CA1250690A - Thermoplasatic polyetherimide ester elastomers - Google Patents
Thermoplasatic polyetherimide ester elastomersInfo
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- CA1250690A CA1250690A CA000493896A CA493896A CA1250690A CA 1250690 A CA1250690 A CA 1250690A CA 000493896 A CA000493896 A CA 000493896A CA 493896 A CA493896 A CA 493896A CA 1250690 A CA1250690 A CA 1250690A
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Abstract
THERMOPLASTIC POLYETHERIMIDE ESTER ELASTOMERS
ABSTRACT OF THE DISCLOSURE
Novel polyetherimide esters are prepared from diols, dicarboxylic acids and polyoxyalkylene diimide diacids and novel modified polyetherimide esters are prepared from diols, dicarboxylic acids and a combination of polyoxyalkylene diimide diacids and dimer acid. These compositions have many excellent properties which make them particularly useful for extrusion and molding applications.
ABSTRACT OF THE DISCLOSURE
Novel polyetherimide esters are prepared from diols, dicarboxylic acids and polyoxyalkylene diimide diacids and novel modified polyetherimide esters are prepared from diols, dicarboxylic acids and a combination of polyoxyalkylene diimide diacids and dimer acid. These compositions have many excellent properties which make them particularly useful for extrusion and molding applications.
Description
~CV 04220 T~lERMOPLASTIC POl~YETHERIMIDE :E:SI'ER ELASTOMERS
The present invention relates to n~uel thermD-plastic elastomers having excellent stress-strain properties, low tensile ~et, high melting temperatures and/or excellent rtrength/toughness characteristics as well as superior flexibility whi~h are especially ~uitable for molding and extrusiDn applications. Spe~
~ifically, novel polyetherimide esters having the above-mentioned properties have been prepared fr~m one or more diols, one or more dicarboxyli~ acids and, mDst importantly, one or more high ~olecular weight polyoxyalkylene diimide diacids.
Polyether ester imides are well known having been described in numerous publications and patents includ-ing for ex~mple, ~onnre et al, "Synthesis and Study of Various Reactive Oligmers and of Poly(ester-imide--ether) 6, ~uropean Pol ~ Vol. 16, pp.
909-916, October 12, 1979; and in Xlui~er et al, U.S.
Patent No. 3,274,1S9 and Wolfe ~r~, U.S. Patent Nos.
4,371,692 and 4,371,693, respecti~ely. However, none of ~he prior art references tea~h or suggest the novel poly(etherimide ester~ compositions ~f the present invention. Fur~hermore, none of these references pro-vide polyetherimide ester resins havin~ the excellent physical properties, including hi~h melting point and ~xcellent flexibili~y, as mentioned above, c~mbined with the rapid crystallizatiDn rate and excellent moldability characteristics of the novel polyether-imide esters of the present inventiDn.
Specifically t applicants ha~e now found a novel 3D class of poly(e~herimide e~ter~ elas~omers which are particularly ~uited for molding and/or extrusion applications and which are ~haracterized a~ ~aving one or more of the following enhanced properti~s: ~ress-~train resistance, toughness/~trength, and tPnsile set ~S~6~
8CV O~Z20 at low flexural modulus combined with rapid crystallization rates and excellent moldability as demonstrated by short cycle times and good mold releasability, respectively~
I~ is an object of the present invention to pro~ide copolyetherimide esters which have improved thermal and oxidative stability without a loss in other physical properties.
It is also an object of the present invention to prcvide copolyetherimide e~ters having improved solvent resistance without sacrificing the superior flexibility of the polyetherimide ester.
Finally, it is an object of the present invention to provide copolyetherimide esters having a high melting point and improved crystallization rates combined with excellent flexibility.
The novel poly(etherimide esters) of the present invention may be either random or block and are prepared by conventional processes from a) one or more diols, b) one or more dicarboxylic acids and c) one or more polyoxyalkylene diimide diacids.
Preferred poly(etherimide esters) compositions encompassed by the present invention may be prepared from a) one or more C2 - C15 aliphatic and/or cycloaliphatic diols, b) one or more C~ - C16 aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids or ester derivatives thereof and c) one or more polyoxyalkylene diimide diacids. The amount of polyoxyalkylene diimide diacid employed is generally dependent upon the ~25~6~
desire~ properties of the resultant polyetherimide ester. In general, the wei~ht ratio of polyoxyalkylene diimide diacid (c) to dicaxboxylic acid (b) is from about 0.25 to 2.0, preferably ~rom about 0.4 to about 1.4. Finally, the compositions may contain and preferably do contain additional stabilizers for even greater stabilization and low temperature impact strength.
It has now also been discovered that modified copolyetherimide esters having improved thermal and oxidative stability, solvent resistance and crystallization and flexibility characteristics can be prepared by conventional processes ~rom a) one or more diols, b) one or more dicarboxylic acids and c) a combination of i) one or more polyoxylakylene diimide diacids and ii) one or more dimer acids, wherein the dimer acid is present in an amount of from about 5 to about 40 weight percent based on the combined weight of ( i ) and ~ii). Pre~erred modified copolyetherimides ester compositions encompassed by the present invention may be prepared ~rom a) one or more C2 - Cl5 aliphatic and/or cycloaliphatic diols, b) one or more C4 - Cl6 aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids or ester derivatives thereof and c) a combination of i) a polyoxyalkenylene diimide diacid and ii) a dimer acid wherein the dimer acid is present in an amvunt of from about 15 to abvut 30 weight percent based on the combined weight of (i) and (ii). The speci~ic amounts o~ i) polyoxyalkylene diimide diacid and ii) dimer acid employed in the practice of the present invention is generally dependent upon the desired properties of 8CV 0~220 the resultant modified polyetherimide ester. In general, the weight ratio of (c) the combination of i) polyoxyalkylene diimide diacid and ii) dimer acid to dicarboxylic acid (b) is from about 0.25 to 2.0, preferably from about 0.4 to about 114.
Finally, the compositions may contain and preferably do contain additional stabilizers for even greater stabilization and low temperature impact strength.
Suitable diols (a) for use in preparing the compositions of the present invention include saturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds as well as aromatic dihydroxy compounds.
These diols are preferably of a low molecular weight, ie. having a molecular weight of about 250 or less~
When used herein, the term "diols" 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 ~e given the acetates of the diols as well as for example ethylene oxide or ethylene carbonate for ethylene glycol.
Preferred saturated and unsatruated alphatic and cycloaliphatic diols are those having from about 2 to 15 carbon atoms.
Exemplary of these diols there may be given ethyleneglycol, propanediol, butanediol, pentanediol, 2-methyl propanediol, 2,2~dimethyl propanediol, hexanediol, decanediol, 1,2-, 1,3-and 1,4- dihydroxy cyclohexane; 1,2-, 1,3-~5~
8CV ~4220-- 5 --and l,~cyclohexane di~ethanol; butene diol;
hexene diol, etc. Especially preferred are 1,4-butanediol and mixtures thereof with hexanediol or butenediol, most preferably 1,4-butanediol.
Aromatic diols suitable for use in the practice of the present invention are generally those having from 6 to about 15 carbon atoms. Included among the aromatic dihydroxy compounds are resorcinol; hydroquinone: 1,5-dihydroxy napthalene; 4,4'-dihydroxy diphenyl;
bis~p-hydroxy phenyl)methane and bis~p-hydroxy phenyl) 2,2-propane.
Especially preferred diols are the saturated aliphatic diols, mixtures thereof and mixtures of a saturated diol(s) with an unsaturated diol( 5 ), wherein each diol contains from 2 to about 8 carbon atoms. W~lere more than 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 ~. ~s mentioned above, the preferred compositions are those in which 1,4- butanediol is present in a predominant amount, most preferably when 1,4-butanediol is the only diol.
Dicarboxylic acids (b) which are suitable for use in the practice of the present invention are aliphatic, clycoaliphatic, and/or aromatic dicarboxylic acids. These acids are preferably of a low molecular 8CV 0~220 weight, i.e., having a molecular weight vf less than ~b~ut 3~0; however, higher molecular weight dicarb~xyl-ic acids, especially dimer acids, may al~o be used.
~he erm ~aicarboxylic acids~ as used herein, includes equivalents ~f dicarboxylic a~ids having two func-tio~al çarboxyl groups which perform substantially like dicar~oxylic acids in rea~tion with glycols and diols in forming polyester p~lymers. These equivalents include esters and ester-forming derivatives, such as lQ acid halides and anhydrides. The molecular weight preference, mentioned a~ove, pertains to the acid and nDt to its equivalent ester or ester-forming deriva-tive. Thu~, an ester ~f a dicarboxylic acid having a molecular weight greater than 300 or an acid equiva-lent of a dicarboxylic acid having a molecular weightgreater than 300 are included provided the acid has a molecular weight below abDut 300. Additionally, the dicarboxylic acids may c~ntain any su~stitue~
group(s) or combinations which do not substantially interfere wikh the p~lymer formation and use of the polymer of this invention.
Aliphatic dicarb~xylic acids, as the term is used herein, refers to carboxylic acids having two carboxyl groups each of which is attached to a satura~ed carbon atom. If the carbon atom t~ which the carboxyl group is attached is ~aturated and is in a ring, the acid is cycloaliphatic.
Aromatic dicarboxylic a~ids, as the term is used herein, are dicarboxylic acids having two carboxyl groups each ~f which i~ attached to a carbo~ atom in an isolated or fused benzene ring system. It is no~
necessary that both functional carboxyl groups be attached to the same aromatic riny and where ~ore than one ring ic pre~ent, they oan be joined by aliphatic or aromatic dival~nt radical6 or divalent radical~
such as ~O- or -SO2-.
6~
7 _ Representative aliphatic an~ ~ycloaliphatlc acids which can be used for this invention are ~ebacic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic aci~, 1,4-cyclohexane clicarb~xyli~ acid, 5 adipic acid, glutaric acid, ~uccinit acid, Dxalic acid, azelaic acid, diethylmalDnic acid, allylmalonic acid, dimer acid, 4-~yclohexene-1,2-- dicarb~xylic acid, 2-ethyl~uberic acid, tetramethylsuccinic acid, cyclopentanedicarboxylic acid, decahydro-1,5-naph-thalene dicarboxylic a~idt 4,4' bicyclohexyl dicar-boxylic acid, decahydro-2,6-naphthalene dicarb~xylic ~cid, 4,4 methylenebis(~yclohexane carboxylic acid), 3,4-furan dicarboxylic acid, and l,l-cyclobutane dicar-boxylic acid. Preferred aliphatic acids are cyclo-hexane dicarboxylic acids,~ebacic acid, dimer acid,glutaric acid, azelaic acid and adipic acid.
