CA2241860A1 - Compatibilized lcp blends - Google Patents
Compatibilized lcp blends Download PDFInfo
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- CA2241860A1 CA2241860A1 CA002241860A CA2241860A CA2241860A1 CA 2241860 A1 CA2241860 A1 CA 2241860A1 CA 002241860 A CA002241860 A CA 002241860A CA 2241860 A CA2241860 A CA 2241860A CA 2241860 A1 CA2241860 A1 CA 2241860A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Abstract
The present invention provides alloys having at least one thermotropic liquid crystalline polymer, at least one thermoplastic aromatic polyester and at least one compatibilizer and methods of making such alloys.
Description
COMPATIBT~ T7h T- I,CP BLENDS
S FIELD OF THE INVEN'IION
The present invention provides alloys comprising thermotropic liquid crystalline polymers (LCPs) and at least one thermoplastic aromatic polyester and at least one compatibilizer.
High pelro,l,la-lce plastics are in widespread use in many intlllstries and there is much interest in developing new plastics which are economical and recyclable, as well as high pe.f~ allce. The blending and alloying of çxistin~ polymers is a cost effective way to produce new high pel~o~ allce 15 plastics which meet these criteria.
Polymer blends cont~inin~ thPrmotropic LCPs have received increasing ~ttention in the sci~ntific and technir~ e~alule. The range of high perforrnance thermoplastic flexible polymers which have been blended with TLCPs include polyimides, polyamides, poly(eth~r.elllfone) (PES~, 20 poly(etherimide) ~PEI), polyetherketone (PEEK), polycarbonate (PC~, poly(ethylene le~},l.Llllate) (PET), poly(ethylene ~ te) (PEN~, polyphenylene sulfide (PPS), and polyarylate.
Thermotropic LCPs are a relatively new class of high performance polymeric m~t~ri~ls which combine the advantages of melt processability 25 and olltct~n~ling mer~h~nil~l plop~-Lies. Recall~e of their rigid backbone structure with flexible spacer groups, co~ ;ially available thermotropic LCPs have far higher tensile strength and flexural moduli than conventional polymers. However, thermotropic LCPs are in many cases difficult to process without specialized equipment and very costly as compared with 30 conventional polymers when used alone.
Blending thermotropic LCPs with other polymers has been shown to improve processability of the other polymers, particularly LCPs based on wholly aromatic chain segments. Fur~ermore, blending with conventional thermoplastic polymers reduces costs, because less of the very costly LCP is SU~;~ ITE SHEET (RULE 26~
W O 97/24403 PCTrUS95/17114 used. Also, because thermotropic LCPs form an ordered phase in the melt (hence, the name thermotropic), they have shear viscosities far lower than other polymers and thus, have potential importance as a proc~s.~ing aid in mixtures with other polymers by red~ inE the melt viscosity of the mixture.
Thermotropic I,CP in blends with polyethylene telepl.~ te (PET), have been reported to act as a "flow aid" at levels of 5-10% by reducing the melt viscosity. In U.S. Patent Nos. 4,386,174, 4,433,083, and 4,438,236, it is disclosed that blending a thermotropic LCP with other polymers such as PET changes the melt viscosity of PET. At 10% loading (LCP) the viscosity of PET is reduced to 25-50% of its original viscosity-. O'Brien and Crosby (O'Brien, G.S. and Crosby, J.M., ProceeAin~ of COMPALLOY '91 CollÇe~ ce, January 30-February 1, 1991, pp. 133-148) described LCP/PTFE blends to improve the flow of PTFE in the melt.
The use of thermotropic LCPs in blends to provide ".eil,ruLcement,"
s~eci~lly where the LCP has a very rigid structure has been reported.
XYDAR'l9 (Poly(oxybenzoyl-co-bisphenyl terephth~l~te), Amoco, and VECTRA~9 Poly(oxybenzoyl-co-o~y . .~ph~ yl), ~oec h~t-Cel~n~se, are thermotropic LCPs which have been much studied as blend components.
Crevecoeur, G. and Groeninckx, G., Polymer Eng. Science, 30, 532 (1990), reported that a thermotropic LCP can be used at 5-30% levels in polystyrene so that the LCP forms a disperse phase. In a 75:25 Poly~lylelle/VECTRA'19 A-950 LCP blend at a draw ratio of 5, the LCP
phase was reported as being slightly elongated. However at a draw ratio of 10 or more, the LCP phase was reported to show a well-developed micro-fibrillar morphology and to display a substantial increase in elastic modulus over a compression or injection-molded sample.
The use of LCPs in blends with thermoplastic polymers, e.g., PC
and PAT, to achieve improved m~ch~nic~l properties over those of ~e Sl~ JTE SHEET (RULE 26) W O 97/24403 rCTrUS95/17114 thermoplastic polymer alone was reported in 1989. See, Bonis, L.J., "Multilayer Thermoplastics Advance ~omposites By Coextrusion", 17.e Polymer Processing Society Summer Meeting, ~mh~rst, M~s~chllcett~, August 16-17, 1989, Paper 10F. See, also Williams, D.J., Proceerlin~ of S COMPALLOY '91 Conference~ January 30 - Februar.,v 1, 1991, pp. 393-408 which describes potential applications for thermotropic liquid crystal polyester blends.
Polymer molding compositions cont~ining polycarbonates, thermoplastic polyester, and liquid crystalline polymers, wherein the liquid crystalline polymer is present as droplets or low aspect ratio particles, are disclosed in U.S. Patent No. 5,262,473. In the process disclosed in U.S.
Patent No. 5,262,473, compatible blends of the polyester and polycarbonate may be used. Other blends are disclosed in, for example, U.S. Patent Nos.
5,070,157 and 5,156,785.
A blend is a physical mixture of two or more components which typically offers a co~ llise of prop~.Lies and economies of the individual components. It is well known that t'ne nature and properties of the interface of components in a blend frequently exert a limiting effect on the bulk properties of a multi-phase blend material. In fact, the physical and mrrh~nir~l properties of a blend are very often inferior to the m~th~m~tic~l average of the properties of the original components. Blend components can be miscible or immi~cihle in their behavior toward each other.
Alloys are different from blends. Although they are also composed of two or more components, alloys exhibit strong intermolecular forces wherein intermolecular bonding between the components of the blend is provided by compatibilizers. This bonding in turn, creates new properties different from those of the original components and often e~cee~ling those of the average of the original ingredients. The types of interaction or SUBSTlTUTE SHEET (RULE 26~
W 097/24403 PCTrUS9~117114 "chemical bonding" between the components can include, for example, one or more of the following me~h~ni~m~: ionic; covalent; molecular inter-penetration; hydrogen bonding; or associative.
Successful compatibilization by one or more of these interactions 5 gives rise to interfacial a&esion to provide the formation of cohesive multi-phase cf mp~tihilized alloys with useful ~lupellies. To achieve compatibilization a number of strategies have emerged.
In one approach, suitable block or graft copolymers are introduced to serve as macromolecular em~ ifiers providing covalent bonds that traverse 10 and fortify the blend interface. Block and gra~t copolymers may be generated in-sit~ through reactive extrusion and blending to gelle,~te a compatibilized blend.
In another approach, polymers having nucleophilic functional groups are interacted with compatibilizers cont~ining hydrogen to form hydrogen 15 bonding. Ionomers have also served as compatibilizers. In some cases, ionic or strong physicoch~mi-~l interactions are generated across the interface, which in turn ~ Pe cr)mp~tibilization.
Compatibilization can also result from the addition of a similar functional group using the "like attract like" theory, such as the use of 20 chlorinated polyethylene to compatibilizer polyvinyl chloride with polyethylene. This has been l~ell~d to as "associative" bonding.
Finally, compatibilization has even been demonstrated by the addition of a third immiscible phase component that exhibits relatively low interfacial tension with each of the L~lilllaly blend components, i.e., those 25 components int~mled to be compat;bilized. The compatibilizing effects of the mutually miscible component may result from its presumed tentlPn~y to become enriched in the vicinity of the blend interface.
SUBSTITUTE SHEET (RULE 26) W O 97/24403 PCTrUS95/17114 Alloying provides a tool to lower the cost of high pelrol.llallce resins while at the same time ret~inin~ many of the desirable L lol~elLies and/or providing improved properties such as increased processability. The most successful alloying procedures result in a controlled and stable morphology with a singular thermodynamic profile. However, even when alloying is not "complete" in the multi-component system use~ul compositions can result.
At present, there is no known direct col~l~atibility between LCPs and thermoplastic aromatic polyesters.
Accordingly, approaches to comp~til~ilize LCPs wi~ thermoplastic aromatic polyesters and, thereby, to provide LCP/thermoplastic aromatic polyester alloys having properties which can be tailored to meet end-use specifications are being sought.
SUMIUARY OF THE INVENTION
The present invention provides alloys CO~ ibillg at least one thermotropic LCP, at least one thermoplastic aromatic polyester, and at least one compatibilizer. In one p~r~ d embodiment, two comp~tikilizers are present.
Preferred compatibilizers include:
(1) copolyester elastomers;
S FIELD OF THE INVEN'IION
The present invention provides alloys comprising thermotropic liquid crystalline polymers (LCPs) and at least one thermoplastic aromatic polyester and at least one compatibilizer.
High pelro,l,la-lce plastics are in widespread use in many intlllstries and there is much interest in developing new plastics which are economical and recyclable, as well as high pe.f~ allce. The blending and alloying of çxistin~ polymers is a cost effective way to produce new high pel~o~ allce 15 plastics which meet these criteria.
