CA2033907A1 - Polyetherimide ester elastomeric molding compositions - Google Patents

Abstract

337-2177 (8CT-4903) ABSTRACT
Polyetherimideester molding compositions comprising a copolyetherimideester (A) and an aromatic thermoplastic polyester (a) and a multistage rubbery elastomer (C) comprising a crosslinked (meth)acrylate phase and an interpenetrating, crosslinked phase are useful for making molded articles with a good balance of modulus and elongation properties.

Description

~33~07 -1- 337-2177 (8CT-4903) CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to the following commonly owned related applications:
Serial No. Filed Attys. Docket Title Applicant(s) 5 152,524 2/5/88 8CT-4901 Polyether- W.J. Peascoe (8CQ-9143) imide Ester J .A. Tyrell Compocitions - concur- 8CT-4902 Copoly- T.A. Morelli rently etherester W.J. Peascoe herewith Elastomeric S.F. Rasch Compositions J.A. Tyrell - concur- 8CT-4904 Copoly- M.R. McCormick rently etherester T.A. Morelli herewith Elastomeric W.J. Peascoe Compositions S.F. Rasch M.T. Wong FIELD OF INVENTION
This invention relates to elastomeric compositions comprising copolyetherimide esters (A) an aromatic thermoplastic polyester (B~ and a multistage elastomer comprised of a crosslinked alkyl acrylate phase which is interpenetrated by a crosslinked styrenic phase (C). Such compositions exhibit good physical properties such as tensile elongation and flexural modulus when molded.
BACKGROUND OF INvENTroN
Thermoplastic elastomers of the type known as polyetherlmide esters provide a variety of unique and excellent properties and are particularly useful in extrusion and molding applications.
Polyeth0rimide esters prepared from diols, dicarboxylic acids and polyoxyalkylene diimide diacids 2~33~07 -2- 337-2177 (8CT-4903) are thermoplastic elastomers having an excellent combination of stress-strain properties, low tensile set, high melting temperatures and excellent strength, toughness and flexibility properties. All of these properties are variously usef~l in many elastomer applications. Polyetherimide esters also process well, due to their rapid crystallization rate and excellent moldability characteristics. Elastomers wi~h low flexural modulus of polyetherimide esters in combination with any of the aforementioned advantageous properties have gained wide acceptance in the field of thermoplastic elastomers.
Dependent upon the application, there are various modulus and durometer requirements. To some extent, these properties can be varied by the constituents of the polyetherimide esters, but such ~custom" synthesis can be costly and impractical when a wide range i8 required.
Nonetheless it has now been found that the utility of polyetherimide esters can be improved or enhanced for certain applications, especially with Eespect to improving the "softnes~" ti.e., lower durometer~ of the elastomer, while retaining satisfactory tensile properties.
The improvements are accomplished by the : incorporation of an aromatic thermoplastic polyester (B) and effective amounts of certain rubber modifiers of the s type known as multistage interpolymers (Cl. It is sur-prising, however, that elastomeric compositions incorpor-ating the selected rubber modifiers can be processed to avoid the delamination or phase s2paration ~or so-called ~cheesine~s~) expected for the combination or thermoplastic elastomers and typical rubber products.
In particular it has been found that copoly-etherimide ester elastomers can be improved by the in-~39~

_3~ 337-2177 ~CT-4903) corporation of an aromatic thermoplastic polyester and rubber modifiers. The instant invention utilizes effective amounts of rubber modifiers characterized as a multi-stage, or se~uentially produced interpolymer product, specifically a thermoplastic elastomer comprised of a- crosslinked polyacrylate rubbery phase which is interpenetrated by a crosslinked styrenic phase. This multistage interpolymer elastomer has been added to thermoplastic resins as an impact strength improving additive, including copolyetherimide esters.
See, for example, above-mentioned U.S. Patent Application S.N. 152,524, filed February 5, lg88.
It is an object of the present invention to provide thermoplastic elastomeric molding compositions which are suitable for a broad range of end use applications having sufficient flexural modulus so as to provide molded part~ with good physical integrity and stiffness.
It has now been found that thermoplastic elastomeric molding compositions may be prepared which overcome the foregoing deficiencies and have good over-all physical characteristics including high stress-strain properties, good elongation and good moldability.
It has been further surprisingly found that effective amounts of the aforementioned multistage polymer modifier can be combined with a rubbery poly etherimide ester elastomer product and a polyester, which will thereby exhibit improved modulus and tensile properties as mentioned above.
SUMMARY OF T~E INVENTION
A thermoplastic elastomer composition is provided comprising the combination of a polyetherimide e~ter copolymer (A), an aromatic thermoplastic 2~33~7 - -4- 337-2177 (8CT-4903) polyester (B), and a modulus reducing amount of a rubbery, multistage interpolymer modifier (C). A
modulus reducing amount of modifier refers to the effectiveness of tne interpolymer modifier for improving the softness of the combination of the polyetherimide ester elastomer and the polyester.
In preferred embodiments compositions are provided wherein the polyetherimide e~ter copolymer (~) is present in an amount of from about 1 to about 99 parts by weight to, correspondingly, from about 99 to about 1 parts by weight of aromatic polyester (B), the rubbery interpolymer (C) is present in an amount of from about 5 to about 95 parts by weight to, correspondingly, from about 95 to about 5 parts by weight of (A) and tB).
In especially preferred embodiments compositions are provided wberein rubbery interpolymer (C) is present in an amount of from about 20 to about 80 parts by weight to, correspondingly, from about 80 to 20 parts by weight of (A) and (B) taken together.
Preferably, the copolyetherimide ester (A) is the reaction product of (i) one or more low molecular weight diols; (ii) one or more dicarboxylic acids: and (iii) one or more polyoxyalkylene diimide diacids.
In p~eferred copolyetherimide e~ter elastomers the diol component (i) will be 60 to 100 mole percent ~ 1,4-butanediol; and the dicarboxylic acid component (ii) ; will be 60 to 100 mole percent dimethyl terephthalate.
Preferred polyoxyalkylene diimide diacids are discussed in detail below.
Preferred aromatic thermoplastic polyesters comprise poly(ethylene terephthalate) poly(butylene terephthalate) copoly(butylene terephthalate-isophthalate) mixture~ of any of the foregoing, and the like.
The rubbery acrylate used in the first step is - 35 peeferably an alkyl or alkoxy alkyl acrylate, hereinafter -5- 337-2177 (8CT-4903) referred to as (meth)acrylate. Of these, butyl acrylate is preferred.
The styrenic resin used in the second stage of the interpolymer is preferably crosslinked polystyrene although copolymers and substituted styrenes may also be utilized. For example, vinyl-type monomers such as acrylonitrile may be utilized depending upon the final use for the product. In such instance the second stage can be a crosslinked styrene-acrylonitrile copolymer (SAN).