Representative ~romatic ~icarboxylic acids which can be used include terephthalic, phthalic and iso-phthalic acids, bi-benzoic acid, su~stituted dicarboxy compounds with two benzene nuclei such as bi~(p-car~-oxyphenyl) methane, oxybis(benzoic acid), ethylene-1,2- bis-(p-oxybenzoic acid~, l,5 naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, ~,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-~ulfonyl dibenzoic acid, and halo ~nd Cl-Cl2 alkyl, alkoxy, and aryl ring substitution deri~atives thereof. Hydroxy acids ~uch as p~ B-hydroxyethoxy~-benzoic acid can also be used provided an aromatic dicarboxylic acid is al~o present.
Pre~erred dicarboxylic acids for ~he preparation ~f the polyetherimide esters of the pre~ent invention are the ~romati~ di~arboxylic ac-d~, mixtures thereof and mixtures of ~ne sr more dicarb~xylic acid with an aliphatic and/or cycloaliphatic di~arboxylic acid, most prefera~ly the aromatic dicarboxylic acids.
8CV 0~220 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.
Finally, where mixtures of dicarboxylic acids are employed in the practice of the present invention, 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. As mentioned above, the preferred compositions are those in which dimethylterephthalate is the predominant dicarboxylic acid, most preferably when dimethylterephthalate is the only dicarboxylic acid.
The third component to be used in the practice of the present invention to produce the modified copoyletherimide esters is a combination (c) of i ) polyoxyalkylene diimide diacid and ii) dimer acid wherein the amount of dimer acid present is from about 5 to about 40 weight percent, preferably from about 15 to about 30 weight percent, based on the combined weight of (i) and ~ii).
Polyoxyalkylene diimide diacids (c) or (c) (i) suitable for use herein are high molecular weight diimide diacids wherein the average molecular weight is greater than about 700, most preferably greater than about 900. They may be prepared by the imidization reaction of one or more tricarboxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl group which must be esterificable and preferably is nonimidizable ~2~
- 9 - 8CV042~0 with a high molecular weight polyoxylalkylene diamine.
In general, the polyoxylalkylene dlimide diacids useful herein may be characterized by the following formula:
O O
R'OOC-R \ N-G-N ~ R-COOR' \ / \/
C / C
O O
where each R is independently a trivalent organic radical, preferably a C2 to C20 aliphatic, aromatic, or cycloali.phatic trivalent organic radical; each R' is independently hydrogen or a monovalent organic radical preferably selected from the group consisting of Cl to C6 aliphatic and cycloaliphatic radicals and C6 to C12 aromatic radicals, e.g. benzyl, mos-t preferably hydrogen; and G is the radical remaining after the removal of the terminal (or as nearly terminal as possible) hydroxy groups of a long chain either glycol having an average molecular weight of from about 6QQ to Y~
~Lo2d 5iq;~ 690 ~CV 04220 about 12000, preferably from about 900 to about 4000, and a carbon~to-oxygen ratio of from about 1.8 to about 4.3.
Representative long chain ether glycols from which the polyoxyalkylene diamine 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, including propylene oxide terminated poly(ethylene ether)glycol; and random or block copolymers o~ tetrahydrofuran with minor a~ounts of a second mono~er 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 and/or propylene oxide.
In general, the polyoxyalkylene dia~ines use.ful within the scope of the ~resent invention will have an ~, ~verage molecular of from abDut 600 to 12000, prefer-ably from ab~ut 900 ts about 4000.
The tricarb~xylic romponent may be alm~st any carb~xylic acid anhydride c~ntaining an additi~nal carboxylic gr~up or the corresp~ndiny acid thereof containing two imide-forming ~icinal carboxyl groups in lieu of the anhydride gr~up. Mixtures thereof are als~ suitable. The addi~ional carboxylic group must be esterifiable and preferably is substantiQlly n~n-imidizable.
Further, while trimellitic anhydride is preferredas the tricarb~xylic comp~nent, any of a number of ~ui~able tricarboxylic acid constituents will o~cur to th~se skilled in the art in~luding 2,6,7 naphthalene tricarb~xylic anhydride; 3,3',4 diphenyl tricarb~xylic anhydride; 3,3',4 benzophenone tricarboxylic ~nhydr-ide; 1,3,4 cyclopentane tricarboxylic anhydride;
The present invention relates to n~uel thermD-plastic elastomers having excellent stress-strain properties, low tensile ~et, high melting temperatures and/or excellent rtrength/toughness characteristics as well as superior flexibility whi~h are especially ~uitable for molding and extrusiDn applications. Spe~
~ifically, novel polyetherimide esters having the above-mentioned properties have been prepared fr~m one or more diols, one or more dicarboxyli~ acids and, mDst importantly, one or more high ~olecular weight polyoxyalkylene diimide diacids.
Polyether ester imides are well known having been described in numerous publications and patents includ-ing for ex~mple, ~onnre et al, "Synthesis and Study of Various Reactive Oligmers and of Poly(ester-imide--ether) 6, ~uropean Pol ~ Vol. 16, pp.
909-916, October 12, 1979; and in Xlui~er et al, U.S.
Patent No. 3,274,1S9 and Wolfe ~r~, U.S. Patent Nos.
4,371,692 and 4,371,693, respecti~ely. However, none of ~he prior art references tea~h or suggest the novel poly(etherimide ester~ compositions ~f the present invention. Fur~hermore, none of these references pro-vide polyetherimide ester resins havin~ the excellent physical properties, including hi~h melting point and ~xcellent flexibili~y, as mentioned above, c~mbined with the rapid crystallizatiDn rate and excellent moldability characteristics of the novel polyether-imide esters of the present inventiDn.
Specifically t applicants ha~e now found a novel 3D class of poly(e~herimide e~ter~ elas~omers which are particularly ~uited for molding and/or extrusion applications and which are ~haracterized a~ ~aving one or more of the following enhanced properti~s: ~ress-~train resistance, toughness/~trength, and tPnsile set ~S~6~
8CV O~Z20 at low flexural modulus combined with rapid crystallization rates and excellent moldability as demonstrated by short cycle times and good mold releasability, respectively~
I~ is an object of the present invention to pro~ide copolyetherimide esters which have improved thermal and oxidative stability without a loss in other physical properties.
It is also an object of the present invention to prcvide copolyetherimide e~ters having improved solvent resistance without sacrificing the superior flexibility of the polyetherimide ester.
Finally, it is an object of the present invention to provide copolyetherimide esters having a high melting point and improved crystallization rates combined with excellent flexibility.
The novel poly(etherimide esters) of the present invention may be either random or block and are prepared by conventional processes from a) one or more diols, b) one or more dicarboxylic acids and c) one or more polyoxyalkylene diimide diacids.
Preferred poly(etherimide esters) compositions encompassed by the present invention may be prepared from a) one or more C2 - C15 aliphatic and/or cycloaliphatic diols, b) one or more C~ - C16 aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids or ester derivatives thereof and c) one or more polyoxyalkylene diimide diacids. The amount of polyoxyalkylene diimide diacid employed is generally dependent upon the ~25~6~
desire~ properties of the resultant polyetherimide ester. In general, the wei~ht ratio of polyoxyalkylene diimide diacid (c) to dicaxboxylic acid (b) is from about 0.25 to 2.0, preferably ~rom about 0.4 to about 1.4. Finally, the compositions may contain and preferably do contain additional stabilizers for even greater stabilization and low temperature impact strength.
It has now also been discovered that modified copolyetherimide esters having improved thermal and oxidative stability, solvent resistance and crystallization and flexibility characteristics can be prepared by conventional processes ~rom a) one or more diols, b) one or more dicarboxylic acids and c) a combination of i) one or more polyoxylakylene diimide diacids and ii) one or more dimer acids, wherein the dimer acid is present in an amount of from about 5 to about 40 weight percent based on the combined weight of ( i ) and ~ii). Pre~erred modified copolyetherimides ester compositions encompassed by the present invention may be prepared ~rom a) one or more C2 - Cl5 aliphatic and/or cycloaliphatic diols, b) one or more C4 - Cl6 aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids or ester derivatives thereof and c) a combination of i) a polyoxyalkenylene diimide diacid and ii) a dimer acid wherein the dimer acid is present in an amvunt of from about 15 to abvut 30 weight percent based on the combined weight of (i) and (ii). The speci~ic amounts o~ i) polyoxyalkylene diimide diacid and ii) dimer acid employed in the practice of the present invention is generally dependent upon the desired properties of 8CV 0~220 the resultant modified polyetherimide ester. In general, the weight ratio of (c) the combination of i) polyoxyalkylene diimide diacid and ii) dimer acid to dicarboxylic acid (b) is from about 0.25 to 2.0, preferably from about 0.4 to about 114.
Finally, the compositions may contain and preferably do contain additional stabilizers for even greater stabilization and low temperature impact strength.
Suitable diols (a) for use in preparing the compositions of the present invention include saturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds as well as aromatic dihydroxy compounds.
These diols are preferably of a low molecular weight, ie. having a molecular weight of about 250 or less~
When used herein, the term "diols" 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 ~e given the acetates of the diols as well as for example ethylene oxide or ethylene carbonate for ethylene glycol.
Preferred saturated and unsatruated alphatic and cycloaliphatic diols are those having from about 2 to 15 carbon atoms.
Exemplary of these diols there may be given ethyleneglycol, propanediol, butanediol, pentanediol, 2-methyl propanediol, 2,2~dimethyl propanediol, hexanediol, decanediol, 1,2-, 1,3-and 1,4- dihydroxy cyclohexane; 1,2-, 1,3-~5~
8CV ~4220-- 5 --and l,~cyclohexane di~ethanol; butene diol;
hexene diol, etc. Especially preferred are 1,4-butanediol and mixtures thereof with hexanediol or butenediol, most preferably 1,4-butanediol.
