to crosslinking of the ~ystem.
To test the thermoplasticity of the compositions a typical material which exhibits the second rubbery plateau was prepared, molded and then heated for 75 minutes at 200 C
in an air circulating oven. The material is then charged into a Brabender mixer and mixed ~o a molten state in which the consistency was observed to be constant as a function of time over a ten minute test period.
Thus, the materials are thermoplastics. If the materials were becoming thermoset above the melting point of the crystalline thermoplastic polyetherimide ester, they would have shear degraded when reprocessed as does a true thermoset material.
The above patents, pa~ent applications, publicatlons and test methods are hereby incorporated by reference.
Many variations of the present invention wLll suggest ~hemselves to those skilled in the art in light of the above~detailed descriptLon. For example, any copolyetherimide ester resin and cros~linkable alkylacrylate elastomer may be employed. Other suitable crosslinkers and accelerators are also contemplated. Additives such as flame re~ardants, light stabilizers and the like may be employed in the compositions of the present invention. All such obvious modifications are within the full in~ended scope of the appended clalms.

Claims (38)

CLAIMS:

1. A thermoplastic elastomer composition comprising:
(A) a polyetherimide ester copolymer;
(B) a crosslinkable rubbery alkylacrylate, and (C) a crosslinking agent.

2. A thermoplastic elastomer composition as defined in Claim 1 wherein said polyetherimide ester copolymer comprises the reaction product of (a) one or more low molecular weight diols; (b) one or more dicarboxylic acids;
and (c) one or more polyoxyalkylene diimide diacids.

3. A thermoplastic elastomer composition as defined in Claim 1 wherein said diol component (a) comprises from about 60 to about 100 mole percent 1,4-butanediol.

4. A thermoplastic elastomer composition as defined in Claim 2 wherein said dicarboxylic acid component (b) comprises from about 60 to about 100 mole percent dimethyl terephthalate.

5. A thermoplastic elastomer composition as defined in Claim 2 wherein said polyoxyalkylene diimide diacid component (c) is derived from one or more polyoxyalkylene diamines and one or more tricarboxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl group, and is characterized by the following formula:

wherein each R is independently selected from the group consisting of C2 to C20 aliphatic and cycloaliphatic trivalent organic radicals and C6 to C20 aromatic trivalent organic radicals; each R' is independently selected from the group consisting of hydrogen, C1 to C6 aliphatic and cycloaliphatic monovalent organic radicals and C6 to C12 aromatic monovalent organic radicals; and G is the radical remaining after removal of the hydroxy groups of a long chain ether glycol having an average molecular weight of from about 600 to 12000.

6. A thermoplastic elastomer composition as defined in Claim 5 wherein said polyoxyalkylene diimide diacid is derived from trimellitic anhydride and a polyoxyalkyl diamine selected from the group consisting of polypropylene oxide diamine and a copoly(ethylene oxide-propylene oxide)diamine having predominantly polyethylene oxide in the backbone.

7. A thermoplastic elastomer composition as defined in Claim 1 wherein said rubbery alkylacrylate consists essentially of repeating units of the formulae:

and where n is 2 or 4 and m is 1 or 2 and a cure site monomer.

8. A thermoplastic elastomer composition as defined in Claim 7 wherein said rubbery alkylacrylate is based on repeating units of the formula:

9. A thermoplastic elastomer composition as defined in Claim 1 wherein said crosslinking agent is selected from the group sodium stearate, potassium stearate and a mixture thereof.

10. A thermoplastic elastomer composition as defined in Claim 1 wherein said polyetherimide ester component (A) comprises from about 20 to about 99 parts by weight and said rubbery alkylacrylate component (B) comprises from about 80 to about 1 part by weight based upon 100 parts by weight of (A) and (B).

11. A thermoplastic elastomer composition as defined in Claim 10 wherein said component (A) comprises from about 20 to about 80 parts by weight and said component (B) comprises from about 80 to about 20 parts by weight.

12. A thermoplastic elastomer composition as defined in Claim 11 wherein said component (A) comprises from about 40 to about 60 parts by weight and said component (B) comprises from about 60 to about 40 parts by weight.

WO 91/10708 PCT/US91/00430 11. A thermoplastic elastomer composition as defined in Claim 10 wherein said component (A) comprises about 50 parts by weight and said component (B) comprises about 50 parts by weight.

14. A thermoplastic elastomer composition as defined in Claim 1 which fur her comprises a filler, a stabilizer, an antidegradent, a processing aid, a plasticizer, a pigment, or mixtures of any of the foregoing.