DETAILED DESCRIPTION OF T~E INVENTION
The polyetherimide esters used herein may be prepared from one or more diols, one or more dicarboxylic acids and one or more high molecular weight polyoxyalkylene diimide diacids. Preparation o~ such materials is described in detail in McCready and Tyrell U.S. Patent Na.
4,556,705.
The poly(etherimide esters) used herein may be prepared by conventional processes, such as esterification and condensation reactions for the production of polyesters, to provide random or block copolymers. Thus, polyether-imide e~ters may be generally characterized as the react-tion product of the aforementioned diols and acids.
Preferred compositions encompassed by the present invention may be prepared from (i) one or more C2-C15 aliphatic or cycloaliphatic diols, (ii) one or more C4-C16 aliphatic, cycloaliphatic or aromatic dicarboxylic acids or ester derivative~ thereof and (iii) one or more polyoxyalkylene diimide diacids. The amount of poly-oxyalkylene diimide diacid employed is generally depen-dent upon the desired properties of the resultant poly-etherimide ester. In general, the weight ratio of poly-oxyalkylene diimide diacid (iii) to dicarboxylic acid (b) is from about 0~25 to 2.0, preferably from about 0.4 ~33~

-6- 337-2177 (8CT-4903) to about 1.4.
Sui~able diols (i~ for use in preparing the compositions of the present invention include sa~urated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds.
These diols are preferably of a low molecular weight i.e. having a molecular weight of about 250 or less.
When u~ed herein, the term "diolsn and ~low molecular weight diols" should be construed to include equivalent ester forming derivatives thereof, provided, however, that the molecular weight requirement pertains to the diol only and not to its derivatives. Exemplary of ester forming derivatives there may be given the acetates of the diols as well as for example ethylene oxide or ethylene carbonate for ethylene glycol.
Especially preferred diols are the saturated aliphatic diols, mixtures thereof and mixtures of a saturated diol(s) with an unsaturated diol~), wherein each diol contains from 2 to about 8 carbon atoms.
Where more than one diol is employed, it is preferred that at lea~t about 60 mole percent, based on the total diol content, to be the sa~e diol, most preferably at least B0 mole percent. As mentioned above, the preferred compo~itions are those in which 1,4-butanediol 25 i8 present in a predominant amount~ most preferably when 1,4-butanediol is the only dicl.
Dicarboxylic acids (ii) which are suitable for use in the practice of the present invention are aliphatic, cycloaliphatic, and/or aromatic dicarboxylic acids. These acids are preferably of a low molecular weight of le~s than about 300; however, higher molecular weight dicarboxylic acids, especially dimer acids, may also be used. The term "dicarboxylic acids" as used herein, includes equivalents of dicarboxylic acids having two functional carboxyl groups which perform 2 ~ ~ 3 ~ 9 ~ r~

-7- 337-2177 (8CT-4903) substantially like dicarboxylic acids in reaction with glycols and diols in forming polyester polymers. These equivalents include esters and ester-forming derivatives, such as acid halides and anhydrides. The molecular weight preference, mentioned above, pertains to the acid and not to its equivalent ester or ester-forming derivative.
Preferred dicarboxylic acids for the preparation of the polyetherimide esters of the present invention are the aromatic dicarboxylic acids, mixtures thereof and mixtures of one or more dicarboxylic acids with an aliphatic or cycloaliphatic dicarboxylic acid, most preferably the aromatic dicarboxylic acidsO Among the aromatic acids, those with 8~16 carbon atoms are preferred, particularly the benzene dicarboxylic acids, i.e., phthalic, terephthalic and isophthalic acids and their dimethyl derivatives. Especially preferred is dimethyl terephthalate.
~inally, where mixture~ of dicarboxylic acids, are employed in the practice of the present invention, it is preferred that at least about 60 mole percent, preferably at least about 80 mole percent, based on 100 mole percent of dicarboxylic acid (ii) be of the same dicarboxylic acid or ester derivative thereof. As mentioned above, the preferred compositions are those in whlch dimethylterephthalate is the predominant dicarboxy-lic acid, most preferably when dimethylterephthalate is the only dicarboxylic acid.
Polyoxyalkylene diimide diacids (iii) suitable for use herein are high molecular weight diacids wherein the average molecular weight is greatçr than about 700, most preferably greater than about 900. They may be pre-pared by the imidization reaction of one or more tricar-boxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl 2~33~J~