Polymer blends cont~inin~ thPrmotropic LCPs have received increasing ~ttention in the sci~ntific and technir~ e~alule. The range of high perforrnance thermoplastic flexible polymers which have been blended with TLCPs include polyimides, polyamides, poly(eth~r.elllfone) (PES~, 20 poly(etherimide) ~PEI), polyetherketone (PEEK), polycarbonate (PC~, poly(ethylene le~},l.Llllate) (PET), poly(ethylene ~ te) (PEN~, polyphenylene sulfide (PPS), and polyarylate.
Thermotropic LCPs are a relatively new class of high performance polymeric m~t~ri~ls which combine the advantages of melt processability 25 and olltct~n~ling mer~h~nil~l plop~-Lies. Recall~e of their rigid backbone structure with flexible spacer groups, co~ ;ially available thermotropic LCPs have far higher tensile strength and flexural moduli than conventional polymers. However, thermotropic LCPs are in many cases difficult to process without specialized equipment and very costly as compared with 30 conventional polymers when used alone.
Blending thermotropic LCPs with other polymers has been shown to improve processability of the other polymers, particularly LCPs based on wholly aromatic chain segments. Fur~ermore, blending with conventional thermoplastic polymers reduces costs, because less of the very costly LCP is SU~;~ ITE SHEET (RULE 26~
W O 97/24403 PCTrUS95/17114 used. Also, because thermotropic LCPs form an ordered phase in the melt (hence, the name thermotropic), they have shear viscosities far lower than other polymers and thus, have potential importance as a proc~s.~ing aid in mixtures with other polymers by red~ inE the melt viscosity of the mixture.
Thermotropic I,CP in blends with polyethylene telepl.~ te (PET), have been reported to act as a "flow aid" at levels of 5-10% by reducing the melt viscosity. In U.S. Patent Nos. 4,386,174, 4,433,083, and 4,438,236, it is disclosed that blending a thermotropic LCP with other polymers such as PET changes the melt viscosity of PET. At 10% loading (LCP) the viscosity of PET is reduced to 25-50% of its original viscosity-. O'Brien and Crosby (O'Brien, G.S. and Crosby, J.M., ProceeAin~ of COMPALLOY '91 CollÇe~ ce, January 30-February 1, 1991, pp. 133-148) described LCP/PTFE blends to improve the flow of PTFE in the melt.
The use of thermotropic LCPs in blends to provide ".eil,ruLcement,"
s~eci~lly where the LCP has a very rigid structure has been reported.
XYDAR'l9 (Poly(oxybenzoyl-co-bisphenyl terephth~l~te), Amoco, and VECTRA~9 Poly(oxybenzoyl-co-o~y . .~ph~ yl), ~oec h~t-Cel~n~se, are thermotropic LCPs which have been much studied as blend components.
Crevecoeur, G. and Groeninckx, G., Polymer Eng. Science, 30, 532 (1990), reported that a thermotropic LCP can be used at 5-30% levels in polystyrene so that the LCP forms a disperse phase. In a 75:25 Poly~lylelle/VECTRA'19 A-950 LCP blend at a draw ratio of 5, the LCP
phase was reported as being slightly elongated. However at a draw ratio of 10 or more, the LCP phase was reported to show a well-developed micro-fibrillar morphology and to display a substantial increase in elastic modulus over a compression or injection-molded sample.
The use of LCPs in blends with thermoplastic polymers, e.g., PC
and PAT, to achieve improved m~ch~nic~l properties over those of ~e Sl~ JTE SHEET (RULE 26) W O 97/24403 rCTrUS95/17114 thermoplastic polymer alone was reported in 1989. See, Bonis, L.J., "Multilayer Thermoplastics Advance ~omposites By Coextrusion", 17.e Polymer Processing Society Summer Meeting, ~mh~rst, M~s~chllcett~, August 16-17, 1989, Paper 10F. See, also Williams, D.J., Proceerlin~ of S COMPALLOY '91 Conference~ January 30 - Februar.,v 1, 1991, pp. 393-408 which describes potential applications for thermotropic liquid crystal polyester blends.
Polymer molding compositions cont~ining polycarbonates, thermoplastic polyester, and liquid crystalline polymers, wherein the liquid crystalline polymer is present as droplets or low aspect ratio particles, are disclosed in U.S. Patent No. 5,262,473. In the process disclosed in U.S.
Patent No. 5,262,473, compatible blends of the polyester and polycarbonate may be used. Other blends are disclosed in, for example, U.S. Patent Nos.
5,070,157 and 5,156,785.
A blend is a physical mixture of two or more components which typically offers a co~ llise of prop~.Lies and economies of the individual components. It is well known that t'ne nature and properties of the interface of components in a blend frequently exert a limiting effect on the bulk properties of a multi-phase blend material. In fact, the physical and mrrh~nir~l properties of a blend are very often inferior to the m~th~m~tic~l average of the properties of the original components. Blend components can be miscible or immi~cihle in their behavior toward each other.
Alloys are different from blends. Although they are also composed of two or more components, alloys exhibit strong intermolecular forces wherein intermolecular bonding between the components of the blend is provided by compatibilizers. This bonding in turn, creates new properties different from those of the original components and often e~cee~ling those of the average of the original ingredients. The types of interaction or SUBSTlTUTE SHEET (RULE 26~
W 097/24403 PCTrUS9~117114 "chemical bonding" between the components can include, for example, one or more of the following me~h~ni~m~: ionic; covalent; molecular inter-penetration; hydrogen bonding; or associative.
Successful compatibilization by one or more of these interactions 5 gives rise to interfacial a&esion to provide the formation of cohesive multi-phase cf mp~tihilized alloys with useful ~lupellies. To achieve compatibilization a number of strategies have emerged.
In one approach, suitable block or graft copolymers are introduced to serve as macromolecular em~ ifiers providing covalent bonds that traverse 10 and fortify the blend interface. Block and gra~t copolymers may be generated in-sit~ through reactive extrusion and blending to gelle,~te a compatibilized blend.
In another approach, polymers having nucleophilic functional groups are interacted with compatibilizers cont~ining hydrogen to form hydrogen 15 bonding. Ionomers have also served as compatibilizers. In some cases, ionic or strong physicoch~mi-~l interactions are generated across the interface, which in turn ~ Pe cr)mp~tibilization.
Compatibilization can also result from the addition of a similar functional group using the "like attract like" theory, such as the use of 20 chlorinated polyethylene to compatibilizer polyvinyl chloride with polyethylene. This has been l~ell~d to as "associative" bonding.
Finally, compatibilization has even been demonstrated by the addition of a third immiscible phase component that exhibits relatively low interfacial tension with each of the L~lilllaly blend components, i.e., those 25 components int~mled to be compat;bilized. The compatibilizing effects of the mutually miscible component may result from its presumed tentlPn~y to become enriched in the vicinity of the blend interface.
SUBSTITUTE SHEET (RULE 26) W O 97/24403 PCTrUS95/17114 Alloying provides a tool to lower the cost of high pelrol.llallce resins while at the same time ret~inin~ many of the desirable L lol~elLies and/or providing improved properties such as increased processability. The most successful alloying procedures result in a controlled and stable morphology with a singular thermodynamic profile. However, even when alloying is not "complete" in the multi-component system use~ul compositions can result.
At present, there is no known direct col~l~atibility between LCPs and thermoplastic aromatic polyesters.
Accordingly, approaches to comp~til~ilize LCPs wi~ thermoplastic aromatic polyesters and, thereby, to provide LCP/thermoplastic aromatic polyester alloys having properties which can be tailored to meet end-use specifications are being sought.
SUMIUARY OF THE INVENTION
The present invention provides alloys CO~ ibillg at least one thermotropic LCP, at least one thermoplastic aromatic polyester, and at least one compatibilizer. In one p~r~ d embodiment, two comp~tikilizers are present.
Preferred compatibilizers include:
(1) copolyester elastomers;
(2) ethylene ester copolymers, such as ethylene-methyl acrylate copolymers;
(3) copolymers of ethylene and a carboxylic acid or acid derivative, such as ethylene-maleic ~hyd.ide copolymers;
(4) ethylene ester copolymers, such as ethylene methyl acrylate copolymers, grafted with functional monomers;
(5) ethylene copolymer-acrylic acid terpolymers, such as ethylene-methyl acrylate-maleic anhydride terpolymers;
SUBSTITUTE SHEET ~RUI E 26~
SUBSTITUTE SHEET ~RUI E 26~
(6) terpolymers of ethylene, ullsaLul~ted ester and a carboxylic acid or acid derivative, such as e~ylene-methyl acrylate-methacrylic acid terpolymers; and (7) acrylic elastomers, such as acrylic rubbers.
s Copolymers and terpolymers comprising ethylene-methyl acrylate, copolyester elastomers and acrylic elastomers are particularly p,ere.led compatibilizers for use in the present invention.
A particularly plel~lled:
(i) copolyester elastomer is HYTREL~ HTR-6108 from DuPont;
(ii~ ethylene-methyl acrylate copolymer is SP 2205TN and 3306~ from Chevron /~hrmir~l G~lllpal~y;
(iii) ethylene maleic anhydride copolymer is Polybond~
3009 from BP Chemir~l~ and Fusabond'l9 E-MB-226D
from DuPont Cl~n~
(iv~ ethylene-me~yl acrylate copolymer grafted with maleic anhydride is DS~ 1328/60 from Chevron ~hrmir~l Company and Fusabond~9 A MG-175D from DuPont ~n~rl~;
(v) ethylene-methyl acrylate-maleic anhydride terpolymer is Lotader~ 2400, Lotader~ 3410, and Lotader~ 5500 from Elf ~torhrm;
(vi) ethylene-methyl acrylate-methacrylic acid terpolymer is Escor'l9 ATX-320, EscorG9 ATX-325 or Escor~ XV-1104 from Exxon (~hemir~l; and (vii~ acrylic rubber is Vamac~ G1 from DuPont.