Aromatic diols suitable for use in the practice of the present invention are generally those having from 6 to about 15 carbon atoms. Included among the aromatic dihydroxy compounds are resorcinol; hydroquinone: 1,5-dihydroxy napthalene; 4,4'-dihydroxy diphenyl;
bis~p-hydroxy phenyl)methane and bis~p-hydroxy phenyl) 2,2-propane.
Especially preferred diols are the saturated aliphatic diols, mixtures thereof and mixtures of a saturated diol(s) with an unsaturated diol( 5 ), wherein each diol contains from 2 to about 8 carbon atoms. W~lere more than 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 ~. ~s mentioned above, the preferred compositions are those in which 1,4- butanediol is present in a predominant amount, most preferably when 1,4-butanediol is the only diol.
Dicarboxylic acids (b) which are suitable for use in the practice of the present invention are aliphatic, clycoaliphatic, and/or aromatic dicarboxylic acids. These acids are preferably of a low molecular 8CV 0~220 weight, i.e., having a molecular weight vf less than ~b~ut 3~0; however, higher molecular weight dicarb~xyl-ic acids, especially dimer acids, may al~o be used.
~he erm ~aicarboxylic acids~ as used herein, includes equivalents ~f dicarboxylic a~ids having two func-tio~al çarboxyl groups which perform substantially like dicar~oxylic acids in rea~tion with glycols and diols in forming polyester p~lymers. These equivalents include esters and ester-forming derivatives, such as lQ acid halides and anhydrides. The molecular weight preference, mentioned a~ove, pertains to the acid and nDt to its equivalent ester or ester-forming deriva-tive. Thu~, an ester ~f a dicarboxylic acid having a molecular weight greater than 300 or an acid equiva-lent of a dicarboxylic acid having a molecular weightgreater than 300 are included provided the acid has a molecular weight below abDut 300. Additionally, the dicarboxylic acids may c~ntain any su~stitue~
group(s) or combinations which do not substantially interfere wikh the p~lymer formation and use of the polymer of this invention.
Aliphatic dicarb~xylic acids, as the term is used herein, refers to carboxylic acids having two carboxyl groups each of which is attached to a satura~ed carbon atom. If the carbon atom t~ which the carboxyl group is attached is ~aturated and is in a ring, the acid is cycloaliphatic.
Aromatic dicarboxylic a~ids, as the term is used herein, are dicarboxylic acids having two carboxyl groups each ~f which i~ attached to a carbo~ atom in an isolated or fused benzene ring system. It is no~
necessary that both functional carboxyl groups be attached to the same aromatic riny and where ~ore than one ring ic pre~ent, they oan be joined by aliphatic or aromatic dival~nt radical6 or divalent radical~
such as ~O- or -SO2-.
6~
7 _ Representative aliphatic an~ ~ycloaliphatlc acids which can be used for this invention are ~ebacic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic aci~, 1,4-cyclohexane clicarb~xyli~ acid, 5 adipic acid, glutaric acid, ~uccinit acid, Dxalic acid, azelaic acid, diethylmalDnic acid, allylmalonic acid, dimer acid, 4-~yclohexene-1,2-- dicarb~xylic acid, 2-ethyl~uberic acid, tetramethylsuccinic acid, cyclopentanedicarboxylic acid, decahydro-1,5-naph-thalene dicarboxylic a~idt 4,4' bicyclohexyl dicar-boxylic acid, decahydro-2,6-naphthalene dicarb~xylic ~cid, 4,4 methylenebis(~yclohexane carboxylic acid), 3,4-furan dicarboxylic acid, and l,l-cyclobutane dicar-boxylic acid. Preferred aliphatic acids are cyclo-hexane dicarboxylic acids,~ebacic acid, dimer acid,glutaric acid, azelaic acid and adipic acid.
Representative ~romatic ~icarboxylic acids which can be used include terephthalic, phthalic and iso-phthalic acids, bi-benzoic acid, su~stituted dicarboxy compounds with two benzene nuclei such as bi~(p-car~-oxyphenyl) methane, oxybis(benzoic acid), ethylene-1,2- bis-(p-oxybenzoic acid~, l,5 naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, ~,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-~ulfonyl dibenzoic acid, and halo ~nd Cl-Cl2 alkyl, alkoxy, and aryl ring substitution deri~atives thereof. Hydroxy acids ~uch as p~ B-hydroxyethoxy~-benzoic acid can also be used provided an aromatic dicarboxylic acid is al~o present.
Pre~erred dicarboxylic acids for ~he preparation ~f the polyetherimide esters of the pre~ent invention are the ~romati~ di~arboxylic ac-d~, mixtures thereof and mixtures of ~ne sr more dicarb~xylic acid with an aliphatic and/or cycloaliphatic di~arboxylic acid, most prefera~ly the aromatic dicarboxylic acids.
8CV 0~220 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.
Finally, where mixtures of dicarboxylic acids are employed in the practice of the present invention, 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. As mentioned above, the preferred compositions are those in which dimethylterephthalate is the predominant dicarboxylic acid, most preferably when dimethylterephthalate is the only dicarboxylic acid.
The third component to be used in the practice of the present invention to produce the modified copoyletherimide esters is a combination (c) of i ) polyoxyalkylene diimide diacid and ii) dimer acid wherein the amount of dimer acid present is from about 5 to about 40 weight percent, preferably from about 15 to about 30 weight percent, based on the combined weight of (i) and ~ii).
Polyoxyalkylene diimide diacids (c) or (c) (i) suitable for use herein are high molecular weight diimide diacids wherein the average molecular weight is greater than about 700, most preferably greater than about 900. They may be prepared by the imidization reaction of one or more tricarboxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl group which must be esterificable and preferably is nonimidizable ~2~
- 9 - 8CV042~0 with a high molecular weight polyoxylalkylene diamine.
In general, the polyoxylalkylene dlimide diacids useful herein may be characterized by the following formula:
O O
R'OOC-R \ N-G-N ~ R-COOR' \ / \/
C / C
O O
where each R is independently a trivalent organic radical, preferably a C2 to C20 aliphatic, aromatic, or cycloali.phatic trivalent organic radical; each R' is independently hydrogen or a monovalent organic radical preferably selected from the group consisting of Cl to C6 aliphatic and cycloaliphatic radicals and C6 to C12 aromatic radicals, e.g. benzyl, mos-t preferably hydrogen; and G is the radical remaining after the removal of the terminal (or as nearly terminal as possible) hydroxy groups of a long chain either glycol having an average molecular weight of from about 6QQ to Y~
~Lo2d 5iq;~ 690 ~CV 04220 about 12000, preferably from about 900 to about 4000, and a carbon~to-oxygen ratio of from about 1.8 to about 4.3.
Representative long chain ether glycols from which the polyoxyalkylene diamine 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, including propylene oxide terminated poly(ethylene ether)glycol; and random or block copolymers o~ tetrahydrofuran with minor a~ounts of a second mono~er 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 and/or propylene oxide.
In general, the polyoxyalkylene dia~ines use.ful within the scope of the ~resent invention will have an ~, ~verage molecular of from abDut 600 to 12000, prefer-ably from ab~ut 900 ts about 4000.
The tricarb~xylic romponent may be alm~st any carb~xylic acid anhydride c~ntaining an additi~nal carboxylic gr~up or the corresp~ndiny acid thereof containing two imide-forming ~icinal carboxyl groups in lieu of the anhydride gr~up. Mixtures thereof are als~ suitable. The addi~ional carboxylic group must be esterifiable and preferably is substantiQlly n~n-imidizable.
Further, while trimellitic anhydride is preferredas the tricarb~xylic comp~nent, any of a number of ~ui~able tricarboxylic acid constituents will o~cur to th~se skilled in the art in~luding 2,6,7 naphthalene tricarb~xylic anhydride; 3,3',4 diphenyl tricarb~xylic anhydride; 3,3',4 benzophenone tricarboxylic ~nhydr-ide; 1,3,4 cyclopentane tricarboxylic anhydride;
2,2',3 diphenyl tricarb~xylic ~nhydride; diphenyl ~ulfone - 3,3',4 tricarboxylic anhydride, ethylene tricarboxylic anhydride; 1,2,5 napthalene tricarb-oxylic anhydride; 1,2,4 butane tricarb~xylic anhyd-ride; diphenyl isopr~pylidene 3,3',4 tricarboxylic anhydride; 3,4 dicarbvxyphenyl 3'-carboxylphenyl eth~r anhydride; 1,3,4 cyclohexane tricarboxylic anhydride, et~. These tricarboxylic acid materials can be chara~terized by the following formula:
/\
III ~'OOC-R ~ / O
where R i~ a trivalent crganic radical, preferably a C2 to C20 aliphatic, aromatic, or ~yclo~liphatic tri-3D valent organic radical and R' is preferably hydr~gen or a m~n~v21ent organic radical pre~era~ly ~ele~ted from the qroup ~nsisting of Cl to C~ aliphatic and/~r , .
8CV 0~220 cycloaliphatic r~dicals and C6 to Cl~
aromatic radicals, e.g. benzy; most preferably hydrogen.
Briefly, these polyoxyalkylene diimide diacids may be prepared by known imidi~ation reactions including melt synthesis or by synthesizing in a solvent system. Such reactions will generally occu~ at temperatures of from 100C. to 300C., preferably at from about 150C. to about 250C.
while drawing off water or in a solvent system at the reflux temperature of the solvent or azeotropic (solvent) mixture.
Although the weight ratio of the above ingredients is not critical, it is preferred in the unmodified composition that the diol be present in at least a molar equivalent amount, preferably a molar excess, most preferably at least 150 mole ~, basecl on the moles of dicarboxylic acid ~b) and polyoxylakylene diimide diacid (c) combined. Such molar excess of diol will allow for optimal yields, based on the amount of acids, while accounting for the loss of diol during esterification/condensation.
Furt~er, while the weight ratio of dicarboxylic acid (b) to polyoxyalkylene diimide diacid (c) is not critical to form the novel polyetherimide esters of the present invention, preferred compositions are those in which the weight ratio of the polyoxyalkylene diimide diacid (c~ to dicarboxylic acid (b) 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 properties of the resultant polyetherimide ester.
In general, the lower the ratio of polyoxyalkylene diimide diester to dicarboxylic acid the hetter the strength, crystallization aIId distortion heat properties of the polymer. Alternatively, the higher the ratio, the better the flexibility, tensile set and low temperature impact characteristics.