-8- 337-2177 (8CT-4903) group which must be esterifiable and preferably is non-imidizable with a high molecular weight polyoxyalkylene diamine. The polyoxyalkylene diimide diacids and proceC~es for the preparation are more fully disclosed 665,192 filed Oct. 26, 1984 entitled "High Molecular Weight Diimide Diacids and Diimide Diecters of Tricarboxylic Anhydrides.
In general, the polyoxyalkylene diimide diacids useful herein may be characterized by the following formula:

O
Il ll R'OOC - R \ / N G N \ / R - COOR' Il 1~
O O

wherein each R is independently a trivalent organic rad-ical preferably a C2 to C20 aliphatic, aromatic or cycloaliphatic trivalent organic radical; each R' is independently hydrogen or a monovalent organic radical preferably selected from the group consistinq of Cl to C6 aliphatic and cycloaliphatic radicals and C6 to C12 aromatic radicals, e.g. phenyl, most preferably hydrogen;
and G i8 the radical remaining after the removal of the terminal (or as nearly terminal as possible)hydroxy groups of a long chain ether glycol having an average molecular weight of from about 600 to about 12000, preferably from about 900 to about 4000, and a carbon-to-oxygen ratio of about 1~8 to about 4.3.
Repre~entative long chain ether glycol~ from which the polyoxyalkylene d$amine is prepared include poly(ethylene ether) glycol; poly(propylene ether)glycol;
poly(tetramethylene ether)glycol; random or block copolymers of ethylene oxide and propylene oxide, -9- 337-2177 ~8CT-4903) including propylene oxide terminated poly(ethylene ether) glycol; and random or block copolymers of tetrahydrofuran with minor amounts of a second monomer such as methyl tetrahydrofuran (used in proportion such that the carbon-to-oxygen mole ratio in the glycol does not exceed about 4.3). Especially preferred poly(alkylene ether)glycols are poly(propylene ether)glycol and poly(ethylene ether) glycols end capped with -poly(propylene ether)glycol or propylene oxide.
In general, the polyoxylalkylene diamines useful within the scope of the present invention will have an average molecular weight of from about 600 to 12000, preferably from a about 900 to 4000.
The tricarboxylic component may be almost any carboxylic acid anhydride containing an additional carboxylic group or the corresponding acid thereof containing two imide-forming vicinal carboxyl groups in lieu of the anhydride group. Mixtures thereof are also ~uitable. The additional carboxylic group must be esterifiable and preferably is ~ubstantially non-imidizable.
The tricarboxylic acid materials can be characterized by the following formula:

O
li ~C~

\IC
.- O

, , ' ' ' ' , ' , ,".

- 2 ~

-10- 337-2177 (8CT-4903) where R is a trivalent organic radical, preferably a C2 to C20 aliphatic, aromatic, or cycloaliphatic trivalent organic radical and r' is preferably hydrogen or a monovalent organic radical preferably selected from the group consisting of Cl to C6 aliphatic or cycloali-iphatic radicals and C6 to C12 aromatic radicals, e.g.
phenyl; most preferably hydrogen. A preferred tricarboxylic component is trimellitic anhydride.
Briefly, these polyoxyalkylene diimide diacids may be prepared by known imidiza~ion reac~ions including melt synthesis or by synthesizing in a solvent system.
Such reaction will generally occur at temperature of from 100 degrees C to 300 degrees C, preferably at from about 150 degrees C to about 250 degrees C while drawing off water or in a ~olvent sy~tem at the reflux tempera-ture of the solvent or azeotropic (solvent) mixture.
Although the weight ratio of the above ingredient~ is not critical, it is preferred that the diol be present in at least a molar equivalent amount, preferably a molar excess, most preferably at least 150 mole percent based on the moles of dicarboxylic acid (ii) and polyoxylalkylene diimide diacid (iii) combined.
Such molar excess of diol will allow for optimal yields, based on the a~ount of acids, while accounting for the 108~ of diol during esterification/condensation.
Further, while the weight ratio of dicarboxylic acid ~ii) to polyoxylalkylene diimide diacid (iii) is not crltical to form the polyetherimide esters uYed in the present invention, preferred compositions are those in which the weight ratio of the polyoxyalkylene diimide diacid (iii) to dicarboxylic acid (ii) is from about 0.25 to about 2, preferably from about 0.4 to about 1.4.
The actual weight ratio employed will be dependent upon the specific polyoxyalkylene diimide diacid used and more importantly, the desired physical and chemical ~33~