SUBSTITUTE SHEET (RULE 26) W O 97124403 PCTrUS95/17114 Thermoplastic aromatic polyesters for use in the present invention are commonly referred to by those skilled in the art as PET polymers and include but are not limited to PET (homopolymers and copolymers), polybutylene terc;~ late (PBT), PETG (PET modified with cyclohex~n~lim~thanol (CHDM)), PCTA copolymers (a polymer of CHDM
and terephth~lic acid with another acid substituted for a po~tion of the terephthalic acid), PBT (polybutylene tere~hth~1~te), APET (amorphous polyethylene), CPET (cyst~11i7~1e PET), PCPT (copolyester cont~ining propylene glycol), PEN (polyethylene n~phth~1~te), and PBN (polybutylene naphth~1~te). Preferred thermoplastic aromatic polyesters include PET
homopolymers and copolymers co~ g terephth~lir acid and isot~re~ 1ic acid, and PCTA. F.~re~i~11y pr~rerfed thermoplastic aromatic polyesters include F~tm~n Kodak Company's Kodar~9 or Eastar~
A150, Kodar~ or Eastar~ 9921, Kodapak~9 or F~t~r~kTM 7352, Kodara9 or Eastar~ 9921W and F~tm~nTM 1339; Shell's Traytuff~ 8006; DuPont's Crystar~ 1927 and Selar~ PT7067; and Shell's Traytuff~ CPET.
Preferred thermotropic LCPs include wholly or partially aromatic polyesters or copolyesters. Particularly pl~;rt:l,ed copolyesters include XYDARTM, VECTRA~ and ZENITE~ (E.I. duPont de Nemours).
Other ~i~re-led thermotropic liquid crystal polymers include SUMIKASUPER~ and EKONO~TM (Sumitomo Ch~mir~l), DuPont HX~, RODRUN'I9 (Unitika) and GRANLARTU (Grandmont).
~f~"ed LCPs for use in the present invention include any such resins with a melt temperature in the range of 250 to 350~C. Particularly pr~r~ d LCPs have a melt temperature in the range of 250 to 280~C.
One pl~rel,ed alloy in accordance with the present invention comprises thermoplastic aromatic polyester, a wholly aromatic LCP
copolyester and an ethylene-methyl acrylate-acrylic acid terpolymer SuBsTlTuTE SHEET (RULF 263 W O 97l24403 PCTrUS95/17114 compatibilizer, for example, Escor~ ATX-320, Escora9 ATX-325, or Escor'~9 XV- 1 104.
Another prt~ ed alloy comprises thermoplastic aromatic polyester, a wholly aromatic LCP copolyester and a ethylene maleic anhydride S copolymer compatibilizer such as Polybond~ 3009 or Fusabond~9 E-MB-226D.
Yet another ~refell~d alloy in accordance with ~is invention comprises ~ermoplastic aromatic polyester, a wholly aromatic LCP
copolyester and an ethylene-methyl acrylate copolymer grafted with maleic anhydride compatibilizer, such as DS~ 1328/60, or an ethylene acrylate terpolymer grafted with maleic anhydride such as Fusabond~ A MG-175D, or a copolyester elastomer such as HYTREL~ HTR 6108.
Alloys con~ g thermoplastic aromatic polyester, LCP and at least two compatibilizers are particularly pl~;felled in ~e practice of the present invention. The u~mr~tihilizers are preferably selected from a copolyester elastomer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl acrylate copolymer grafted with maleic anhydride, ethylene-methyl acrylate-maleic anhydride terpolymer, ethylene-methylacrylate-methacrylic acid terpolymer, or acrylic rubber.
Preferred two compatibilizer alloys include a PCTA copolymer such as KodarG9 or Eastar~ A150, a wholly aromatic LCP copolyester, an ethylene-methyl acrylate-acrylic acid terpolymer and ethylene maleic anhydride copolymer compatibilizer. Exemplary ethylene-methyl acrylate-acrylic acid terpolymers include Escora9 ATX-320, Escor$ ATX-325, or Escor~D XV-1104 and an exemplary ethylene maleic anhydride copolymers are Polybond~ 3009 and Fusabond'l9 E-MB-226D.
In other ~l~relled thermoplastic aromatic polyester/LCP alloys, the LCP comprises a wholly aromatic copolyester and the compatibilizers are a JTE SHEE~ tRULE 26~
WO 97/24403 PCT~US95/17114 unsatureated ethylene ester copolymer grafted with maleic anhydride and/or an ethylene-maleic anhydride copolymer. Lxemplary ~ t~d ethylene ester copo1ymers grafted with maelic anhydride are the ethylene-methyl acrylate copolymers SP 2205~ and 3306TM, and exemplary ethylene-maleic S anhydride copolymers are Polybond'M 3009 and Fusabond'~9 E-MB-226D.
Another plere~.ed thermoplastic aromatic polyester/LCP alloy of the present invention comprises a wholly aromatic LCP copolyester and ethylene ester copolymer grafted with maleic anhydride and an ethylene-maleic anhydride copolymer compatibilizer.
Yet another ~lerelled alloy comprises thermoplastic aromatic polyester, wholly aromatic LCP copolyester, and a copolyester elastomer such as HYTREL~ HTR 6108 and an ethylene rnaleic anhydride copolymer, such as PolybondsY 3009 and Fusabond~ E-MB-226D.
The ethylene-methyl acrylate copolymers grafted with maleic anhydride, DS~ 1328/60 and Fusabond~9 A MG-175D, and the ethylene maleic anhydride copolymers, PolybondsM 3009 and Fusabond'~9 E-MB-226D, are particularly ~lefelled when the LCP is VECTRATM A-95~. Also e~lled when the LCP is VECTRA~ A-950 are the compatibilizers PolybondTY 3009 or Pusabonda9 E-MB-226D and a second compatibilizer, Escor~9 ATX-320, Escor~ ATX-325, DSTM 132~/60, Fusabond~ A MG-175D, EscoP XV-1104, or HYTREL~ HTR-6108.
The plupellies of the LCP and thermoplastic aromatic polyester, as well as desired ~o~ ies of the res lhin~ alloy, are all taken into consideration in selecting suitable compatibilizers for use in the present invention. The properties of the thermoplastic arornatic polyester/LCP
alloys of the present invention are adjusted by adjusting the amount of compatibilizer and, in some ~l~r~ d embotlin~nt~ by the manner in which the components are combined.
SUBSTITUTE SHEET (RULE 26 W O 97/24403 PCTrUS9~/17114 Because the most expensive component in the alloys of the present invention typically is the LCP, in order to reduce costs it is preferable to keep the LCP content o~ the composition as low as possible while achieving the desired effect. Hence, in the present alloys the LCPs are used as the disperse phase, whereas thermoplastic aromatic polyester is used as the predominant or bulk phase.
When no cu~ a~ibilization exists between thermoplastic aromatic polyester and LCP, such as when no colll~tibilizer is present, the, m~rh~nic~l properties of the rçs~ltin~ blend are low. For example, in films extruded from blends comprising 10% LCP / 90% PCTA (KodarG9 or Eastar~ ~-150) a m~rhinP direction (MD) tensile strength of only about 6,000 psi and MD tensile modulus of only about 300,000 psi are obtained.
l~urthermore, the oxygen barrier properties are poor, for example, around 35 to 40 cc-mil/lOin2-24 hours-1 atm. It was unexpectedly found that when 15 thermoplastic aromatic polyester/LCP alloys were formed by adding suitable c~ mp~ihilizers in accordance with the tearhing~ of the present invention, improved mech~nic~l properties and/or lower gas permeation (harrier) numbers were obtained.
The present invention also provides methods of preparing the alloys 20 described above. These methods include:
i. LCP, thermoplastic aromatic polyester and at least one compatibilizer are mixed and melt blended to form an alloy;
ii. LCP, thermoplastic aromatic polyester and a 2~ portion of the total compatibilizer to be used are mixed and melt blended, the rçm~in~ler of the compatibilizer is added at a later time and further melt blended;
SI~S ~ JTE SHEET (RULE 26 W O 97/24403 PCTrUS9C/17114 iii. LCP, thermoplastic aromatic polyester and a first compatibilizer are mixed and melt blended. A second compatibilizer is added to the melt blend at a later time and ~urther melt S blended;
iv. LCP and thermoplastic aromatic polyester are mixed and melt blended and at least one compatibilizer is added at a later time to the melt blend and further melt blended;
v. Thermoplastic aromatic polyester is melted under al~p~ ;ate conditions in an extruder and at a later time LCP and at least one compatibilizer are added to the thermoplastic aromatic polyester and fur~er melt blended;
vi. Thermoplastic aromatic polyester and a first c~ hilizer are melt blended and at a later time LCP and a second co~ alil)ilizer are added to the melt blend and fur~er mixed and melt blended;
vii. Thermoplastic aromatic polyester and LCP are mixed and melt blended and two co~ Libilizers are added to the melt blended and further melt blended; and viii. Thermoplastic aromatic polyester, LCP and 2~ two compatibilizers are mixed and ~imlllt~n~ously melt blended.
SUBSTITUTE SHEET (RULE 26 _ CA 0224l860 l998-06-26 W 097/24403 PCT~US95/17114 DETAI~ED DESCRIPI'ION OF l~; INVENTION
The LCPlthermoplastic aromatic polyester alloys of ~e present invention are formed by use of at least one compatibilizer. In one preferred embodiment, two compatibilizers are used to form~ the a~loys.
The alloys of the present invention comprise from about 0.5 to about 10 weight percent thermotropic liquid crystalline polymer, from about 40 to about 90 weight percent thermoplastic aromatic polyester, and from about 1 to about 50 weight percent compatibilizer.
The liquid crystalline polymer is preferably present in amounts from about 5 to about 10 weight percent, thermoplastic aromatic polyester is preferably present in amounts from about 70 to about 93 weight percent and one or more compatibilizers are present in amounts from about 2 to about 20 weight percent.