In its preferred embodiments, the unmodified compositions of the present invention will comprise the reaction product of dimethylterephthalate, optimally with up to 40 percent mole ~ of another dicarboxylic acid; 1,4-butanediol, optionally with up to 40 mole % of another saturated or unsaturated aliphatic and/or cycloaliphatic diol; and a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene dimine of molecular weight of from about 600 to about 120~0, preferably from about 900 to about 4000, and trimellitic anhydride. In its most preferred embodiments, the diol will be 100 mole ~ 1,4- butanediol and the dicarboxylic acid 100 mole % dimethylterephthalate.
Dimer acids (ii) useful in the preparation of the modified copolyetherimide esters of the present invention are themselves prepared by the dimerization of unsaturated fatty acids of 18 carbons. Exemplary of fa~ty acids from which they are prepared there may be given oleic acid, linoleic acid and linolenic acid. The preparation and structure of dimer acid is described in Journal of the American Oil Chemists Society, 39, 535-545 (1962), Journal of the American Chemcial Society 66, 84 (1944) and United States Patent Number 2,347,562. Suitable dimer 8CV ~4220 acid may be employed in its unhydrogenat~d or hydrogenated form and include the acid functioning derivatives thereof.
Several grades of dimer acid are available commercially which vary in mono~er and trimer content. Inclusive of suitable commercial dimer acids there may be given those available fxom Emery Industries under the tradenames EMPOL~ 010 (a ~ "".....
hydrogenated dimer acid) and EMPOL 1014. EMPOL 1010 is reported as typically containing 97% dimer acid, 3 trimer acid and essentially no monobasic acid and extremely low unsaturation, whereas EMPOL 1014 is typified as containing 95~, 4~ and 1% of dimer, trimer and monobasic acids respectively. Also available are the dimer acids sold under the tradename HYSTRENE from the Humko Products Division of Witco Chemical Corporation, especially HYSTRENE 3695 which typically contain 95% dimer acid and a weight ratio of dimer to trimer of 36:1. Preferred grades are substantially free of such monomer and trimer fractions, most preferably less than 5~ by weight, and are fully saturated, or substantially so.
~ here desirable, the dimer acid member may be substantially freed of monomer and trimer fractions by molecular distillation or other suitable means. In general, the dimer acid exists in the copolyetherimide ester as a soft or rubbery segment and accordingly dimer acids of relatively high molecular weight (preferably greater than about 500) are preferred 50 that the modified copolyetherimide esters are resilient, but do not deform until relatively high temperatures are reached.
The modified copolyetherimide esters may be prepared having high melting temperatures, faster 8C~ 04220 crystalli~ation rates and greater flexlbility than unmodified copolyetherimide esters by incorporating therein dimer acid. Specifically, copolyetherimlde esters having comparable levels of polyoxyalkylene diimide diacid incorporated therein have less flexibility/ resilience and impact propertiesl including, for example, low temperature impact.
Alternatively, unmodified composition having essentially the same flexibility properties, resilience and so forth suffer from greater susceptabili~y to oxidative and thermal degradation as well as manifest poorer solvent resistance, as a c~nsequence of the higher levels of polyether component in the polymer. Thus by the practice of applicant's inventions one is able to achieve compositions of greater flexibility, crystalization rate solvent resistance and thermal and oxidative stability.
In general, the benefits of the modified copolyetherimide esters can be achieved by incorporating into the copolyetherimide ester from about 5 to about 40 weight percent, preferably from about 15 to about 30 weight percent, based on the combined weight of dimer acid and polyoxyalkylene diimide diacid of dimer acid.
Although the weight ratio of the above ingredients 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 %, based on the moles of dicarboxylic acid (b) and the combination (c) of i) polyoxyalkylene diimide diacid and ii) dimer acid, combined. Such molar excess of diol will allow for optimal yields~
based on the amount of acids, while accounting for the ~ $~ 8CV 0~220 los~ of diol during esterification/condensation.
Further, whi 1P the amount by which the combination(s) of (i) polyoxyalkylene diimide diacid and ii) dimer acid incorporated into the polymer is not critical to make the modified copolyetherimide esters of the present invention, it is preferred that the combination (c) be present in weight ratio to dicarboxylic acid (b) of from about 0.25 to about 2, preferably from about 0.4 to 1.4. The actual weight ratio employed will be dependent upon the amount of dimer acid used, the specific polyo~yalkylene diimide diacid used and more importantly, the desired physical and chemical properties of the resultant polyetherimide ester. In general, the lo~er the ratio of the combination (c) of (i) polyoxyalkene diimide diaced (ii) and dimer acid to dicarboxylic acid the better the strength, crystallization and heat distortion properties of the polymer.
Alternatively, the higher the ratio, the better the flexibility, tensile set and low temperature impact characteristics.
In its preferred embodiments, the modified copolyetherimide ester compositions of the present invention will comprise the reaction product of dimethylterephthalate, optimally with up to 40 mole of another dicarboxylic acid; 1,4-butanediol, optionally with up to 40 mole % of another saturated or unsaturated aliphatic and/or cycloaliphatic diol;
and a combination of i) a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene diamine of molecular weight of from about 600 to 12000, preferably from about 900 to about 4000 and ii) dimer acid in an amount of from about 10 to about 40~ by weight, most preferably from about 15 to about 30~
~25~
.~
by weight based on the combined weight of ~i) and (ii), and optionally trimellitic anhydride. In its most preferred embodiments, the diol will be 100 mole ~ 1,4- butanediol and the dicarboxylic acid 100 mole ~ dimethylterephthalate.
The novel polyetherimide esters described herein may be prepared by conventional esterification/condensation reactions for the production of polyesters. Exemplary of the processes that may be practiced are set forth in, for example, United States Patent Numbers 3,023,192; 3,761,109; 3,651,014; 3,563,653 and 3,801,547. Additionally, these compositions may be prepared by such processes and other known processes to effect random copolymers, block copolymers or hybrids thereof wherein both random and block units 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 separate catalysts or catalyst systems may be used, one for ester interchange and one for polycondensation, it is preferred, where appropriate, to use one catalyst or catalyst system for both. In those instances where two separate catalysts are used, it is preferred and advantageous to render the ester-interchange catalyst ineffective following the com-, . . .
.
. .
"
~'~5~ 8CV 0~220 - lB - .
pletion of the precondensation reaction ~y means of known catalys~ inhibi~ors or quenchers, in particular, phosphorus compounds ~uch as phosphoric acid, phos-phenic acid, phosph~nic acid and the alkyl or aryl esters or salts thereof, in order to increase the thermal ~tability of the resultant polymer.
~ x~mplary of the suitable kno~l ~a alysts there may be given the acetates, casboxylates, hydroxides, ~xides, alcoholates ~r ~rganic comp:Lex compounds of 1~ zinc, manganese, antimony, ~obalt, lead, ~alcium and the alkali metals insofar as these compounds are soluble in the reaction mixture. 5pecific examples include, zinc acetate, calcium acetate and combina-tions thereof with antimony tri-~xide and the li~e.
These catalysts as well as additional useful catalysts are described in United States Patent Nu~ers 2,465,319; 2,534,028; 2,850,483;. -2,892,815; :3,937,1~0; 2,998,412; 3,047,539;
/\
III ~'OOC-R ~ / O
where R i~ a trivalent crganic radical, preferably a C2 to C20 aliphatic, aromatic, or ~yclo~liphatic tri-3D valent organic radical and R' is preferably hydr~gen or a m~n~v21ent organic radical pre~era~ly ~ele~ted from the qroup ~nsisting of Cl to C~ aliphatic and/~r , .
8CV 0~220 cycloaliphatic r~dicals and C6 to Cl~
aromatic radicals, e.g. benzy; most preferably hydrogen.
Briefly, these polyoxyalkylene diimide diacids may be prepared by known imidi~ation reactions including melt synthesis or by synthesizing in a solvent system. Such reactions will generally occu~ at temperatures of from 100C. to 300C., preferably at from about 150C. to about 250C.
while drawing off water or in a solvent system at the reflux temperature of the solvent or azeotropic (solvent) mixture.
Although the weight ratio of the above ingredients is not critical, it is preferred in the unmodified composition that the diol be present in at least a molar equivalent amount, preferably a molar excess, most preferably at least 150 mole ~, basecl on the moles of dicarboxylic acid ~b) and polyoxylakylene diimide diacid (c) combined. Such molar excess of diol will allow for optimal yields, based on the amount of acids, while accounting for the loss of diol during esterification/condensation.
Furt~er, while the weight ratio of dicarboxylic acid (b) to polyoxyalkylene diimide diacid (c) is not critical to form the novel polyetherimide esters of the present invention, preferred compositions are those in which the weight ratio of the polyoxyalkylene diimide diacid (c~ to dicarboxylic acid (b) 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 properties of the resultant polyetherimide ester.
In general, the lower the ratio of polyoxyalkylene diimide diester to dicarboxylic acid the hetter the strength, crystallization aIId distortion heat properties of the polymer. Alternatively, the higher the ratio, the better the flexibility, tensile set and low temperature impact characteristics.
In its preferred embodiments, the unmodified compositions of the present invention will comprise the reaction product of dimethylterephthalate, optimally with up to 40 percent mole ~ of another dicarboxylic acid; 1,4-butanediol, optionally with up to 40 mole % of another saturated or unsaturated aliphatic and/or cycloaliphatic diol; and a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene dimine of molecular weight of from about 600 to about 120~0, preferably from about 900 to about 4000, and trimellitic anhydride. In its most preferred embodiments, the diol will be 100 mole ~ 1,4- butanediol and the dicarboxylic acid 100 mole % dimethylterephthalate.
Dimer acids (ii) useful in the preparation of the modified copolyetherimide esters of the present invention are themselves prepared by the dimerization of unsaturated fatty acids of 18 carbons. Exemplary of fa~ty acids from which they are prepared there may be given oleic acid, linoleic acid and linolenic acid. The preparation and structure of dimer acid is described in Journal of the American Oil Chemists Society, 39, 535-545 (1962), Journal of the American Chemcial Society 66, 84 (1944) and United States Patent Number 2,347,562. Suitable dimer 8CV ~4220 acid may be employed in its unhydrogenat~d or hydrogenated form and include the acid functioning derivatives thereof.