-11- 337-2177 (8CT-4903) properties of the resultant polyetherimide ester. In general, the lower the ratio of polyoxyalkylene diimide diester to dicarboxylic acid the better the strength, crystallization and heat distortion properties of the S polymer. A$ternatively, the higher the ratio, the bet~er the flexibility, tensile set and low temperature impast characteristics.
In preferred embodiments, the polyetherimide ester product will comprise the reaction product of dimethylterephthalate, optionally with up to 40 mole percent of another dicarboxylic acid; 1,4-butanediol, optionally with up to 40 mole percent of another saturated or unsaturated aliphatic or cycloaliphatic diols and a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene diamine of molecular weight 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 percent 1,4-butanediol and dicarboxylic acid 100 mole percent dimethylterephthalate.
The polyetherimide esters described herein may be prepared by conventional esterification/condensation reaction~ for the production of polyesters. Exemplary of the process that may be practiced are as set forth in, for example, U.S. Pat. Nos. 3,023,192; 3,763,109;

3,651,014~ 3,663,653 and 3,801,547. Additionally, these compositions may be prepared by Ruch processes and other known processes to effect random copolymers, block copolymers or hybrids thereof wherein both random and block unit~ are present.
It is customary and preferred to utilize a catalyst in the process for the production of the polyetherimide esters of the present invention. In general, any of the known ester-interchange and polycondensation catalysts may be used. Although two -12- 337-2177 (8CT-4903) separate catalysts or catalyst systems may be used, one for ester interchange and one for polycondensation, it is preferred, where appropriate, to u~e one catalyst or catalyst system for both. In those instances where two separate catalysts are used~ it is preferred and advantageou-# to render the ester-interchange catalyst ineffective following the completion of the precondensation reaction by mean~ of known catalyst inhibitors or quenchees, in particular, phosphorus compounds such as phosphoric acid, pho#-phenic acid, phosphonic acid and the alkyl or aryl este~s of salts thereof, in order to increace the thermal stability of the re~ultant polymers.
Exemplary of the suitable known catalysts there may be given the acetates, carboxylates, hydroxides, oxide~, alcoholates or organic complex compounds of zinc, manganese, antimony, cobalt, lead, calcium and the alkali metals insofar as these compounds are soluble in the reaction mixture. Specific examples include, zinc acetate, calcium acetate and combinations thereof with antimony tri-oxide and the like. These catalyst~ as well a~ additional useful cataly~ts are described in U.5~ Patent Nos. 2,465,319; 2,534,0238 2,850,483;
2,892,8715; 2,937,160; ~,998,412; 3,047,539; 3,110,693;
and 3~385,830, among others.
Where the reactants and reactions allow, it is pre~erred to use the titanium catalysts including the inorganic an organic titanium containing catalysts, such as those described in, for example, U.S. Patent Nos.
2,720,502; 2,727,881; 2,729,619; 2,~22,348; 2,906,737;
3,047,515; 3,056,817; 3,056,818; and 3,075,952 among others. ~specially preferred are the organic titanates such as tetra-butyl titanate, tetraisopropyl titanate and tetra-octyl titanate and the complex titanates derived from alkali or alkaline earth metal alkoxides -13- 337-2177 (8C~-4903) and titanate esters, most preferably the organic titanates. These too may be used alone or in combination with other catalysts such as for example, zinc acetate, manganese acetate or antimony trioxide, and/or with a catalyst quencher as described above.
Although these polyetherimide esters possess many desirable properties, it is often preferred to stabilize the compositions to heat, oxidation, radiation by W light and the like, a~ descrlbed in the afore-mentioned U.S. Patent No. 4,556,705.
The foregoing thermoplastic elastomers (A) aremodified in accordance wit~ the teachings of the instant invention by ad~ixing therewith one or more thermoplastic aromatic polyesters (B) derived from an aliphatic and/or cycloaliphatic diol and an aromatic dicarboxylic acid or its ester derivative and including interpolymer (C).
While most any of the abovementioned aliphatic and/or cycloaliphatic diols and aromatic dicarboxylic acids or ester derivatives thereof may be used in the preparation of the thermoplastic aromatic polyester, preferred polyesters will have repeating units o the following general formula:
O
D- 0 - C ~

where D is the divalent radical remaining after removal of the hydroxy groups from a low molecular weight diol, as deflned above. Additionally, these polye~ters may also contain minor amounts of other units such as aliphatic dicarboxylic acids and/or aliphatic polyols.
Preferred polyesters include poly(butylene terephthal-ate), poly(ethylene terephthalate) and blends thereof most preferably poly(butylene terephthalate).