In a particularly plel~ d embodiment, the compositions of the present invention contain from about 9 to about 12 weight percent LCP, from about 78 to about 86 weight percent thermoplastic aromatic polyester, and from about 5 to about 10 weight percent compatibilizer.
Thermoplastic aromatic polyesters suitable for use in the present invention are prepared by methods well known in the art. .A variety of methods for making suitable PET homopolymers and copolymers are well known in the art. For example, one suitable PET for use in the present invention is prepared by the reaction of either terephth~lic acid or d;methyl terephth~l~te with ethylene glycol. Various copolymers of PET have been developed and are also ~ ,d~ed by mPth~ well known to the skilled artisan. Suitable thermoplastic aromatic polyester is also available commercially from a number of vendors. Especially preferred commercially available therrnoplastic aromatic polyesters include F~tm~n Kodak Company's Kodar'l9 or Eastar~ A150, Kodar~ or Eastar~ 9921, SUBSTITUTE SHEET (RULE 26~
CA 0224l860 l998-06-26 Koc~ k'9Or F~t~p~k~ 7352, Kodar~ or Eastar~ 9921W and F~tm~n~
1339; Shell's TraytuffrY 8006; DuPont's Cly~ TM 1927 and Selar~ PT7û67;
and Shell's TraytufflM CPET.
Suitable PCTA copolymers e.g., Kodar~9 or Eastar~ A150, for use in S the present invention are prepared by the reaction of terephth~tic acid iso~hth~lic acid, and cycloh~ n~ ~lim~thznnl. Kodar'~9 or Eastarm A150 is one plc:r~ d con~ ;ially available PCTA for use in the present invention. Preferred comlllelcially available PETs include a PET
homopolymer produced from dimethyl terephth~lz~te and ethylene glyçol 10 such as Kodapak~ or F~t~p~k~ 7352; a PET copolymer comprising terephth~lic acid, isotel~l h~lalic acid and ethylene glycol such as Shell's Traytuff~ 8006; and a CPET such as Shell's T~ayLurr CPET.
Suitable thermotropic LCPs for use in the present invention include wholly and partially aromatic polyesters and co-polyesters such as those lS disclosed in U.S. Patent Nos. 3,991,014, 4,067,852, 4,083,829, 4,130,545, 4,161,470, 4,318,842, and 4,468,364. Plt;fe.led thermotropic ~CPs include wholly or partially aromatic polyesters or copolyesters. Particularly ~lerell~d copolyesters include XYDAR~, VECTRA~ and ZENITE~ (E.I.
duPont de Nemours). Other pl~relled thermotropic liquid crystal polymers 20 include SUMIKASUPER~ and EKONOL~ (Sulllik~lllo Chemi~l), DuPont HXTU, RODRUN'~9 (Unitika) and GRANLAR~ (~r~n-lm~,nt) Vectra~ A950, sold by ('~ nese Research Corporation, Summit, New Jersey is one ~lerelled wholly aromatic copolyester. This polymer has been reported to consist es~enti~lly of about 25-27 percent of 6-oxy-2-25 naphthoyl moieties and about 73-7~ percent of p-oxybenzoyl moieties, as described in example 4 of U.S. Patent No. 4,468,364 and in G. W.
(~alllnr1~nn et al., "Anisotropic Polymers, Their Synthesis and Properties", .lillLed from Procee~lin~ of the Robert A. Welch Co~ l-ces on SUBSTITUTE SHEET (RULE 26) CA 0224l860 l998-06-26 W O 97/24403 PCT~US95/17114 Ch~mic~l Research, XXVI Synthetic Polymers, November 15-17, ~982, ~ouston, Texas, pp. 247-291 (see especially pp. 263-265).
Another particularly ~r~r~led thermotropic LCP is ZENITE~. This polymer has been reported to consist of hydroxy-benzoic acid/phenyl 5 hydroquinone/dimethyl-napthylene dicarboxylate units.
In form~ ting the composition of the alloys of the present invention a number of variables jnrlll~lin~, the properties of the polymers to be blended, ~lu~eliies of the compatibilizers, and the amount and ratio of the components, are taken into consideration. These variables are tailored and 10 o~ d in accordance with the present tç~chin~ to provide alloys to meet a particular end use specification. For example, if high gas barrier properties are desired, then polymers having high individual gas barrier properties are preferably selecte~l The amount of c(~...~~ il>ilizer is adjusted to provide intermolecular 15 bonding among the components of the alloy to enh~nre properties and at the same time, to avoid the formation of a quasi- or pseudo-cross linlced network which is not readily processable.
The compatibilizers for use in the present invention are either rniscible with each of the LCP and the thermoplastic aromatic polyester 20 through, e.g., covalent, ionic, molecular inter-pen~tr~tinn~ hydrogen bonding or associative interactions as mentioned above, or have interactive miscibility when the LCP and thermoplastic aromatic polyester are present in a common phase. In other words, the functional groups of the comp~tihilizer, LCP, and thermoplastic aromatic polyester for use in the 25 alloys are also rh~mic~lly compatible. For example, if the LCP to be alloyed with thermoplastic aromatic polyester has an ~liph~tic type of polyester functionality, such as acrylate or methacrylate, or an aromatic functionality, such as a benzoate or phth~l~t~ ester linkage, then ~ref~,led SuBsTlTuTE SHEET (RULE 26~
W O 97/24403 PCTrUS9S/17114 compatibilizers will have a functionality, such as a polyester functional group or a maleic anhydride functional group, that is capable of reacting with the polyester group.
C~-mp~tihilizers for use in the present invention are also processable in the melting and processing range of thermoplastic aromatic polyester and the LCP and exhibit l~ elaLul~ stability at the int~ ied processing temperature. By temperature stability is meant that a component of the alloy es~enti~lly retains its ch~ l functionality and, hence, its interfacial interaction with the other components of the alloy with which it interacts. If one of the components were not th~ lly stable, it is possible that the compatibilization achieved could fail on subsequent proces~in~.
Preferred alloys of the present invention comprise at least one thermotropic LCP, thermoplastic aromatic polyester, and at least one compatibilizer. Particularly plerelred embo~ ; include two or more compatibilizers, wherein at least one colll~aLibilizer interacts with the LCP
and at least one interacts with the thermoplastic aromatic polyester. The ratios of compatibilizers to each other and in the total composition are adjusted to achieve alloys having the desired pL~ Lies as is shown in the examples which follow.
The following compatibilizers are particularly ~ ed in the practice of the present invention wherein components of the alloy comprise thermoplastic aromatic polyesters and wholly aromatic esters and copolyesters liquid crystal polymers, such as VECTRA~ and XYDAR~:
i. Copolyester elastomers such as HYTREL~
HTR-6108 from DuPont;
ii. Ethylene maelic arlhydride copolymers including HDPE grafted with maleic anhydride, such as Polybond~ 3009 from BP Chlomir~
S~J~ 111 ~JTE SHEET (RULE 26) W O 97/24403 PCT~US95/17114 and a linear low density polyethylene-maleic anhydride graft such as Fusabond~ E-MB-226D
from DuPont of C~n~
iii. Ethylene-methyl acrylate copolymers, such as S SP 2205~ and SP3306~ from Chevron Chemi-~l Co~ lly;
iv. Ethylene-methyl acrylate copolymers grafted with maleic anhydride, such as DS~ 1328/60 from Chevron Chemi~ :ll Colllpal-y and Fusabond~ A MG-175D from DuPont (~n~
v. Ethylene-methyl acrylate copolymer, such as Lotader~ 2400, Lotader~ 3410 and Lotader~
5~00 from Elf Atocll~rn;
vi. E~ylene-methyl-methacrylic acid terpolymers (ethylene-methyl acrylate-acrylic acid terpolymers) such as Escor'l9 ATX-320, EscoP
ATX-325, and EscoP XV-1104 from Exxon Chemi~l; and vii. Acrylic rubber such as VAMACTM G1 from DuPont.
The alloys of the present invention can be extruded to form various articles of m:~mlf~ re such as films and tubes useful, e.g., in food pack~ging, electronic circuit sllbstr~tPs and structural applications. The 25 films can be therrnoformed to provide, e.g., trays, blow molded to, e.g., form containers, and otherwise processed by known methods. In some embo-limPnts, articles of m~mlf~ctnre COlll~liSillg the alloys of the present invention are provided with a thin coating of, e.g., glass, metal or another 51u~5 ~ 1 1 UTE SHEET ~RULE 26) W O 97/24403 PCTrUS95/17114 polymer both to protect the article and to provide suitable means to affix labels and the like.
To illustrate the i~ oved properties of the alloys of the present invention, various alloys were prepared as taught herein and extruded to 5 form films having improved tensile strength, tensile modulus and/or oxygen barrier properties over films extruded from thermoplastic arornatic polyester or LCP and thermoplastic aromatic polyester blends without compatibilizers.
In some films, tensile strength was increased by up to more than 2 times and tensile mmlnlllc was increased up to more than 3 times over that of the blend without cnmp~tihilizer. In many in~nrPc, values above 10,000 psi and tensile strength and/or above 500,000 psi and tensile modulus were obtained.
Films extruded from alloys CO~ ;Sil~g thermoplastic aromatic polyesters in~ rlin~ PCTA and PET homopolymers, a wholly aromatic 15 copolyester LCP, and a co.~ Libilizer selected from a copolyester elastomer; a copolyester elastomer and an ethylene ester copolymer grafted with maleic anhydride; or an ethylene-methyl acrylate-mPfh~crylic acid terpolymer.
Films extruded from alloys c~ ing therrnoplastic aromatic 20 polyester, and an anhydride-grafted ethylene-methyl acrylate copolymer, thermotropic LCP wholly aromatic copolyester and a ethylene ester copolymer grafted with maleic anhydride showed improved mf~rh~nir~l properties.