Several grades of dimer acid are available commercially which vary in mono~er and trimer content. Inclusive of suitable commercial dimer acids there may be given those available fxom Emery Industries under the tradenames EMPOL~ 010 (a ~ "".....
hydrogenated dimer acid) and EMPOL 1014. EMPOL 1010 is reported as typically containing 97% dimer acid, 3 trimer acid and essentially no monobasic acid and extremely low unsaturation, whereas EMPOL 1014 is typified as containing 95~, 4~ and 1% of dimer, trimer and monobasic acids respectively. Also available are the dimer acids sold under the tradename HYSTRENE from the Humko Products Division of Witco Chemical Corporation, especially HYSTRENE 3695 which typically contain 95% dimer acid and a weight ratio of dimer to trimer of 36:1. Preferred grades are substantially free of such monomer and trimer fractions, most preferably less than 5~ by weight, and are fully saturated, or substantially so.
~ here desirable, the dimer acid member may be substantially freed of monomer and trimer fractions by molecular distillation or other suitable means. In general, the dimer acid exists in the copolyetherimide ester as a soft or rubbery segment and accordingly dimer acids of relatively high molecular weight (preferably greater than about 500) are preferred 50 that the modified copolyetherimide esters are resilient, but do not deform until relatively high temperatures are reached.
The modified copolyetherimide esters may be prepared having high melting temperatures, faster 8C~ 04220 crystalli~ation rates and greater flexlbility than unmodified copolyetherimide esters by incorporating therein dimer acid. Specifically, copolyetherimlde esters having comparable levels of polyoxyalkylene diimide diacid incorporated therein have less flexibility/ resilience and impact propertiesl including, for example, low temperature impact.
Alternatively, unmodified composition having essentially the same flexibility properties, resilience and so forth suffer from greater susceptabili~y to oxidative and thermal degradation as well as manifest poorer solvent resistance, as a c~nsequence of the higher levels of polyether component in the polymer. Thus by the practice of applicant's inventions one is able to achieve compositions of greater flexibility, crystalization rate solvent resistance and thermal and oxidative stability.
In general, the benefits of the modified copolyetherimide esters can be achieved by incorporating into the copolyetherimide ester from about 5 to about 40 weight percent, preferably from about 15 to about 30 weight percent, based on the combined weight of dimer acid and polyoxyalkylene diimide diacid of dimer acid.
Although the weight ratio of the above ingredients 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 %, based on the moles of dicarboxylic acid (b) and the combination (c) of i) polyoxyalkylene diimide diacid and ii) dimer acid, combined. Such molar excess of diol will allow for optimal yields~
based on the amount of acids, while accounting for the ~ $~ 8CV 0~220 los~ of diol during esterification/condensation.
Further, whi 1P the amount by which the combination(s) of (i) polyoxyalkylene diimide diacid and ii) dimer acid incorporated into the polymer is not critical to make the modified copolyetherimide esters of the present invention, it is preferred that the combination (c) be present in weight ratio to dicarboxylic acid (b) of from about 0.25 to about 2, preferably from about 0.4 to 1.4. The actual weight ratio employed will be dependent upon the amount of dimer acid used, the specific polyo~yalkylene diimide diacid used and more importantly, the desired physical and chemical properties of the resultant polyetherimide ester. In general, the lo~er the ratio of the combination (c) of (i) polyoxyalkene diimide diaced (ii) and dimer acid to dicarboxylic acid the better the strength, crystallization and heat distortion properties of the polymer.
Alternatively, the higher the ratio, the better the flexibility, tensile set and low temperature impact characteristics.
In its preferred embodiments, the modified copolyetherimide ester compositions of the present invention will comprise the reaction product of dimethylterephthalate, optimally with up to 40 mole of another dicarboxylic acid; 1,4-butanediol, optionally with up to 40 mole % of another saturated or unsaturated aliphatic and/or cycloaliphatic diol;
and a combination of i) a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene diamine of molecular weight of from about 600 to 12000, preferably from about 900 to about 4000 and ii) dimer acid in an amount of from about 10 to about 40~ by weight, most preferably from about 15 to about 30~
~25~
.~
by weight based on the combined weight of ~i) and (ii), and optionally trimellitic anhydride. In its most preferred embodiments, the diol will be 100 mole ~ 1,4- butanediol and the dicarboxylic acid 100 mole ~ dimethylterephthalate.
The novel polyetherimide esters described herein may be prepared by conventional esterification/condensation reactions for the production of polyesters. Exemplary of the processes that may be practiced are set forth in, for example, United States Patent Numbers 3,023,192; 3,761,109; 3,651,014; 3,563,653 and 3,801,547. Additionally, these compositions may be prepared by such processes and other known processes to effect random copolymers, block copolymers or hybrids thereof wherein both random and block units 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 separate catalysts or catalyst systems may be used, one for ester interchange and one for polycondensation, it is preferred, where appropriate, to use one catalyst or catalyst system for both. In those instances where two separate catalysts are used, it is preferred and advantageous to render the ester-interchange catalyst ineffective following the com-, . . .
.
. .
"
~'~5~ 8CV 0~220 - lB - .
pletion of the precondensation reaction ~y means of known catalys~ inhibi~ors or quenchers, in particular, phosphorus compounds ~uch as phosphoric acid, phos-phenic acid, phosph~nic acid and the alkyl or aryl esters or salts thereof, in order to increase the thermal ~tability of the resultant polymer.
~ x~mplary of the suitable kno~l ~a alysts there may be given the acetates, casboxylates, hydroxides, ~xides, alcoholates ~r ~rganic comp:Lex compounds of 1~ zinc, manganese, antimony, ~obalt, lead, ~alcium and the alkali metals insofar as these compounds are soluble in the reaction mixture. 5pecific examples include, zinc acetate, calcium acetate and combina-tions thereof with antimony tri-~xide and the li~e.
These catalysts as well as additional useful catalysts are described in United States Patent Nu~ers 2,465,319; 2,534,028; 2,850,483;. -2,892,815; :3,937,1~0; 2,998,412; 3,047,539;
3,110,693 and 3i385,830, among others.
Where the reactants and reactions allow, it is preferred to use the tit~nium catalysts including the inorganic and ~rganic titanium containing catalysts ~uch as those described in, for ex~mple, - .
2,720,502; 2,727,881; 2,729,619; 2,822,348;
2,906,737; 3,047,515; 3,056,817; 3,056,818;
and 3,075,952, a~ong others. Espe2ially preferred are the organic titanates such as tetra-butyl titan-ate, tetra-isopropyl titanate and tetra-D~tyl titanate and the complex titanates derived fr~m alkali or alka-line earth metal alkoxides and titanate esters, most preferably the organic titanat~s. These too may be u~ed al~ne or in com} ination with o~her c2t31y5ts such as for example, zin~ acetate, ~anganese ~ce~ate cr antimony trioxide, and/or with a ~a~aly~ quencher as described above.
~ 8CV 0~220 Although the n~vel p~lyetherimide ester ~f the present inventi~n p~ssess many desirable properties, it i~ preferred ~ s~a~ ze certain of the c~mp~si-ti~ns t~ heat, ~xidatiDn, radiativ~ by W light and the like. This can be accomplished by incorp~rating 6tabilizer material~ int~ the c~mpositions either dur-i~g pr~ducti~n ~r while in a hot melt ~tage following p~lymerizati~n~ The particular stabilizers useful herein are any ~f th~se ~nown in the art which are ~uitable for polyetherimide esters.
Satisfact~ry stabilizers comprise phenols and their derivatives, amines and their derivatives, com-p~unds c~ntaining ~oth hydroxyl and amine gr~ups, hydroxyazines, oximes, p~lymerie phen~lic esters and ~alts of multivalent metals in which the mPtal is in its lower valence state.
Representative phenol derivatives useful as sta-bilizers include 3,5-di-tert-butyl-4-hydroxy hydr~-cinnamic triester with 1,3,5-tris-(2-hydroxyethyl)-s-triazine-2,4,6-l1~,3~,5H)trione; 4,4'-bis(2,6-diter-tiary~butylphen~l); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tertiary-butyl-4-hydroxybenzyl)benzene and 4,4'-butyl-idene-bis(6-tertiary-butyl-m-cresol). Vari~us in3rgan-ic metal salts or hydr~xides can be used as well as ~5 ~rgani~ c~mplexes ~uch as nickel dibutyl dithi~carbon-ate, manganous ~alicylate and copper 3-phenyl-salicy-late. ~ypical amine ~tabilizers include N,N'-bis(~eta-naphthyl)-p-phenylene diamine; N,N' bi~ methyl-heptyl) -p-phenylene diamine and ~ither phe~yl-beta-naphthyl amine or its reacti~n pr~ducts with~ldehydes. Mixtures ~f hindered phen~l~ wi~h es~ess of thi~dipr~pionic acid, mercaptides and phosphite esters ~re particularly useful. Additional ~tabiliza-ti~n t~ ultravi~let light can be obtained by comp~und-ing with varivus W ~bs~rber~ 6uch ~s substitutedbenz~phen~nes and/~r ben~tsia2sles.
8Cv 04220 Opti~nally, it m~y be desirable to ~dd a minor am~unt, up to ab~ut 20 mole ~, preferably up to about 10 mole ~, ~ased on the moles 4f the polyoxyalkylene diimide diacid, Df a tricar~oxylic c:omponent to the reaction mixture. While higher amounts of the tri-carboxylic component may be used, this has the dis-~dvantage Df reduciny ~ome of th~ beneficial proper-ties of the present p~lymers. Suita~le tricarb~xylic components are the ~ame as identified above for the preparation of the pDly~xyalkylene diimide diacid.
While it is preferred that the additional tricarboxyl-ic component be th~ same as used in the preparation ~f the polyoxyalkylene diimide diacid, it is not neces-~ary. The addition of the tricarboxylic acid com-ponent will have the added benefit of picking up andreacting with any residual, unreacted amine groups and, consequen~ly, aiding in the viscosity build of the polymer itself.
~urther, the properties of these polyesters can be modified by incorporation of various conventional inorganic fillers such as carbon black, silica gel, alumina, clays and chGpped fiberglass. These may be incorporated in amounts up to ~0~ by wei~ht, prefer-ably up to about 30~ by weight. In general, these additives have the effect of increasing the modulus of ~he material at various elo~gations.
DETAI~ED DESCRIPTION _~ THE PREFERRED EMBODIMENTS
The following examples are presented as illustra-tive of the present invention and are not to be con-~trued ~s limiting thereof.