15. A thermoplastic elastomer composition as defined in Claim 14 wherein said filler is selected from the group consisting of carbon blacks, silicas, clays and minerals.

16. A thermoplastic elastomer composition as defined in Claim 14 wherein said plasticizer comprises a low molecular weight plasticizer or a high molecular weight plasticizer or both.

17. A thermoplastic elastomer composition a defined in Claim 1 which further comprises an accelerator.

18. A thermoplastic elastomer composition as defined in Claim 17 wherein said accelerator is selected from the group consisting of sulfur, sulfur donors, magnesium oxide, tertiary amines, quaternary ammonium compounds and mixtures of any of the foregoing.

19. A thermoplastic elastomer composition as defined in Claim 18 wherein the crosslinker comprises sodium stearate and the accelerator comprises a quaternary ammonium compound.

20. A process for producing a thermoplastic elastomer composition comprising:
(I) mixing (i) a polyetherimide ester copolymer, and (ii) a crosslinkable rubbery alkylacrylate; and (II) curing the mixture obtained in step (I) by adding a crosslinking agent.

21. A process as defined in Claim 20 wherein said polyetherimide ester comprises the reaction product of (a) one or more low molecular weight diols; (b) one or more dicarboxylic acids; and (c) one or more polyoxyalkylene diimide diacids.

22. A process as defined in Claim 21 wherein said diol component (a) comprises from about 60 to about 100 mole percent 1,4-butanediol.

23. A process as defined in Claim 21 wherein said dicarboxylic acid component (b) comprises from about 60 to about 100 mole percent dimethyl terephthalate.

24. A process as defined in Claim 21 wherein said polyoxyalkylene diimide diacid component (c) is derived from one or more polyoxyalkylene diamines and one or more tricarboxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl group, and is characterized by the following formula:

wherein each R is independently selected from the group consisting of C2 to C20 aliphatic and cycloaliphatic trivalent organic radical and C6 to C20 aromatic trivalent organic radicals; each R' is independently selected from the group consisting of hydrogen, C1 to C6 aliphatic and cycloaliphatic monovalent organic radicals and C6 to C12 aromatic monovalent organic radicals; and G is the radical remaining after removal of the hydroxy groups of a long chain ether glycol having an average molecular weight of from about 600 to 12000.

25. A process as defined in Claim 24 wherein said polyoxyalkylene diimide diamine is derived from trimellitic anhydride and a polyoxyalkyl diamine selected from the group consisting of polypropylene oxide diamine and a copoly(ethylene oxide-propylene oxide)diamine having predominantly polyethylene oxide in the backbone.

26. A process as defined in Claim 20 wherein said rubbery alkylacrylate consists essentially of repeating units of the formulae:

and where n is 2 or 4 and m is 1 or 2 and a cure site monomer.

27. A process as defined in Claim 26 wherein said rubbery alkylacrylate is based on repeating units of the formula:

28. A process as defined in Claim 20 wherein said crosslinking agent is selected from the group sodium stearate, potassium stearate and a mixture thereof.

29. A process as defined in Claim 20 wherein said polyetherimide ester component (i) comprises from about 20 to about 99 parts by weight and said rubbery alkylacrylate component (ii) comprises from about 80 to about 1 part by weight based upon 100 parts by weight of (i) and (ii).

30. A process as defined in Claim 29 wherein said component (i) comprises from about 20 to about 80 parts by weight and said component (ii) comprises from about 80 to about 20 parts by weight.

31. A process as defined in Claim 30 wherein said component (i) comprises from about 40 to about 60 parts by weight and said component (ii) comprises from about 60 to about 40 parts by weight.

32. A process as defined in Claim 29 wherein said component (i) comprises about 50 parts by weight and said component (ii) comprises about 50 parts by weight.

33. A process as defined in Claim 30 wherein step (I) further comprises mixing (iii) a filler, a stabilizer, an antidegradent, a processing aid, a plasticizer, a pigment, or mixtures of any of the foregoing.

34. A process as defined in Claim 33 wherein said filler is selected from the group consisting of carbon blacks, silicas, clays and minerals.

35. A process as defined in Claim 33 wherein said plasticizer comprises a low molecular weight plasticizer or a high molecular weight plasticizer or both.

36. A process as defined in Claim 20 wherein said step (II) further comprises adding an accelerator.

37. A process as defined in Claim 36 wherein said accelerator is selected from the group consisting of sulfur, sulfur donors, magnesium oxide, tertiary amines, quarternary ammonium compounds and mixtures of any of the foregoing.

38. A process as defined in Claim 37 wherein the crosslinker comprises sodium stearate and the accelerator comprises a quarternary ammonium compound.