Films extruded ~rom three component alloys colll~lisi~g 25 thermoplastic aromatic polyester, wholly aromatic copolyester and an ethylene-methyl-methacrylic acid terpolymer, e.g., Escor~ ATX-320 or -325, had superior mPch~nir~ vpel~ies. Also, three component blends con~li~ g thermoplastic aromatic polyester, wholly aromatic copolyester SUBSTITUTE SHEET (RULE 26~
W O 97/24403 PCTrUS9Stl7114 and a copolyester elastomer such as HYTRELTM HTR-6108 were extruded to produce films having superior m~ch~nif~l ~rop~:llieS.
A number of films extruded from the alloys of the present invention yielded low oxygen permeation values, ranging from about 18 to 30, well below the 36 to 40 cc-mil/lOin~-24 hours-l atm expected for Kodar~ or Eastar~ A150 and in another case ranging from about 8 to 22, well below the about 28 cc-mil/lOin2-24 hours-latm expected for Kodapaka9 or F~ct~p~kTM 7352.
Films extruded from alloys CO~ liSillg PCTA such as Kodar'~9 or EastarlM A150, a wholly aromatic copolyester LCP and a copolyester elastomer such as HYTRELTU HTR-6108 had excellent barrier properties.
Also, films extruded from alloys com~ g thermoplastic aromatic polyester, a copolyester elastomer, such as HYTRELTU HTR-6108, a wholly aromatic copolyester, and ethylene maleic anhydride copolymer, such as Polybond~ 3009, had excellent oxygen barrier p~ ellies, e.g., from about 21 to 23 cc-mil/lOin2-24 hours-l atm. Excellent barrier l)L~pelLies were also obtained with films extruded from alloys c~,lllprising KodapakZ9 or F~t~r~k~ 7352, VECTRAsU A-950 and Escor~9 ATX-325 or HYTREL~
HTR-6108. One preferred alloy comprised Kodapak'~9 or F~tS~r~k~ 7352 at about 87%, HYTRELTM HTR-6108 at about 3~'o, and VECTRA~A-950 at about 10%. Another pl~lled alloy comprised Kl-d~r~k'l9 or F.~t~p~k~ 7352 at between about 88-89%, Escor'lDATX-325 at about 2 to 4%, and VECTRA~ A-950 at 10%. See Table Q. The over 3 times improvement in barrier equal to over 3 times reduction in permeability was unexpected.
2~ The o~linlulll amount of compatibilitizer to obtain the desired reduction in permeability will vary depending upon run conditions but such opLilllulll amounts are readily determined by the skilled artisan in view of the present te~rhin~ .
SUBSTITUTE SHEET ~RULE 26) CA 0224l860 l998-06-26 Optional components well known to the skilled artisan may be added to alloys of the present invention provided that ~ey do not i~ LÇ~l~ with formation or with the desired final properties of an alloy. Such additives includes ~lllers and pigments, lubricants, mold release agents, plasticizers, 5 ultraviolet stabilizers and so forth.
~ n the methods of the present invention, co...~ ilizers are used either alone or in various combinations with LCP and thermoplastic aromatic polyester to achieve the desired results. They are also used in single step and sequential compatibilization methods as described below.
The following methods have been found to provide alloys having improved properties which can be used, e.g., to provide films having improved ~n~pe~lies over films of LCP and thermoplastic aromatic polyester blends. These methods include:
i. LCP, thermoplastic aromatic polyester 1~ and at least one compatibilizer are mixed and melt blended to form an alloy;
ii. LCP, thermoplastic aromatic polyester and a portion of the total compatibilizer to be used are mixed and melt blended, the rem~in~ler of the comp~tihilizer is added at a later time and further melt blended;
iii. LCP, thermoplastic aromatic polyester and a first compatibilizer are mixed and melt blended. A second compatibilizer is added to the melt blend at a later time and further melt blended;
SU~ I ~ I UTE SHEET (RULE 2 W O 97t24403 PCT~US95117114 iv. LCP and thermoplastic aromatic polyester are mixed and melt blended and at least one compatibilizer is added at a later time to the melt blend and furt'ner melt blended;
v. Thermoplastic aromatic polyester is melted under applol liate conditions in an extruder and at a later time LCP and at least one con~ ibilizer are added to the thermoplastic aromatic polyester and further melt blended;
vi. Thermoplastic aromatic polyester and a first compatibilizer are melt blended and at a later time LCP and a second comp~tihilizer are added to the melt blend and further mixed and melt blended;
vii. Thermoplastic aromatic polyester and LCP are mixed and melt blended and two compatibilizers are added to the melt blended and further melt blended; and viii. Thermoplastic aromatic polyester, LCP
and t~,vo compatibilizers are mixed and simlllt,.n~ously melt blended.
25 By controlling the order in which ~e components of the alloys are mixed and melt blended the properties of the alloy are controlled to enable the production of articles of m~mlf~-~t~lre, e.g., films, which have improved properties over the plup~l~ies of a similar article of m~m~f~ct~lre composed SUBSTITUTE SHEET (RULE 26) W O 97/24403 PCT~US95/17114 solely of thermoplastic aromatic polyester or of LCP and thermoplastic aromatic polyester.
In the production of films from the alloys described above, the meld blend is extruded, e.g., through a slot die, a circular, counter-rotating die, or a circular rotating trimodal die.
In alloys cont~ining two compatibilizers, sequential compatibilization according to methods (iii) and (vi) above are pler~l,ed pl~a.dLion methods.
It was unexpectedly discovered that these unique methods of combining two or more compatibilizers, provided alloys having irnproved properties.
While not wishing to be bound by theory, it is believed that in this novel process, two compatibilizers interact sequentially to provide the desired compatibilization and in some cases also interact with each other. In the case of thermoplastic aromatic polyester-LCP blends of the present invention, the interaction is between the thermoplastic aromatic polyester and a first comp~tihilizer, and the LCP int~r~ts with a second comr~tihilizer. The products of these two interactions, then seq~nti~lly react with one another to form an alloy.
The methods of the present invention provide a great deal of flexibility to achieve the desired compatibilization through the wide array of possibilities for the compatibilizers to interact with the major colllponellL~ of the alloy, which is the object of the co,-,p~lihilization. The methods of the present invention provide an innovative yet efficient way to achieve the desired end results.
In one ~ rell~d embodiment of the present invention, Chevron DSTU
1328/60, an a-ll~ydlide-grafted ethylene-methyl acrylate copolymer, was melt blended with thermoplastic aromat;c polyester and then Polybond~
3009, and VECTRA~ A-950 were added to the mixture and further melt blended to produce alloys which were extruded to produce films having SUBSTITUTE SHEFT (RULE 26~
W 097/24403 PCTrUS95/17il4 greatly improved mP-~h~nic~l properties. For example, a tensile strength of 14,800 psi was obtained in one i~llm extruded from an alloy made by feeding 5% of the Chevron DS~ 1328/60 in the hopper with the thermoplastic aromatic polyester, and then by feeding 2% Polybond~ 3009 S with the LCP VECTRA~ A-950 into the vent feed port.
In another preferred embo~limf~nt~ Escor~9 ATX-325, an ethylene-methyl-mPth~crylic acid terpolymer, was melt blended with thermoplastic aromatic polyester and then Polybondn' 3009 and VectraTM A950 were added to the mixture and further melt blended. A tensile m~ lhlC value of 1.09 10 million psi was obtained in a film extruded from an alloy made by feeding ~% of Exxon ATXTY 320 in the hopper with the PAT, and then feeding 2%
Polybond~ 3009 with the LCP VECTRA~ A-950 into the vent feed port.
Accol.lhlgly, it can be seen that films produced from the alloys of the present invention have surprisingly improved plu~llies over films of 15 LCP and PAT blends or of PAT alone.
Conventional extrusion e~lui~ ellt was used to produce the alloys of the present invention and to extrude films from these alloys. Mixing and melt blending of components to form the alloys of the present invention is carried out using conventional single or double screw extruders. It is 20 pl~fellc:d that the extruder system has not less than 25/l L/D ratio.
Extrusion conditions such as processing tempeldLul~ s, rotation speed of the screw, feed rate and through put were optimized for the particular alloy by taking into consideration the pl~")elLies of the polymers being melt blended to form the alloy, including res~llting viscosity of the melt blend. Typically, 25 higher shear screw configurations were found to give better dispersions of the LCP and better compatibilization remlting in alloys that could be used to produce films having improved properties. Typical L~ Lules SuBsTlTuTE SHEET (RULE 26~
W O 97/24403 PCTrUS95/17114 employed for the processing were 525 to 620~F. The rotation rate of the screw was, typically between 50 to 300 rpm.
The alloy components are ~Iu~iately conditioned, e.g., dried and then fed to the extNder using convPntio~l methods. For example, the S components can be melt blended and extruded to form pellets. The pellets can then be extruded or injection molded to form the desired article of m~mlf~ lre. ~ ;vely, the dry components can be blended, fed into the extruder, and extruded, e.g., to a film directly.
The rnasterblending or masterb~tching technique in which typically, a 10 blend of two components is processed into pellets to form the "masterblend"
can also be used. The masterblend can be run through an extruder a second time with additional components added in accordance with the tP~rhin~c of the present invention. This is a convenient method of m~mlf~rtllre, because an inventory of masterblend material can be made and then combined with 15 dirrel~llL components as desired. One advantage to the masterblending process is that small and very controlled amounts of additional components can be added to the l,la~L~ lend. For example, if the llla~L~.l,atch has 10%
LCP, the ma~LelbaLcll can be passed through the extruder again with, for example, 10% of the masterbatch and 90% of the other polymers, providing 20 a masterbatch that is 1 ~o in LCP.