Physical properties were determined ~ccording theproper ASTM methods as follows:
~ 8Cv 04220 Flexural Modulus AS~M D 790 Tensile Strength ASTM D 638 Tensile Elongation ASTM D 63~
Shore D Hardness ASTM :D 224D
5 Tensile Set ASTM D 412 In general, all compositi~ns wlere prepared by placing all reactant~ in ~he rea~tion vessel and heat-ing to 180~C. After the theoretica.l amount of methanol was removed, the pot temperature was in-creased t~ about 250~C. and a vacuum applied ( l~m ~g~
until the desired vi~cosity polymer was ~btained. All reacticns, unless otherwise specified were catalyzed with te~raoctyl ti~anate catalyst.
Diimide Diacid A
1~ A polyoxyalkylene diimide diacid was prepared by the imidization of trimellitic anhydride with Texaco Chemical Company 16 Jeffamine~ D2000, a polypropylene ether diamine, average molecular weight 2000, Diimide Viacid B
A second polyoxyalkylene diimide diacid was pre-pared by the imidiza~ion of trimellitic anhydride with Texaco Chemical Company'~ 3effamine ED-900, a predom-inately polyethyl~ne oxi~e backbone, copoly~ethylene ~xide-propylene oxide) diamine, average molecular weight 900.
Diimide Diacid C
A third polyoxyalkylene diimide diacid was pre-pared by the imidization of trimellitic anhyaride with Texaco Chemical Company'~ Jeffami~e ED-2~1, a predom-inately polyethylene oxide backbone, ~opoly(ethyleneoxide-propylene oxide)diamine~ average molecular weiyht 2000~
EXAMPL~S 1-9 : Two ~eries of c~mpo~itions were pr*pared, ~ne with Diimide Diacid A and the other with Diimide Di-~cid B at variou~ weight rati~s to di~arboxylio a~id.
;.;. -The comp~sitions were as presented :in Table 1. All reactants are i~ parts by weigh~n AdditiDnally, each composition contained about 3 % by weight based on the diimide diacid ~f a ~hermal ~tabili:zer.
S The elast~meric p~lymers ~f these examples had excellent physical properties and had surpri~ingly superior processability and moldabi.lity characteristics.
5~9~
~n ~ ~1 N C~ ~ t~
11~ ~1 In u~
U)l ~ ~ ~I O
U~
c: m ~ m ~r ~ ~ o~
'~F I ~ ~ ~ I O _I
I~ ~
_1 ~ ~ 1` ~ o ~ u~, ~ 1 ~ ~ . I N 1~
~` ~
U~~D ~ ~r ~ OD
I~ ~
-~a ~
_~ C
X
a) rl ~ ~ tq --I ~ ~ ~ O
o ~
~I h V
C~ C J~
~ c: e~ a o ~ ~ cn E~ ~ 0 E~ ~ _I
~ ~ ~ ~ 0 ~ ~ ~ ~ ~ G) U2 ~ ~ o ~ c~
a c Æ 6 E~
~E ~ I
C~ ~ 1 ~ h t:;
~ ~ c:~ ~a a æ E~ ~
8Cv 04220 ~ 24 -EXAMPLES 1~-22 Several ~dditional compositi~ns within he ~cope Df the present in~ention were prepared d~monstrating verious different embodiments hereof~ ~or example, Example 10 demons~rates a cvmposi~iDn derived fro~ a mixture of dimethylterephthalate and i ophthalic acid and Examples 11, 15, 17 and 21 demonstrates the u~e of dimer acid (Hystre2le~ 3695 - Witco Chemical Corporation).
Finally, Example 16 demonstrate the use of ethylene glycol as the diol component Ithis reaction used antimony oxide and zinc acetates as ~atalysts with a phosphite cata}yst quencher)~ Only those examples as indicated contained a thermal stabilizer. The composition and physical properties of these examples were as set forth in Table 2. All amounts are in parts by weight unless otherwise specified~ A comparison vf Example 6, above, with Example 12 demonstrates the improved properties obtained by use of stabilizer and excess tximellitic 2~ anhydride.
, ~ _ i0`~ 8CV 04220 C:7 0 ~ 1~') ~ r~l N
t~
~ l J I N
f`J I t~
r _~ ~
u~ cr. ~r _11 N _l 1 r ~ u~
_I _I ~ _I
~r) t~l cr o u~ r~
,:1 t` Cr~
tn O O c ) ~ r c 2 ~rl ~. I ~ I I I I ~ I ~ ~D t, r- ~D 0 ~U
N Ul 'C1 'O
_/ ~ D O
_ --I ~
a ~ ~ oP o X t~
0 ~ _~ o ~ ~ ~
O ~-,) N _I h 'O O ~n .. t ~ 0 Lq ~ ~ ~ u ~ x u ~ V
z q ~ O ' ~3 ~ ~ ~ ~ ~ --( ~ ~ ~ ~o ~ u~ O
X ~ X ~ ~
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8Cv 04220 E~AMP~S 23-2?
Additional compositions were p.repared ~gain further demonstrating the broad ~cope ~f-the present invention wherein both ~tabilizer and additional trimellitic anhydride were added to the rea~tion mix.
The compositions and the physical properties thereof were as ~hown in Example 3.
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.~, ~9 ~ ~ Z
U~
u~
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.
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N ¦ O
c) R 1::
a ~rl O
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~ _I ~ t~ "5 _I C
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t43 ~ D~ p E' ) ~ 9E ~ ~
~CV 0~220 EX~MPLES El-E4, COMPARATIVE EXAMPLES CEl CE6 A series of examples were prepared typifying the modified copolyetherimide esters of the present invention and unmodified copolyetherimide esters. In addition to demonstrating the benefits attributed to these compositions, these examples demc,nstrate the broad application of the present teaching giving examples with different amounts of dimer, varying weight ratio of i) polyoxyalkylene diimide diacids and ii) dimer to dicarboxylic acid (b) and various polyoxyalkylene diimide diacids. The specific compositions of each example and comparative example as well as the physical properties therPof are set forth in Table 4. All component~ are expressed in parts by weight unless otherwise stated.
~ _ ___ ~ o ~ ~ ~ rl ~ O
UI ~ r ~
Il') O 0~ N t~ ~ ~ ~D
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.
~ ~ O U~ ~ I O
IL1 Il) E~
al ~ ~ o ~ a N C) O ,l X _O
G ~5 al a e ~ O ~ tn O ~ ~ ~ ~ 10 ~ a s ~ R
~rl a Ç~ t~ V t~ ~ ~ ~ ç G ~P
., `D ~ ~a ~.) . t o o h N Q) rl _I ~
:~ c a~ l ~ ~ ~
Ei E~ .CI IE~ Cl ~ X ~ h ~r ~ o ~ 0 5~
8CV 04~20 From the examples in Table 4 it is clear that the modified compositions of the present invention have improved flexibility at the same or about ~he same levels of incorporation of polyoxyalkylene diimide diacid. For example comparison of Example El, E3 and E4 with comparative Examples CEl, CE3 and CE4 respectively demonstrates the improved flexibility of the composition of the present invention.
Altern~tively, unmodified compositions having about the same flexibility as the modified polyetherimide ester compositions of the present invention require about a 20% increase in the amount of polyoxyalkylene diimide diacid component. Because of tne susceptability of the polyether component to thermal and oxidative degredation as well as attack by solv~nts, applicant's composition by virtue of lesser amounts of polyether will have enhanced thermal and oxidative stability as well as improved solvent resistance as compared to the unmodified compositions~
Obviously, other modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that changes may be made in the particular embodiments of the invention described which are within the full intended scope as defined by the appended claims.
Where the reactants and reactions allow, it is preferred to use the tit~nium catalysts including the inorganic and ~rganic titanium containing catalysts ~uch as those described in, for ex~mple, - .
2,720,502; 2,727,881; 2,729,619; 2,822,348;
2,906,737; 3,047,515; 3,056,817; 3,056,818;
and 3,075,952, a~ong others. Espe2ially preferred are the organic titanates such as tetra-butyl titan-ate, tetra-isopropyl titanate and tetra-D~tyl titanate and the complex titanates derived fr~m alkali or alka-line earth metal alkoxides and titanate esters, most preferably the organic titanat~s. These too may be u~ed al~ne or in com} ination with o~her c2t31y5ts such as for example, zin~ acetate, ~anganese ~ce~ate cr antimony trioxide, and/or with a ~a~aly~ quencher as described above.
~ 8CV 0~220 Although the n~vel p~lyetherimide ester ~f the present inventi~n p~ssess many desirable properties, it i~ preferred ~ s~a~ ze certain of the c~mp~si-ti~ns t~ heat, ~xidatiDn, radiativ~ by W light and the like. This can be accomplished by incorp~rating 6tabilizer material~ int~ the c~mpositions either dur-i~g pr~ducti~n ~r while in a hot melt ~tage following p~lymerizati~n~ The particular stabilizers useful herein are any ~f th~se ~nown in the art which are ~uitable for polyetherimide esters.
Satisfact~ry stabilizers comprise phenols and their derivatives, amines and their derivatives, com-p~unds c~ntaining ~oth hydroxyl and amine gr~ups, hydroxyazines, oximes, p~lymerie phen~lic esters and ~alts of multivalent metals in which the mPtal is in its lower valence state.
Representative phenol derivatives useful as sta-bilizers include 3,5-di-tert-butyl-4-hydroxy hydr~-cinnamic triester with 1,3,5-tris-(2-hydroxyethyl)-s-triazine-2,4,6-l1~,3~,5H)trione; 4,4'-bis(2,6-diter-tiary~butylphen~l); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tertiary-butyl-4-hydroxybenzyl)benzene and 4,4'-butyl-idene-bis(6-tertiary-butyl-m-cresol). Vari~us in3rgan-ic metal salts or hydr~xides can be used as well as ~5 ~rgani~ c~mplexes ~uch as nickel dibutyl dithi~carbon-ate, manganous ~alicylate and copper 3-phenyl-salicy-late. ~ypical amine ~tabilizers include N,N'-bis(~eta-naphthyl)-p-phenylene diamine; N,N' bi~ methyl-heptyl) -p-phenylene diamine and ~ither phe~yl-beta-naphthyl amine or its reacti~n pr~ducts with~ldehydes. Mixtures ~f hindered phen~l~ wi~h es~ess of thi~dipr~pionic acid, mercaptides and phosphite esters ~re particularly useful. Additional ~tabiliza-ti~n t~ ultravi~let light can be obtained by comp~und-ing with varivus W ~bs~rber~ 6uch ~s substitutedbenz~phen~nes and/~r ben~tsia2sles.