2~3~
-14- 337-2177 (8CT-4903) The polyesters described above are either commercially available or can be produced by methods well known in the art, sucA as those set forth in United States Patent NosO 2,465,319; 3,047,539; and 2,910,466.
The rubbery, multistage interpolymer (C) is comprised of a crosslinked acrylate rubbery phase and an interpenetrating crosslinked phase. The two phases, produced in sequential fashion, maintain integrity as a result of the crosslinking of the interpenetrating polymer chains. As a consequence, it is not necessary to graft the second phase onto the first although such a graf~ing step could be u~ilized if desired~ The exact structure of the multistage is not known but a ceasonable conjecture maintains that a core of crosslinked acrylate rubber is formed in the first step which is then surrounded and interpenetrated by styrenic resin, which is crosslinked thereby forming the integral mult$stage interpolymer.
Whether this crosslinked styrenic phase forms a complete or discontinuous ~shell~ around the core depends on reaction condition~ as well as quantitie~ of pslymer utiliæed.
Illustratively, the multistage, interpolymer modifiers of the present invention are thoce having a - cros~linked (meth)-acrylate rubbery phase, preferably butyl acrylate. Associated with this crosslinked rubbery phase is a phase comprised of crosslinked qtyrenic resin, preferably styrene, which interpenetrates the cros~linked rubbery phase. Incorporation of small amounts of other monomers such a~ acrylonitrile or (meth)acrylonitrile within the resin also provides products within the scope of this invention. The interpenetrating network i5 provided when the monomers form$ng the resin phase are polymerized and crosslinked in the presence of the previously polymerized and crosslinked (meth)acrylate rubbery phase.

2~3~

-15- 337-2177 (8CT-4903) The interpolymer compositions may be formed by the following two-step, sequential polymerization process:
1. emulsion polymerizing an acrylate monomer charge of at least C -ClO alkyl or alkoxyalkyl acrylate, C -C12 alkyl or alkoxyalkyl methacrylate~ or compatible mixtures thereof (all of which may be referred to as (meth) acrylate~, in an aqueous polymerization medium in the presence of an effective amount of a suitable di or polyfunctional ethyleneically unsaturated crosslinking agent for cuch type of monomer, with the C4-C8 alkyl or alkoxyalkyl acrylates being the preferred acrylate monomers for use in this step;
2. emulsion polymerizing a monomer chaege of styrene or styrene/(meth)acrylonitrile in an aqueous lS polymerization medium, al~o in the presence of an ef~ective amount of a suitable di or polyfunctional ethyleneically unsaturated crosslinking agent for such monomers, said polymerization being carried out in the presence of the product in Step 1 so that the crosslinked (meth)acrylite and crosslinked vinyl aromatic, e.g., styrene or styrene/(meth3acrylonitrile components from an interpolymer wherein the respective phases interpenetrate one another.
The final multistage rubbery product that is formed thereby can be i~olated and dried.
In greater detail, in conducting the aqueous emul~ion polymerization step leading to the preparation of the crosslinked (meth)acrylate rubbery phase, there is preferably fir~t prepared a monomer charge comprising an aqueous mixture containing about 10 to 50 percent by weight, of one or more monomers, the identity of which will be described in detail hereinbelow and from about 0.2 to 2.0 percent weight of the monomer weight mixture, of a water-soluble catalyst, such as ammonium, sodium or potassium persulfate, hydrogen peroxide or a redox system, :, 2~3~

-1~ 337-2177 (8CT-4903) such as a mixture of a persulfate with an alkali metal bisulfite, thiosulfate or hydrosulfite. The mixture is then heated at a temperature of from about 40 degrees to 95 degrees C for a period of about 0.5 to about 8 hours.
The (meth~acrylic elastomer phase co~prises crosslinked(meth)acrylic polymers or copolymers having a Tg, i.e., a glass transition temperature, of less than about 25 degree C. These can be polymerized by means of free radical initiated emulsion techniques. These (meth)-acrylic elastomer polymers should be crosslinked so that they can retain their integrity during subsequent polymer proce~sing steps. This crosslinking can be achieved during the polymerization of the elastomer if a polyfunctional ethylenically unsaturated monomer is included in the polymerization recipe. As used in this disclosure, the term "crosslinked" denotes a poly~er which at ambient temperatures is subctantially insoluble in such organic solvents as tetrahydrofuran or cyclo-hexanone.
Examples of (meth)acrylic elastomers that can be used include the crosslinked polymers of the C -C

alkyl acrylate and the C8-C12 alkyl methacrylate monomers, preferably the C2-C8 alkyl acrylates, such as poly(n-butyl acrylate), poly(ethyl acrylate) and poly (2-ethylhexylacrylate). As least one acrylate monomer i9 utilized in thi~ step. If desired, the monomer charge may contain small amounts, i.e., 1 to 20 percent by weight of the amount of acrylate monomer, o~ optional monomers including styrene, acrylonitrile, methacrylo-nitrile, methyl methacrylate, methacrylic acid, acrylicacid, vinylidene chloride, vinyl toluene and any other ethyleneically unsaturated monomer copolymerizable with the acrylate monomer selected for u e. Special mention is made of alkoxyalkyl (meth)acrylates, specifically ethoxyethyl and methoxymethyl (meth)acrylates, and 2~33~07 -17- 337-2177 (8CT-4903) acrylonitrile which will improve oil resistance while maintaining a low Tg.
In order to crosslink the (meth)acrylate monomer, from about 0.05 to about 10, preferably 0.1 to 5 percent by weight ba~ed on the weight of acrylate monomer, of at least one crosslinking agent is used.
This crosslinking agent is for the purposes of this invention a di or polyfunctional ethyleneically unsatu-rated monomer having at least one vinyl group of the formula:

~ C - C /

wherein R is hydrogen or lower alkyl. A~ is well known in the art the vinyl groups on the cro~slinking monomer triacrylate, etc., or different e.g. allyl methacrylate, diallyl fumarate, diallyl maleate, etc. Examples of other suitable crosslinking monomers which are known to persons in the art and which can be used are triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dime~hacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, diethylene glycol di~ethacrylate, 1,6-hexanediol di-acrylate, 2,2-dimethylpropane 1,3-diacrylate, triallyl isocyanurate, divinyl benzene, pentaerythritol tetrameth-acrylate, dipentaerythritol monohydroxy-penta-acrylate, pentaerythritol triacrylate, ethoxylated trimethylol-propane triacrylate, polyethylene glycol diacrylate,tetraethylene glycol diarylate, pentaerythritol tetra-acrylate, 1,3-butylene glycol dimethacrylate, tripropy-lene glycol diacrylate, exthoxylated bisphenol-A-dimethy-acrylate, ethoxylated bisphenol A diacrylate, trimethy-2 ~ 3 3 ~ ~ ri -18- 337-2177 (8CT-4903) lolpropane triacrylate, trimethylolpropane trimethacry-late, mixtures of any of the foregoing, and the like.
Optimum re~ults are obtained by the use of a crosslinked copolymer containing from about 95 to about 99.9 percent by weight of n-butyl acrylate and from about 0.1 to about 5 percent by weight, of butylene glycol di-acrylate.
The emulsifier which is used is at least one of the following conventional types: an anionic emulsifier, e.g., the C2-C22 carboxylic acids, the sulfates or, sulfonates of C -C22 alcohol~ or allyl phenols; a non-ionic emulsifier, e.g., the addition products of alky-lene oxides to addition products of alkylene oxides to fatty acid3, amines or amides; a combination o~ the foregoing anionic and non-ionic emulsifiers; o~ the cationic emulsifiers, e.g., a quarternary ammonium containing compound. The amount of emulsi~ier should be present from about 0.5 to about 5 percent by weight in the emul~ion.
In the prior di~closure of Yu et al., U.S.
3, 944, 631, it has been found that regardless of the particular emulsifier being utilized in preparing the rubber polymer latex, its polymerization in large scale commercial equipment is greatly facilitated by introducing the monomer charge to the system in several portions over a period from 1 to 3 hours. Thus, where this is not done and the total monomer charge is introduced in one portion, the resulting exothermic polymerization reaction often becomes virtually uncontrollable leading to overheating which, in turn, may set up, i.e., coagulate, the re~ulting polymer latex. However, by dividing the monomer charge and introducing it in about several portions, the resulting polymerization reaction remains controllable and overheating and coagulation can be prevented. An initiator is also present in the ~3~

-19- 337-2177 (8CT-4903) emulsion in an amount ranging from about 0~0005 to 2 percent by weight of the (meth)acrylate monomer.
Suitable for use are water soluble peroxidic compounds, e.g., hydrogen peroxide and alkali metal and ammonium persulfates, oil soluble organic peroxide~ and azo compounds, e.g., benzoylperoxide, azobisisobutyronitrile and the like, used singly or in combination. Redox catalysts, e.g., mixtures of peroxidic catalysts with reducing agents, such as hydrazine, alkali metal b$sulfites, thiosulfates, and hydrosulfites, and soluble oxidizable sulfoxyl compounds can also be used.
Preferred as the initiator herein is ammonium persulfate.
A chain transfer agent as an alkyl mercaptan~
e.g., t-dodecyl mercaptan, toluene, xylene, chloroform, halogenated hydrocarbons an the like may also be used.
A buffer to adjust the pH may be used.
The next step in the preferred embodiment of preparing the interpolymers used herein is the emulsion polymerization of a mixture of vinyl aromatic monomers, e.g., styrene or styrene and acrylonitrile, in the presence of minor portion of at least one difunctional or polyfunctional crosslinking monomer to form, for example, a crosslinked styrene homopolymer or styrene-acrylonitrile co-polymer. This emulsion polymerization i~ carried out in the presence of the crosslinked (meth)-acrylate rubbery phase by adding the styrene or styrene-acrylonitrile charge to the previously prepared aqueous emulsion of crosslinked (meth)acrylate rubbery phase.
The amount of styrene or styrene-acrylonitrile which is added ranges from about 60 to about 10, preferably from about 50 to about 20 percent based upon the weight of the final product which will be formed. When present, (meth)acrylonitrile preferably comprises from about 15 to about 45 parts by weight to, correspondingly, about 85 to about 55 parts of vinyl aromatic monomer.

2~3~
-20- 337-2177 (8C~-4~03) The monomer char~e of styrene-acrylonitrile, when such a combination is used, can comprise from about 55:45 to about 85sl5 weight parts of styrene to acrylonitrile with the most preferred ratio being about 7:24. If de~ired, minor amountQ, e.g., below about 20 percent by weight, of optional monomers can be included.
Examples are t-butyl styrene, p-chlorostyrene, alpha-methylstyrene, methyl methacrylate, alkyl acrylate vinylidene chloride, ethylene, propylene, isobu~ylene and other ethyleneically compounds copolymerizable with styrene and styrene-acrylonitrile.
The crosslinking agent, emulsifiers, initiators and chain transfer agent discussed in the previous step can also be used in this step in the same amounts to form the interpenetrating crosslinked styrene-acrylonitrile resin phase associated with the rubbery phase.
Other additives can be used such a~ conventional light, thermal and ultraviolet light stabilizers, flame retardants, antioxidants, dyes, pigments~ mineral addi-tives and extending fillers and reinforcing agents.