Through ma~L~lb~ hinp, controlled low concentration of a component in the alloy can be obtained; and ~ itiQn~l mixing and ~h~ring through multi-passes in the extruder can be achieved, if desired.
Masterbaching also provides advantages when working with a 25 component having a low melt temperature, such as the compatibilizer Fusabond~9 A MG-175D which has a melt temperature of about 45~C. It can be added over time at the vent feed with the LCP. However, in one pl~Lred method of the present invention the LCP and low melt SUBSTITUTE SHEET ~RULE 26~
W O 97/24403 PCTrUS95/17114 temperature compatibilizer are masterb~trhPc~, thus allowing greater control over the processing of this low melt temperature component which is also present at a low conr~ntr~tion.
The present invention will be fur~er illustrated with reference to the S following example which is inten-le(l to aid in the underst~n(iin~ of the present invention, but which is not to be construed as a limitation thereof.
E~LE
The alloy components should be appioL~liately treated, e.g., dried, before processing as would be readily apparent to the skilled artisan.
The work described in the following exarnple was carried out using a conventional 25 mm or 40 mm co-rotating, non-hl~ p~ twin screw extruder m~nnf~rtllred by Berstorff Corporation. Mixing and knP~(1ing elemPnt~ for the screw configuration were varied according to conventional wisdom to achieve the desired degree of mixing.
E~ilms were extruded from a slot die, approximately 8 inches wide with die gap of approximately 0.010 to 0.020 inches. Also, a counter-rotating die or circular trimordal die ~see, U.S. Patents 4,975,312 and 5,288,529) can be used to extrude films coll~lisillg one or more alloys of the present invention. Since the degree of llni~xi~l orient~ti~ n produced in the extruded film has an impact on the properties, films having similar extrusion conditions were cOlll~al~d in the work cli~r~c~e~ below.
A universal testing m~rhin~ was used for testing the tensile properties based on ASTM standard tests, e.g., ASTM #0882.
The LCP used was Vectra~ A-950 from Hoechst-Cel~n~se Corporation. A PCTA copolymer purchased from F~ctm~n Chemiral~
under the tr~(len~m~ Kodar'9 or Eastar~ A150 was used in the following work. Also used was a PET homopolymer purchased from F~tm~n SlJ~ JTE SHEET (RULE 26) W O 97/24403 PCTrUS95/17114 l~hPmir~l under the tr~den~m~ Kodapak~ or F~t~r~k~ 7352 and a CPET
purchased from Shell under the tr~ n~m~ Traytuf~ CPET. The compatibilizers used included: HYTRELTM HTR-6108; PolybondTY 3009; and Fusabond~ E-MB-226D; SP 2205TU and 3306TM; DSsM 1328/60 and S Fusabond39 A Mal75D; Lotader~ 240~); Escor'l9 ATX-320, Escor~9 ATX-325, and; Escor39 XV-1104; and Vamac~ G1.
The run conditions and results are shown in Tables I-VII. In the Tables, the thermoplastic aromatic polyesters used are inr1ie~terl as follows:
Kodar'l9 or Eastar~ A150 as "A150," or Kodar'l9 or Eastar~ 9921 as "9921,"
or Kodapak~9 or F~t~r~krM 7352 as "7352" and Shell's TraytuffrM CPFT as "CPET." The VECTRA~ LCP is in~ tt-d as "A950." "Ten Yld St."
intli(~t~s Tensile Yield Streng~; and "Ten. Mod. " in-lir~t~s Tensile Modulus Values. In ~e Tables, compatibilizers listed are itl~.ntifi~cl as ~ollows: HYTl~ELTU HTR-6108 as Hytrel 6108; Polybond~ 3009 as "BP3009"; SP 2205TU as "SP2205"; DS~ 1328/60 as "Chev DS"; Lotader~
2400 as "Lotader 2400"; Escor~9 ATX-320, ATX-325 and XVl104s "ATX320", "ATX325" and "XVllO4" respectively, and Fusabond~9 E-MB-226D as "Fusabond226".
SUBSTITUTE SHEET (RULE 26) W O 97/24403 PCTrUS95/17114 TABLE A
LCP, themoplastic aromatic polyester and at least one compatibilizer are mixed and melt blended to forrn an alloy.
s RUN # HOPPER ~ ;D TEN YLD TEN MOD OX-ST MD(Kpsi)MD(Kpsi) BARRlER
6299-7 85.7%A150+9.5%A950 10.6 800 27.2 +4.8%ATX320 6299-9 85.7%A150+9.5%A950 9.7 810 +4.8%ATX325 6299-10 8S.7%A150+9.5%A950 9.1 570 25.3 +4.8 %Chevron 8249-9 95%8006+4%A9507.1 209 +4%Hy~rel6108 TABLE B
LCP, thermoplastic aromatic polyester and a portion of ~e total compatibilizer to be used are mixed and melt blended, the rem~in~ler of the compatibilizer is added at a later time and further melt blended.
R~ ~ HOPPER FEED VENT FEED TEN YLDTEN MOD OX-ST MD MD BAR
(Kpsi) (Kpsi) RIER
6249-3 85.7%A150+ 2.4%ATX325 10.0 421 25.5 9.5 %A950 + 2.4 %ATX325 6249-7 85.7%A150+ 2.4%BP3009 12.9 460 26.8 9.S %A950 +2.4%BP3009 8319-2 91 %8006+2% 1 %Fusabond226D6.9 320 Hyt}el6108 +7%A950 9085~ 86%7352+1% 10%A950+ 7.19 263 8.4 Hytrel6108 2%F~ )n~1'7~6D
2~i SUBSTITUTE SHEET (RULE 263 W O 97/24403 PCT~US95/17114 TABLE C
LCP, thermoplastic aromatic polyester and a first compatibili~er are mixed and melt blended. A second S comp~tt~lilizer is added to the melt blend at a later time and further melt blended.
RUN # HOPPER FEED VENT FEED TEN YLD TEN MOD
ST MD(Kpsi) MD(Kpsi) 6249-8 85.7%Al50+ 2.4%Lotader7.2 233 9.5 %A950 2400 +2.4%ATX325 TABLE D
LCP and thermoplastic aromatic polyester are mixed and melt blended and at least one compatibilizer is added at a later time to the melt blend and further melt blended.
RUN # HOPPER FEED VENT TEN YLD TEN OX-FElEDST MOD BARRIER
MD(Kpsi) MD(Kpsi) 6299-14 85.7%Al50+ 7.8% 9.1 530 26.6 9.5 %A950 ATX320 TABLE E
Thermoplastic aromatic polyester is melted under ~I ~r~ ial~
conditions in an extruder and at a later time LCP and at least one compatibilizer are added to the PET and further melt blended.
RUN # HOPPER FEED VENT FEED TEN YLD TEN
ST MOD
MD(Kpsi)MD(Kpsi) 6309-12 85.7%Al50 9.7%A950 7.1 460 +4.8 %ATX325 8249-4 94%8006 4%A950 7.16 233 +0.75 %SP2260 S~ TE SHEET(RULE 26) TABLE F
Thermoplastic aromatic polyester and a first compatibilizer are melt blended and at a later time LCP and a second cnmr~tibilizer are added to the melt blend and further mixed and melt blended.
RUN #HOPPER FEEDVENT FEED TEN YLD TEN OX-ST MOD RARR~.R
MD(Kpsi)MD(Kpsi) 7019-789%A150 9.3%A950 12.7 810 29.6 +4.7%ATX320 +2%BP3009 7069-889%A150 9.3 %A950 11.2 960 25.7 +4.7% +2%BP3009 ChevronDS
7069-989%A150 9.3%A950 9.6 740 +4.7%XV11.04 +2%BP3009 7069-1089%Al50 9.3 %A950 9.3 850 20.3 +4.7% +2%BP3009 Hyt~el6108 7079-189%A150 9.3%A950 14.8 840 29.8 +4.7% +2%BP3009 ChevronDS
8259-3939ta8006 4%A950 7.73 278 +2%Hytrel6108 + 1 %
Fusabond TABLE G
Thermoplastic aromatic polyester & LCP are mixed and melt blended and two compatibilizers are added to the melt blended and further melt blended.
RUN #HOPPER VENT FEED TEN YLD TEN OX-FEED ST MOD l~ARRTF,R
MD(Kpsl)MD(Kpsi) 7069-685.7%A1502.4%Hyt}el6108 6.2 420 26.3 +9.5%A950 +2.4%BP3009 SuBsTlTuTE SHEFT (RULE 26 W O 97/24403 PCT~US95/17114 TABLE H
Thermoplastic arom~tic polyester, LCP and two S compa~ibilizers are mixed and .~iml-lt~nPously melt blended in an extruder and extruded through a slot die.
RUN # HOPPER FEED TEN YLD T~N MOD OX-ST ~DD~Kpsi) BARRUER
h1D(Kpsi) 7169-3 80%A150+10%A950 7.9 370 25.3 +~.5%Hytrel6108+~.5%BP3009 TABLE J
Thermoplastic aromatic polyester, LCP and two co~ )aLil)ilizers are mixed and ~imlllt~nPously melt blended and extruded through a circular, counter-rotating die.
RUN # HOPPER FEED TEN YLD TEN MOD
ST ~DD(Kpsi) ~DD(Kpsi) 1199~3 83%A150+10%A950+5%ATX320 6.2 440 +2%BP3009 H99-4 81%A150+10%A950+5%SP2205 5.9 370 +4 %BP3009 1199-5 81%A150+10%A950+5%SP2205 7.2 440 +4%Hysrel6108 SUBSTITUTE S~IEET (RULE 26 W O g7/24403 PCTrUS95117114 TABLE K
Thermoplastic aromatic polyester and a first co~ a~ibilizer are S melt blended and, at a later time, LCP and a second comp~tihlizer are added to the melt and fur~er mixed and melt blended and extruded using a circular rotating trimodal die.