8Cv 04220 Opti~nally, it m~y be desirable to ~dd a minor am~unt, up to ab~ut 20 mole ~, preferably up to about 10 mole ~, ~ased on the moles 4f the polyoxyalkylene diimide diacid, Df a tricar~oxylic c:omponent to the reaction mixture. While higher amounts of the tri-carboxylic component may be used, this has the dis-~dvantage Df reduciny ~ome of th~ beneficial proper-ties of the present p~lymers. Suita~le tricarb~xylic components are the ~ame as identified above for the preparation of the pDly~xyalkylene diimide diacid.
While it is preferred that the additional tricarboxyl-ic component be th~ same as used in the preparation ~f the polyoxyalkylene diimide diacid, it is not neces-~ary. The addition of the tricarboxylic acid com-ponent will have the added benefit of picking up andreacting with any residual, unreacted amine groups and, consequen~ly, aiding in the viscosity build of the polymer itself.
~urther, the properties of these polyesters can be modified by incorporation of various conventional inorganic fillers such as carbon black, silica gel, alumina, clays and chGpped fiberglass. These may be incorporated in amounts up to ~0~ by wei~ht, prefer-ably up to about 30~ by weight. In general, these additives have the effect of increasing the modulus of ~he material at various elo~gations.
DETAI~ED DESCRIPTION _~ THE PREFERRED EMBODIMENTS
The following examples are presented as illustra-tive of the present invention and are not to be con-~trued ~s limiting thereof.
Physical properties were determined ~ccording theproper ASTM methods as follows:
~ 8Cv 04220 Flexural Modulus AS~M D 790 Tensile Strength ASTM D 638 Tensile Elongation ASTM D 63~
Shore D Hardness ASTM :D 224D
5 Tensile Set ASTM D 412 In general, all compositi~ns wlere prepared by placing all reactant~ in ~he rea~tion vessel and heat-ing to 180~C. After the theoretica.l amount of methanol was removed, the pot temperature was in-creased t~ about 250~C. and a vacuum applied ( l~m ~g~
until the desired vi~cosity polymer was ~btained. All reacticns, unless otherwise specified were catalyzed with te~raoctyl ti~anate catalyst.
Diimide Diacid A
1~ A polyoxyalkylene diimide diacid was prepared by the imidization of trimellitic anhydride with Texaco Chemical Company 16 Jeffamine~ D2000, a polypropylene ether diamine, average molecular weight 2000, Diimide Viacid B
A second polyoxyalkylene diimide diacid was pre-pared by the imidiza~ion of trimellitic anhydride with Texaco Chemical Company'~ 3effamine ED-900, a predom-inately polyethyl~ne oxi~e backbone, copoly~ethylene ~xide-propylene oxide) diamine, average molecular weight 900.
Diimide Diacid C
A third polyoxyalkylene diimide diacid was pre-pared by the imidization of trimellitic anhyaride with Texaco Chemical Company'~ Jeffami~e ED-2~1, a predom-inately polyethylene oxide backbone, ~opoly(ethyleneoxide-propylene oxide)diamine~ average molecular weiyht 2000~
EXAMPL~S 1-9 : Two ~eries of c~mpo~itions were pr*pared, ~ne with Diimide Diacid A and the other with Diimide Di-~cid B at variou~ weight rati~s to di~arboxylio a~id.
;.;. -The comp~sitions were as presented :in Table 1. All reactants are i~ parts by weigh~n AdditiDnally, each composition contained about 3 % by weight based on the diimide diacid ~f a ~hermal ~tabili:zer.
S The elast~meric p~lymers ~f these examples had excellent physical properties and had surpri~ingly superior processability and moldabi.lity characteristics.
5~9~
~n ~ ~1 N C~ ~ t~
11~ ~1 In u~
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U~
c: m ~ m ~r ~ ~ o~
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~` ~
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I~ ~
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o ~
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a c Æ 6 E~
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C~ ~ 1 ~ h t:;
~ ~ c:~ ~a a æ E~ ~
8Cv 04220 ~ 24 -EXAMPLES 1~-22 Several ~dditional compositi~ns within he ~cope Df the present in~ention were prepared d~monstrating verious different embodiments hereof~ ~or example, Example 10 demons~rates a cvmposi~iDn derived fro~ a mixture of dimethylterephthalate and i ophthalic acid and Examples 11, 15, 17 and 21 demonstrates the u~e of dimer acid (Hystre2le~ 3695 - Witco Chemical Corporation).
Finally, Example 16 demonstrate the use of ethylene glycol as the diol component Ithis reaction used antimony oxide and zinc acetates as ~atalysts with a phosphite cata}yst quencher)~ Only those examples as indicated contained a thermal stabilizer. The composition and physical properties of these examples were as set forth in Table 2. All amounts are in parts by weight unless otherwise specified~ A comparison vf Example 6, above, with Example 12 demonstrates the improved properties obtained by use of stabilizer and excess tximellitic 2~ anhydride.
, ~ _ i0`~ 8CV 04220 C:7 0 ~ 1~') ~ r~l N
t~
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u~ cr. ~r _11 N _l 1 r ~ u~
_I _I ~ _I
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tn O O c ) ~ r c 2 ~rl ~. I ~ I I I I ~ I ~ ~D t, r- ~D 0 ~U
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z q ~ O ' ~3 ~ ~ ~ ~ ~ --( ~ ~ ~ ~o ~ u~ O
X ~ X ~ ~
E-~ ill al ~ ~1 t) ~ al H _~ 3 P~ I :~ O t~ E~ ~J ~ ~X u~ sn h ;q :~ ~ ~ E o ~ ~ e o c~ -~ ~ a ~ a E~ ~
8Cv 04220 E~AMP~S 23-2?
Additional compositions were p.repared ~gain further demonstrating the broad ~cope ~f-the present invention wherein both ~tabilizer and additional trimellitic anhydride were added to the rea~tion mix.
The compositions and the physical properties thereof were as ~hown in Example 3.
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N ¦ O
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t43 ~ D~ p E' ) ~ 9E ~ ~
~CV 0~220 EX~MPLES El-E4, COMPARATIVE EXAMPLES CEl CE6 A series of examples were prepared typifying the modified copolyetherimide esters of the present invention and unmodified copolyetherimide esters. In addition to demonstrating the benefits attributed to these compositions, these examples demc,nstrate the broad application of the present teaching giving examples with different amounts of dimer, varying weight ratio of i) polyoxyalkylene diimide diacids and ii) dimer to dicarboxylic acid (b) and various polyoxyalkylene diimide diacids. The specific compositions of each example and comparative example as well as the physical properties therPof are set forth in Table 4. All component~ are expressed in parts by weight unless otherwise stated.
~ _ ___ ~ o ~ ~ ~ rl ~ O
UI ~ r ~
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.
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IL1 Il) E~
al ~ ~ o ~ a N C) O ,l X _O
G ~5 al a e ~ O ~ tn O ~ ~ ~ ~ 10 ~ a s ~ R
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:~ c a~ l ~ ~ ~
Ei E~ .CI IE~ Cl ~ X ~ h ~r ~ o ~ 0 5~
8CV 04~20 From the examples in Table 4 it is clear that the modified compositions of the present invention have improved flexibility at the same or about ~he same levels of incorporation of polyoxyalkylene diimide diacid. For example comparison of Example El, E3 and E4 with comparative Examples CEl, CE3 and CE4 respectively demonstrates the improved flexibility of the composition of the present invention.
Altern~tively, unmodified compositions having about the same flexibility as the modified polyetherimide ester compositions of the present invention require about a 20% increase in the amount of polyoxyalkylene diimide diacid component. Because of tne susceptability of the polyether component to thermal and oxidative degredation as well as attack by solv~nts, applicant's composition by virtue of lesser amounts of polyether will have enhanced thermal and oxidative stability as well as improved solvent resistance as compared to the unmodified compositions~
Obviously, other modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that changes may be made in the particular embodiments of the invention described which are within the full intended scope as defined by the appended claims.
Claims (61)
1. A polyetherimide ester composition comprising the reaction product of (a) one or more low molecular weight diols, (b) one or more dicarboxylic acids, and (c) a component being one selected from the group comprising a first said component consisting of one or more polyoxyalkylene diimide diacids and a second said component consisting of a combination of (i) one or more polyoxyalkylene diimide diacids and (ii) one or more dimer acids wherein the amount of dimer is from about 5 to about 40 percent by weight based on the combined weight of (i) and (ii).
2. A composition of claim 1 wherein component c) is one or more dicarboxylic acids.
3. The composition of claim 2 wherein the diol component (a) is a C2 to C15 aliphatic or cycloaliphatic diol or a mixture thereof.
4. The composition of claim 3 wherein the diol component (a) is from about 60 to 100 mole %
1,4-butanediol.
1,4-butanediol.
5. The composition of claim 3 wherein the diol component (a) is from about 80 to 100 mole %
1,4-butanediol.
1,4-butanediol.
6. The composition of claim 3 wherein the diol component is 1,4-butanediol.
7. The composition of claim 2 wherein the dicarboxylic acid component (b) is selected from the group consisting of C2 to C16 aliphatic and/or cycloaliphatic dicarboxylic acid or a C6 to C16 aromatic dicarboxylic acid or the ester equivalents thereof and mixtures thereof.
8. The composition of claim 7 wherein the dicarboxylic acid component (b) is from about 60 to 100 mole % dimethyl terephthalate.
9. The composition of claim 7 wherein the dicarboxylic acid component (b) is from about 80 to 100 mole % dimethyl terephthalate.
10. The composition of claim 7 wherein the dicarboxylic acid components (b) is dimethyl terephthalate.
11. The composition of claim 2 wherein the 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.
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.
12. The composition of claim 11 wherein the polyoxyalkylene diimide diacid is such that each R is a C6 trivalent aromatic hydrocarbon radical, each R' is hydrogen 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 900 to 4000.
13. The composition of claim 2 wherein the polyoxyalkylene diimide diacid is derived from trimelletic anhydride and a polyoxyalkylene diamine selected from the group consisting of polypropylene oxide diamine and a copoly(ethylene oxide-propylene oxide) diamine having predominately polyethylene oxide in the backbone.