DESCRIPTION OF THE PREFERRED EMBODI~ENTS
The following examples show preferred embodimentsof the compositions and processes of the claimed invention and the products formed therefrom. They are illustrative and are not intended to limit the clai~s in any way what-soever. In the following example~, given without limitation, all parts are by weight unless otherwise specified.
The polyetherimide ester elastomer, the aromatic thermoplastic polyester, and the rubbery multistage inter-polymer modifier can be combined in the desired proport-ions by conventional means as by mixing, blending or ex-trusion under conditions of sufficient heat, shear and pressure to provide a relatively uniform mixture. The 2~3~7 -21- 337-2177 (8CT-4903) resulting low modulus elastomer product may be fabricated into finished products~ also by conventional means such as injection or compression molding.

PREPARATION OF COPOLYETHERIMIDE ESTER
A polyetherimide ester copolymer may be made by reacting 27 parts by weight 1,4-butanediol, 34 parts by weisht dimethyl terephthalate and 39 parts by weight of a polyoxyalkylene diimide diacid prepared by the imidization of trimellitic anhydride and a propylene ether diamine having an average molecular weight of 2000 (e.g., Jeffamine- D2000, available from Texaco Che~ical Company). The weight ratio of diimide diacid to dimethyl terephthalate is 1.15. The polyetherimide ester c4polymer prepared has an ASTM flexural modulus of about 14,500 p~i.

PREPARATION OF XL ACRYLATE/XL STYRENE INTERPOLYMER
A thermoplastic elastomer comprising a crosslinked poly(butyl acrylate) and an interpenetrating, crosslinked polystyrene resin phase is prepared in a five liter, three-necked flask equipped with a heating/
cool~ng jacket, a Teflon blade agitator, a thermometer and a nitrogen purge.
The following solutions are prepared:
Solution As n-butyl acrylate 751.4 g 1,3-butyleneglycol diacrylate 1.27 g Solution B: ~odium metabisulfite 1.75 g deionized water 27.4 g Solution C: ammonium persulfate 4.84 g deionized water 76.1 g Solution D: styrene 250.6 g divinyl benzene 2.65 g 35 (55%active solution from Dow Chemcial) ~36~7 -22- 337~2177 ( 8CT-4903 ) Into the reaction flask is charged: 3,460 g deionized g Sipex UB sodium lauryl sulfate (from Alcolac, Inc.) and 4.2 g Aersol A-268, a disodium sulfosuccinate (from American Cyanamid), and 1~.6 g of Solution B. The flask is stirred and sparged with N~ at coom temperature for 30 minutes, to reduce the 2 content.
Thereafter, 150.5 g of N2 sparged Solution A
is added. The flask contents are heated to 55 degrees C.
and then 13.5 g solu~ion C is added to inititate poly-merization.
After 1.5 hours of reaction, a sample shows 4.1% resin solids indicating approximately 96% percent conversion. The remainder of Solution A as well as 14.6 g Solution B and 40.4 g solution C are added. After 2.5 hours of additional reaction time at 55 degrees C., a ample shows 17.2 percent resin solids, indicating greater then 97 percent conversion.
The reaction mixtu,re ic cooled to 35 degrees C. and Solution D i~ added and mixed for 15 minutes at 35 degrees C. The reaction mixture is then heated to 60 degrees C. and the remainder of Solution C. is added.
The mixture wa~ reacted for 1.25 hours. The temperature is raised to 75 degrees C. and maintained for 45 minutes.
A final sample shows 22.4 percent re~in solids indicating a conversion greater than 98 percent.
The product latex is coagulated in a solution of 0.25 weight percent CaC12 in methanol at rate of 1600 ml methanol per 800 ml latex. The coagulum is filtered, rinsed with fresh water, and dried in a vacuum oven at 60 degrees C.

2~39~7 -23- 337-2177 (8CT-4903) The product has a rubber content of 75% by weight, a number average latex particle diameter of 211 nanometers, a swell index in methyl ethyl ketone (MEK) of 8.1 percent gel fraction from ME~ extraction of 91.1 percent.

PREPARATION OF XL ACRYLATE/XL STYRENE-ACRYLONITRILE
INT~RPOLYMER
A thermoplastic elastomer comprising a cross-linked poly(butyl acrylate) rubbery phase and a cross-linked poly(styrene-co-acrylonitrils) resin phase is pre-pared according to the method of the previous preparation except that 30 weight percent of the styrene is replaced with acrylonitrile and 70 weight percent styrene monomers are u~ed in Solution D.