RUN # HOPPER FEED VENT FEED TEN YLD TEN
ST MOD
MD(Kpsi) MD(Kpsi) 3249-2 83.6%A150 10%A950+2%BP3009 9.0 290 + 4.4 %ATX320 3249-5 83.6%A150 10%A950+2%BP3009 6.5 220 +4.4%ChevronDS
TABLE L
Control thermoplastic aloll~Lic polyester RUN # HOPPER FEEDTEN YLD TEN OX-ST MOD RARV~R
MD(Kpsi)MD(Kpsi) 6249-1 100%A150 5.5 162 5269-0 100%A150 5.4 190 5119-0 100%A150 5.8 169 4239-1 100%A150 6.2 176 31.5 6299-1 100%A150 5.2 320 7069-1 100%A150 5.3 320 29.9 3189-1 100%A150 6.2 200 SlJ3~ 111 ulTE SHEET (RULE 26 TABLE M
Control thermoplastic aromatic polyester & LCP, No Com?atibilizer RUN #HOPPER FEED l~:N YLD TEN OX-ST MOD B,~RRni.R
MD(Kpsi)MD(Kpsi) 3189-2 90%A150+10%A950 6.9 290 3189-5 90%A150+10%A950 5.5 210 22.7 3189-9 90%A150+ 10%A950 5.8 231 6249-2 90%A150+ 10%A950 7.4 251 7069-2 90%A150+10%A950 6.1 420 24.9 7019-5 90%A150+10%A950 6.1 440 TABLE N - Ma~ lJa~ch RUN # HOPPER FEED VENT TEN YLD TEN OX-FEED ST MOD BARR
MD~Kpsi) ~DD(Kpsi ) 8129-1 83%A150 10%A950 8.0 550 20.6 +5%Hytrel6108 +2%BP3009 8129-5 78%A150 10%A950 7.8 230 19.6 +10%Hytrel6108 +2%BP3009 8129-10 83%A150 10%A950 5.6 430 22.1 +5%Hytrel6108 +2%BP3009 8129-16 78%A150 10%A950 5.9 420 18.5 + 10%Hytrel6108 +2%Hytrel6108 8129-17 78%A150 10%A950 5.8 430 18.4 + 10%Hytrel6108 +2%Hytrel6108 8129-18 78%A150 10%A950 7.4 600 19.5 + 10%Hytrel6108 +2%BP3009 8129-19 78%A150 10%A950 7.6 710 18.0 + 10%Hytrel6108 +2%BP3009 8289-5 94~o7352 1 %A950 7.37 268 +2%Hytrel6108 +3 %Fusabond SuBsTlTuTE SHEET (RULE 26 W O 97/24403 PCTrUS95/17114 TABLE O
In some runs, LCP, thermoplastic aromatic polyester and one S co~ libilizer are added to the hopper feed and melt blended to form an alloy. In other runs, thermoplastic aromatic polyester and one comr~tihilzer are added to the hopper feed and LCP and Fusabond 226 are added at the vent feed and melt blended to form an alloy.
0 RIJN # HOPPER ~ED VENT FEEDTEN YLD TEN
ST MD MOD
~Kpsi~MD(Kpsi) 9259-1 100%A150 - 5.5 180 9259-2 90%A150+10%A950 - 7.3 560 9259-3 85%A150+10%A950 - 8.7 740 + 5 %ATX325 9269-1 100%7352 - 5.8 250 9269-2 90%7352+10%A950 - 6.2 290 9269-3 85%7352+10%A950 - 7.0 290 +5 %ATX325 9269-4 88%7352+10%A950 - 6.7 300 +2%Escor325 9269-5 86%7352+ 10%A950 - 7.3 300 +4%Escor325 9269-6 86%7352 10%A950 7.3 320 +2%Escor325 +2%Fusabond226 9269-7 84%7352 10%A950 7.2 310 +4%Escor325 +2%Fusabond226 9269-8 86%7352 10%A950 7.2 310 +2%Hytrel6108 +2%Fusabond226 9269-9 84%7352 10%A950 6.5 260 +4%Hytrel6108 +2%Fusabond226 9269-lOA 85 %7352 10 %A950 6.7 280 +4%Hytrel6108 + 1 %Fltr ~hont~ 6 SUBSTITUTE SHEET (RULE 21;~
W O 97t24403 PCT~US95/17114 TABLE O - cont'd RUN # HOPPER Fl~;ED VENT FEED TEN YLD TE;N
ST MD MOD
(Kpsi)MD(Kpsi) 5 9269-lOB85%7352 10%A950 7.0 340 +4%Hytrel6108 +1%r~ 6 9269-11 82%7352 10%A950 7.0 320 +5%Hytrel6108 +3%F~ h-n~ 6 9269-1286%7352+10%A950 - 6.4 310 +4%Hytrel6108 9269-1387%7352+10%A950 - 7.3 340 +3 %Hytrel6108 9269-1488%7352+ 10%A950 - 6.9 330 +2%Hyt~el6108 109269-1589%7352+10%A950 - 7.3 320 + 1 %Hytrel6108 TABLE P
LCP, thermoplastic aromatic polyester and comp~tihilizer are added to the hopper feed and melt blended to form an alloy.
20 RUN # HOPPER FEED TEN YLD TEN MOD
ST MD (Kpsi) MD (Kpsi) 04059-1 90%CPET+10%950 10 610 04059-2 86~h%CPET+10%A950+31h%ATX320 11 640 04059-3 85 %CPET + 10 %A950 + 5 %ATX32011.7 620 S~J~a 1 l l UTE SHEET (RULE 26) TABLE Q
s LCP, thermoplastic aromatic polyester and cc ...p;1lihilizer are added to the hopper feed and melt blended to form an alloy RUN # HOPPER FEED OXYGEN-pF,Rl~lAR~ ,lTY
cc-milllOOin2-d ,.' 11169-1 100%7352 28 9269-3 85 %7352 + 5 %ATX325 + 10 %A950 9 92694 88%7352+2%ATX325+10%A9S0 9 9269-S 86%7352+4%ATX325+10%A9S0 9 9269-12 86%7352+4%Hytrel6108+109t0A9S0 21 9269-13 87%7352+3%Hyt~el6108+ 10%A950 8 9269-14 88%7352+2%Hytrel6108+10%A950 20 9269-15 89%7352+1%Hytrel+10%A95022 The present invention has been described in detail inr~ ing the p,~;re,led embotlim~nt~ thereof. EIowever, it would be a~pl~.;idled that those 2~ skilled in the art, upon c~m~ider~tion of the present disclosure, may ~ke modifif ~tinns and/or improvements on this invention and still be within the scope and spirit of ~is invention as set for~ in the following claims.
SUBSTITUTE SHEET (RULE 26~
s Copolymers and terpolymers comprising ethylene-methyl acrylate, copolyester elastomers and acrylic elastomers are particularly p,ere.led compatibilizers for use in the present invention.
A particularly plel~lled:
(i) copolyester elastomer is HYTREL~ HTR-6108 from DuPont;
(ii~ ethylene-methyl acrylate copolymer is SP 2205TN and 3306~ from Chevron /~hrmir~l G~lllpal~y;
(iii) ethylene maleic anhydride copolymer is Polybond~
3009 from BP Chemir~l~ and Fusabond'l9 E-MB-226D
from DuPont Cl~n~
(iv~ ethylene-me~yl acrylate copolymer grafted with maleic anhydride is DS~ 1328/60 from Chevron ~hrmir~l Company and Fusabond~9 A MG-175D from DuPont ~n~rl~;
(v) ethylene-methyl acrylate-maleic anhydride terpolymer is Lotader~ 2400, Lotader~ 3410, and Lotader~ 5500 from Elf ~torhrm;
(vi) ethylene-methyl acrylate-methacrylic acid terpolymer is Escor'l9 ATX-320, EscorG9 ATX-325 or Escor~ XV-1104 from Exxon (~hemir~l; and (vii~ acrylic rubber is Vamac~ G1 from DuPont.
SUBSTITUTE SHEET (RULE 26) W O 97124403 PCTrUS95/17114 Thermoplastic aromatic polyesters for use in the present invention are commonly referred to by those skilled in the art as PET polymers and include but are not limited to PET (homopolymers and copolymers), polybutylene terc;~ late (PBT), PETG (PET modified with cyclohex~n~lim~thanol (CHDM)), PCTA copolymers (a polymer of CHDM
and terephth~lic acid with another acid substituted for a po~tion of the terephthalic acid), PBT (polybutylene tere~hth~1~te), APET (amorphous polyethylene), CPET (cyst~11i7~1e PET), PCPT (copolyester cont~ining propylene glycol), PEN (polyethylene n~phth~1~te), and PBN (polybutylene naphth~1~te). Preferred thermoplastic aromatic polyesters include PET
homopolymers and copolymers co~ g terephth~lir acid and isot~re~ 1ic acid, and PCTA. F.~re~i~11y pr~rerfed thermoplastic aromatic polyesters include F~tm~n Kodak Company's Kodar~9 or Eastar~
A150, Kodar~ or Eastar~ 9921, Kodapak~9 or F~t~r~kTM 7352, Kodara9 or Eastar~ 9921W and F~tm~nTM 1339; Shell's Traytuff~ 8006; DuPont's Crystar~ 1927 and Selar~ PT7067; and Shell's Traytuff~ CPET.
Preferred thermotropic LCPs include wholly or partially aromatic polyesters or copolyesters. Particularly pl~;rt:l,ed copolyesters include XYDARTM, VECTRA~ and ZENITE~ (E.I. duPont de Nemours).