14. The composition of claim 2 wherein the weight ratio of polyoxyalkylene diimide diacid (c) to dicarboxylic acid (b) is from about 0.25 to about 2.
15. The composition of claim 2 wherein the weight ratio of polyoxyalkylene diimide diacid (c) to dicarboxylic acid (b) is from about 0.4 to about 1.4.
16. The composition of claim 2 wherein up to a minor amount of a tricarboxylic component selected from the group consisting of carboxylic acid anhydrides having an additional carboxyl group and tricarboxylic acid components having two vicinal carboxyl groups.
17. The composition of claim 16 wherein the tricarboxylic components is characterized by the following formula:
where R is selected from the group consisting of C2 to C20 aliphatic and cycloaliphatic trivalent organic radicals and C6 to C20 aromatic trivalent organic radicals and R' is selected from the group consisting of hydrogen, C1 to C6 aliphatic and cycloaliphatic monovalent organic radicals and C6 to C10 aromatic monovalent organic radicals.
where R is selected from the group consisting of C2 to C20 aliphatic and cycloaliphatic trivalent organic radicals and C6 to C20 aromatic trivalent organic radicals and R' is selected from the group consisting of hydrogen, C1 to C6 aliphatic and cycloaliphatic monovalent organic radicals and C6 to C10 aromatic monovalent organic radicals.
18. The composition of claim 16 wherein the tricarboxylic component is trimellitic anhydride.
19. The composition of claim 16 wherein the tricarboxylic component is present in an amount up to 20 mole percent based on the moles of polyoxyalkylene diimide diacid.
20. The composition of claim 16 wherein tricarboxylic compound is present in an amount up to 10 mole percent based on the moles of polyoxyalkylene diimide diacid.
21. The composition of claim 2 which further contains a stabilizer.
22. The composition of claim 21 wherein the stabilizer is 3,5-di-tert-butyl 4-hydroxy hydrocinnamic triester with 1,3,5-tris-(2-hydroxy ethyl)-3-triazine-2,4,6-(1H,3H,5H)trione.
23. The composition of claim 16 which further contains a stabilizer 3,5-di-tert-butyl-4-hydroxy hydrocinnamic triester with 1,3,5-tris-(2 hydroxy ethyl)-3-triazine-2,4,6-(1H,3H,5H)trione.
24. A polyetherimide ester composition comprising the reaction product (a) 1,4-butanediol (b) dimethylterephthalate and (c) a polyoxyalkylene diimide diacid derived from trimellitic anhydride and a polyoxyalkylene diamine having the formula:
wherein G is the divalent radical remaining after removal of the hydroxy groups of a long chain ether glycol having a molecular weight of from about 600 to about 12000.
wherein G is the divalent radical remaining after removal of the hydroxy groups of a long chain ether glycol having a molecular weight of from about 600 to about 12000.
25. The composition of claim 24 wherein the long chain ether glycol has a molecular weight of from about 900 to about 4000.
26. The composition of claim 24 wherein the long chain ether glycol is selected from the group consisting of polypropylene ether glycol and co(poly-ethylene ether - propylene ether)glycol having a predominately polyethylene ether backbone.
27. The composition of claim 24 in which trimellitic anhydride is added as an additional reactant.
28. The composition of claim 24 which contains a stabilizer 3,5-di-tert-butyl-4-hydroxy hydrocinnamic triester with 1,3,5-tris-(2-hydroxy-ethyl)-3-triazine-2,4,6-(1H,3H,5H)trione.
29. A composition of claim 1 wherein component (c) is a combination if (i) one or more polyoxyalkylene diimide diacids and (ii) one or more dimer acids wherein the amount of dimer is from about 5 to about 40 percent by weight based on the combined weight of (i) and (ii).
30. The combination of claim 29 wherein the amount of dimer acid is from about 15 to about 30 percent by weight based on the combined weight of (i) and (ii).
31. The composition of claim 29 wherein the dimer acid is selected from the group consisting of dimerized, unsaturated fatty acids, the hydrogenated derivatives thereof and the acid functioning derivatives of either.
32. The composition of claim 31 wherein the dimer acid is hydrogenated.
33. The composition of claim 29 wherein the dimer acid is at least about 95% by weight hydrogenated dimer acid.
34. The composition of claim 29 wherein the diol component (a) is a C2 to C15 aliphatic or cycloaliphatic diol or a mixture thereof.
35. The composition of claim 34 wherein the diol component (a) is from about 60 to 100 mole %
1,4-butanediol.
1,4-butanediol.
36. The composition of claim 34 wherein the diol component (a) is from about 80 to 100 mole %
1,4-butanediol.
1,4-butanediol.
37. The composition of claim 34 wherein the diol is 1,4-butanediol.
38. The composition of claim 29 wherein the dicarboxylic acid component (b) is selected from the group consisting of C2 to C16 aliphatic and/or cycloaliphatic dicarboxylic acid or a C6 to C16 aromatic dicarboxylic acid or the ester equivalents thereof and mixtures thereof.
39. The composition of claim 38 wherein the dicarboxylic acid component (b) is from about 60 to 100 mole % dimethyl terephthalate.
40. The composition of claim 38 wherein the dicarboxylic acid component (b) is from about 80 to 100 mole % dimethyl terephthalate.
41. The composition of claim 38 wherein the dicarboxylic acid component (b) is dimethyl terephthalate.
42. The composition of claim 39 wherein the polyoxyalkylene diimide diacid component (i) 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.
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.
43. The composition of claim 42 wherein the polyoxyalkylene diimide diacid is such that each R is a C6 trivalent aromatic hydrocarbon radical, each R' is hydrogen 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 900 to 4000.
44. The composition of claim 29 wherein the polyoxyalkylene diimide is derived from trimellitic anhydride and a polyoxyalkylene diamine selected from the group consisting of polypropylene oxide diamine and a copoly(ethylene oxide-propylene oxide)diamine having predominately polyethylene oxide in the backbone.
45. The composition of claim 29 wherein the weight ratio of polyoxyalkylene diimide diacid (i) to dicarboxylic acid (b) is from about 0.25 to about 2.
46. The composition of claim 29 wherein the weight ratio of polyoxyalkylene diimide diacid (i) to dicarboxylic acid (b) is from about 0.4 to about 1.4.
47. The composition of claim 29 wherein up to a minor amount of a tricarboxylic component selected from the group consisting of carboxylic acid anhydrides having an additional carboxyl group and tricarboxylic acid compounds having two vicinal carboxyl groups.
48. The composition of claim 37 wherein the tricarboxylic component is characterized by the following formula where R is selected from the group consisting of C2 to C20 aliphatic and cycloaliphatic trivalent organic radicals and C6 to C20 aromatic trivalent organic radicals and R' is selected from the group consisting of hydrogen, C1 to C6 aliphatic and cycloaliphatic monovalent organic radicals and C6 to C10 aromatic monovalent organic radicals.
49. The composition of claim 37 wherein the tricarboxylic component is trimellitic anhydride.
50. The composition of claim 37 wherein the tricarboxylic component is present in an amount up to 20 mole percent based on the moles of polyoxyalkylene diimide diacid.
51. The composition of claim 37 wherein tricarboxylic compound is present in an amount up to 10 mole percent based on the moles of polyoxyalkylene diimide diacid.
52. The composition of claim 29 which further contains a stabilizer.
53. The composition of claim 32 wherein the stabilizer is 3,5-di-tert-butyl-4-hydroxy hydrocinnamic triester with 1,3,5-tris-(2-hydroxy ethyl) 3-triazine-2,4,6-(1H,3H,5H)trione.
54. The composition of claim 37 which further contains a stabilizer 3,5-di-tert butyl-4-hydroxy hydrocinnamic triester with 1,3,5-tris-(2-hydroxy ethyl)-3-triazine-2,4,6-(1H,3H,5H)trione.
55. A polyetherimide ester composition comprising the reaction product (a) 1,4-butanediol (b) dimethylterephthalate and (c) a combination of (i) a polyoxyalkylene diimide diacid derived from trimellitic anhydride and a polyoxyalkylene diamine having the formula:
wherein G is the divalent radical remaining after removal of the hydroxy groups of a long chain ether glycol having a molecular weight of from about 600 to about 12000 and (ii) a dimer acid wherein the amount of dimer is from about 5 to about 40 percent by weight based on the combined weight of (i) and (ii).
wherein G is the divalent radical remaining after removal of the hydroxy groups of a long chain ether glycol having a molecular weight of from about 600 to about 12000 and (ii) a dimer acid wherein the amount of dimer is from about 5 to about 40 percent by weight based on the combined weight of (i) and (ii).
56. The composition of claim 55 wherein the dimer acid is present in an amount of from about 15 to about 30 percent by weight based on the combined weight of (i) and (ii).
57. The composition of claim 55 wherein the dimer is the hydrogenated derivative of a dimerized unsaturated fatty acid.
58. The composition of claim 55 wherein the long chain ether glycol has a molecular weight of from about 900 to about 4000.
59. The composition of claim 55 wherein the long chain ether glycol is selected from the group consisting of polypropylene ether glycol and co(polyethylene ether - propylene ether)glycol having a predominately polyethylene ether backbone.
60. The composition of claim 55 in which trimellitic anhydride is added as an additional reactant.
61. The composition of claim 55 which contains a stabilizer 3,5-di-tert-butyl-4-hydroxy hydrocinnamic triester with 1,3,5 tris-(2-hydroxy-ethyl)-3-triazine-2,4-6-(1H,3H,5H)trione.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US665,315 | 1984-10-26 | ||
| US06/665,277 US4556705A (en) | 1984-10-26 | 1984-10-26 | Thermoplastic polyetherimide ester elastomers |
| US665,277 | 1984-10-26 | ||
| US06/665,315 US4544734A (en) | 1984-10-26 | 1984-10-26 | Modified thermoplastic copolyetherimide ester elastomers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1250690A true CA1250690A (en) | 1989-02-28 |
Family
ID=27099166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000493896A Expired CA1250690A (en) | 1984-10-26 | 1985-10-25 | Thermoplasatic polyetherimide ester elastomers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1250690A (en) |
-
1985
- 1985-10-25 CA CA000493896A patent/CA1250690A/en not_active Expired
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