Compositions indicated by Ta~le l are prepared by combining a polyetherimide ester copolymer as prepared above, an aromatic thermoplastic polyester modifier such as polybutyleneterephthalate, and a multi-stage interpolymer identified as XL acrylate/ XL styrene.
This interpolymer is a crosslinked butyl acryl~te which i8 interpenetrated by a crosslinking polystyrene, as prepared above. Also used is the interpolymer above des~gnated XL acrylate/XL styrene-acrylonitrile. The compositions are made by melt blending in an extruder at 240C. Shore hardness and tensile propertie4 on injectlon molded parts are determined by ASTM D2240 and D638. The formulations used and the re~ults obtained are set forth in the Table as follows:

2 ~ 0 7 -24-337-7177 ~8CI'-~903) ~a I ~ I o o I I ~
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r.~ o 0 o o ~ o I o ~rl I O ~ 1 ~ ~ I .o I o~ ~ I
. l . ..
I r~ O I O O I _~ I I ~
~a _olrlrll l 1 r~ I 1`0 1 ~ .
oo l -~

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I J O I "~ I ¦ n v U I U o I I ,~ O ID C O
o I o " I o o c a I

r~ ~a I o I~ _ _ r- o ~ o o 1 ~ I ~ ~ ~ _ _ _ ~ ~

¦r ~n I u Io~ O ~o ~o n n ~o I o o 1 3 ~ u o o ~ O el. -- :~U D ~
u o o o ~ ~ o o ~ a . ' I ~ L ~ o(l- ~__Oon n c ~ " o ~9 o c c ~ ~ o o ~
1~ ~ a. o, ~ ~ _ ~ 1.

2 ~

-25- 337-2177 (8CT-4903) The foregoin~ data demonstrate that compositions ~Examples 1-19) achieve a wide variation in flexural modulus and durometer. It is unexpected that the compositions of Exa~ples 1-7 of this invention would have such good tensile elongations, ranging from 130 percent to greater than 340 - percent. The compositions exhibited no evidence of delamination or phase separation as might be expected for blends including rubbery components.
The above-mentioned patents, applications and publication3, if any, are incorporated herein by reference.
Many variations will suggest themselYes to those skilled in the art in light of the above, detailed description.
All such variations are within the full intended scope of the appended claims.

Claims (17)

1. A thermoplastic elastomeric composition comprising:
(A) a polyetherimide ester copolymer;
(B) an aromatic thermoplastic polyester having repeating units of the following formula:

wherein D is the divalent radical remaining after removal of the terminal hydroxy groups of a C2 to C20 aliphatic or cycloaliphatic diol; and (C) a modulus reducing amount of a rubbery inter-polymer comprising a crosslinked (meth)acrylate rubbery phase and an interpenetrating, crosslinked styrenic resin phase.

2. A composition as defined Claim 1 wherein said polyetherimide ester copolymer is the reaction product of (i) one or more low molecular weight diols; (ii) one or more dicarboxylic acids; and (iii) one or more polyoxyalkylene diimide diacids.

3. A composition as defined Claim 2 wherein the diol component (i) is 60 to 100 mole percent 1,4-butanediol.

4. A composition as defined Claim 2 wherein the dicarboxylic acid component (ii) is from 60 to 100 mole percent dimethyl terephthalate.

-27- 337-2177 (8CT-4903)

5. A composition as defined Claim 2 wherein the polyoxyalkylene diimide diacid component (iii) 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 triva-lent organic radicals and C6 to C20 aromatic trivalent organic radicals; each R' i8 independently selected from the group consisting of hydrogen, Cl to C6 aliphatic and cyclo-aliphatic monovalent organic radicals and C6 to C12 aromatic monovalent organic radicals, and G is the radical remaining after removal or the hydroxy groups of a long chain ether glycol having an average molecular weight of from about 600 to 12000.

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

-28- 337-2177 (8CT-4903)

7. A composition as defined Claim 1 wherein the aromatic thermoplastic polyester is represented by repeating units of the following formula:

wherein D is the divalent radical remaining after removal of the terminal hydroxy groups of a C2 to C6 aliphatic diol.

8. A composition as defined Claim 7 wherein the aromatic thermoplastic polyester is selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), copoly(butylene terephthalate-isophthalate) and blends thereof.

9. A composition as defined Claim 8 wherein the aromatic thermoplastic polyester is poly(butylene terephthalate).

10. A composition as defined Claim 1 wherein the rubbery phase of said crosslinked (meth)acrylate comprises a crosslinked alkyl or alkoxyalkyl (meth)acrylate.

11. A composition as defined in Claim 10 wherein said (meth)acrylate comprises butyl acrylate.

12. A composition as defined in Claim 1 wherein said crosslinked styrenic resin is crosslinked polystyrene.

13. A composition as defined in Claim 1 wherein said crosslinked styrenic resin is crosslinked styrene-acrylonitrile copolymer.

-29- 337-2177 (8CT-4903)

14. A composition as defined in Claim 1 wherein the polyetherimide ester copolymer (A) is present in an amount of from about 1 to about 99 parts by weight to, correspondingly, from about 99 to about 1, parts by weight of aromatic polyester (B), the rubbery interpolymer (C) is present in an amount of from about 5 to about 95 parts by weight to, correspondingly, from about 95 to about 5 parts by weight of (A) and (B) taken together.

15. A composition as defined in Claim 14 wherein rubbery interpolymer (C) is present in an amount of from about 20 to about 80 parts by weight to, correspondingly, from about 80 to about 20 parts by weight of (A) and (B) taken together.

16. An article comprising a thermoplastic elastomeric composition as defined in Claim 1.

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