Other ~i~re-led thermotropic liquid crystal polymers include SUMIKASUPER~ and EKONO~TM (Sumitomo Ch~mir~l), DuPont HX~, RODRUN'I9 (Unitika) and GRANLARTU (Grandmont).
~f~"ed LCPs for use in the present invention include any such resins with a melt temperature in the range of 250 to 350~C. Particularly pr~r~ d LCPs have a melt temperature in the range of 250 to 280~C.
One pl~rel,ed alloy in accordance with the present invention comprises thermoplastic aromatic polyester, a wholly aromatic LCP
copolyester and an ethylene-methyl acrylate-acrylic acid terpolymer SuBsTlTuTE SHEET (RULF 263 W O 97l24403 PCTrUS95/17114 compatibilizer, for example, Escor~ ATX-320, Escora9 ATX-325, or Escor'~9 XV- 1 104.
Another prt~ ed alloy comprises thermoplastic aromatic polyester, a wholly aromatic LCP copolyester and a ethylene maleic anhydride S copolymer compatibilizer such as Polybond~ 3009 or Fusabond~9 E-MB-226D.
Yet another ~refell~d alloy in accordance with ~is invention comprises ~ermoplastic aromatic polyester, a wholly aromatic LCP
copolyester and an ethylene-methyl acrylate copolymer grafted with maleic anhydride compatibilizer, such as DS~ 1328/60, or an ethylene acrylate terpolymer grafted with maleic anhydride such as Fusabond~ A MG-175D, or a copolyester elastomer such as HYTREL~ HTR 6108.
Alloys con~ g thermoplastic aromatic polyester, LCP and at least two compatibilizers are particularly pl~;felled in ~e practice of the present invention. The u~mr~tihilizers are preferably selected from a copolyester elastomer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl acrylate copolymer grafted with maleic anhydride, ethylene-methyl acrylate-maleic anhydride terpolymer, ethylene-methylacrylate-methacrylic acid terpolymer, or acrylic rubber.
Preferred two compatibilizer alloys include a PCTA copolymer such as KodarG9 or Eastar~ A150, a wholly aromatic LCP copolyester, an ethylene-methyl acrylate-acrylic acid terpolymer and ethylene maleic anhydride copolymer compatibilizer. Exemplary ethylene-methyl acrylate-acrylic acid terpolymers include Escora9 ATX-320, Escor$ ATX-325, or Escor~D XV-1104 and an exemplary ethylene maleic anhydride copolymers are Polybond~ 3009 and Fusabond'l9 E-MB-226D.
In other ~l~relled thermoplastic aromatic polyester/LCP alloys, the LCP comprises a wholly aromatic copolyester and the compatibilizers are a JTE SHEE~ tRULE 26~
WO 97/24403 PCT~US95/17114 unsatureated ethylene ester copolymer grafted with maleic anhydride and/or an ethylene-maleic anhydride copolymer. Lxemplary ~ t~d ethylene ester copo1ymers grafted with maelic anhydride are the ethylene-methyl acrylate copolymers SP 2205~ and 3306TM, and exemplary ethylene-maleic S anhydride copolymers are Polybond'M 3009 and Fusabond'~9 E-MB-226D.
Another plere~.ed thermoplastic aromatic polyester/LCP alloy of the present invention comprises a wholly aromatic LCP copolyester and ethylene ester copolymer grafted with maleic anhydride and an ethylene-maleic anhydride copolymer compatibilizer.
Yet another ~lerelled alloy comprises thermoplastic aromatic polyester, wholly aromatic LCP copolyester, and a copolyester elastomer such as HYTREL~ HTR 6108 and an ethylene rnaleic anhydride copolymer, such as PolybondsY 3009 and Fusabond~ E-MB-226D.
The ethylene-methyl acrylate copolymers grafted with maleic anhydride, DS~ 1328/60 and Fusabond~9 A MG-175D, and the ethylene maleic anhydride copolymers, PolybondsM 3009 and Fusabond'~9 E-MB-226D, are particularly ~lefelled when the LCP is VECTRATM A-95~. Also e~lled when the LCP is VECTRA~ A-950 are the compatibilizers PolybondTY 3009 or Pusabonda9 E-MB-226D and a second compatibilizer, Escor~9 ATX-320, Escor~ ATX-325, DSTM 132~/60, Fusabond~ A MG-175D, EscoP XV-1104, or HYTREL~ HTR-6108.
The plupellies of the LCP and thermoplastic aromatic polyester, as well as desired ~o~ ies of the res lhin~ alloy, are all taken into consideration in selecting suitable compatibilizers for use in the present invention. The properties of the thermoplastic arornatic polyester/LCP
alloys of the present invention are adjusted by adjusting the amount of compatibilizer and, in some ~l~r~ d embotlin~nt~ by the manner in which the components are combined.
SUBSTITUTE SHEET (RULE 26 W O 97/24403 PCTrUS9~/17114 Because the most expensive component in the alloys of the present invention typically is the LCP, in order to reduce costs it is preferable to keep the LCP content o~ the composition as low as possible while achieving the desired effect. Hence, in the present alloys the LCPs are used as the disperse phase, whereas thermoplastic aromatic polyester is used as the predominant or bulk phase.
When no cu~ a~ibilization exists between thermoplastic aromatic polyester and LCP, such as when no colll~tibilizer is present, the, m~rh~nic~l properties of the rçs~ltin~ blend are low. For example, in films extruded from blends comprising 10% LCP / 90% PCTA (KodarG9 or Eastar~ ~-150) a m~rhinP direction (MD) tensile strength of only about 6,000 psi and MD tensile modulus of only about 300,000 psi are obtained.
l~urthermore, the oxygen barrier properties are poor, for example, around 35 to 40 cc-mil/lOin2-24 hours-1 atm. It was unexpectedly found that when 15 thermoplastic aromatic polyester/LCP alloys were formed by adding suitable c~ mp~ihilizers in accordance with the tearhing~ of the present invention, improved mech~nic~l properties and/or lower gas permeation (harrier) numbers were obtained.
The present invention also provides methods of preparing the alloys 20 described above. These methods include:
i. LCP, thermoplastic aromatic polyester and at least one compatibilizer are mixed and melt blended to form an alloy;
ii. LCP, thermoplastic aromatic polyester and a 2~ portion of the total compatibilizer to be used are mixed and melt blended, the rçm~in~ler of the compatibilizer is added at a later time and further melt blended;
SI~S ~ JTE SHEET (RULE 26 W O 97/24403 PCTrUS9C/17114 iii. LCP, thermoplastic aromatic polyester and a first compatibilizer are mixed and melt blended. A second compatibilizer is added to the melt blend at a later time and ~urther melt S blended;
iv. LCP and thermoplastic aromatic polyester are mixed and melt blended and at least one compatibilizer is added at a later time to the melt blend and further melt blended;
v. Thermoplastic aromatic polyester is melted under al~p~ ;ate conditions in an extruder and at a later time LCP and at least one compatibilizer are added to the thermoplastic aromatic polyester and fur~er melt blended;
vi. Thermoplastic aromatic polyester and a first c~ hilizer are melt blended and at a later time LCP and a second co~ alil)ilizer are added to the melt blend and fur~er mixed and melt blended;
vii. Thermoplastic aromatic polyester and LCP are mixed and melt blended and two co~ Libilizers are added to the melt blended and further melt blended; and viii. Thermoplastic aromatic polyester, LCP and 2~ two compatibilizers are mixed and ~imlllt~n~ously melt blended.
SUBSTITUTE SHEET (RULE 26 _ CA 0224l860 l998-06-26 W 097/24403 PCT~US95/17114 DETAI~ED DESCRIPI'ION OF l~; INVENTION
The LCPlthermoplastic aromatic polyester alloys of ~e present invention are formed by use of at least one compatibilizer. In one preferred embodiment, two compatibilizers are used to form~ the a~loys.
The alloys of the present invention comprise from about 0.5 to about 10 weight percent thermotropic liquid crystalline polymer, from about 40 to about 90 weight percent thermoplastic aromatic polyester, and from about 1 to about 50 weight percent compatibilizer.
The liquid crystalline polymer is preferably present in amounts from about 5 to about 10 weight percent, thermoplastic aromatic polyester is preferably present in amounts from about 70 to about 93 weight percent and one or more compatibilizers are present in amounts from about 2 to about 20 weight percent.
In a particularly plel~ d embodiment, the compositions of the present invention contain from about 9 to about 12 weight percent LCP, from about 78 to about 86 weight percent thermoplastic aromatic polyester, and from about 5 to about 10 weight percent compatibilizer.
Thermoplastic aromatic polyesters suitable for use in the present invention are prepared by methods well known in the art. .A variety of methods for making suitable PET homopolymers and copolymers are well known in the art. For example, one suitable PET for use in the present invention is prepared by the reaction of either terephth~lic acid or d;methyl terephth~l~te with ethylene glycol. Various copolymers of PET have been developed and are also ~ ,d~ed by mPth~ well known to the skilled artisan. Suitable thermoplastic aromatic polyester is also available commercially from a number of vendors. Especially preferred commercially available therrnoplastic aromatic polyesters include F~tm~n Kodak Company's Kodar'l9 or Eastar~ A150, Kodar~ or Eastar~ 9921, SUBSTITUTE SHEET (RULE 26~
CA 0224l860 l998-06-26 Koc~ k'9Or F~t~p~k~ 7352, Kodar~ or Eastar~ 9921W and F~tm~n~
1339; Shell's TraytuffrY 8006; DuPont's Cly~ TM 1927 and Selar~ PT7û67;
and Shell's TraytufflM CPET.
Suitable PCTA copolymers e.g., Kodar~9 or Eastar~ A150, for use in S the present invention are prepared by the reaction of terephth~tic acid iso~hth~lic acid, and cycloh~ n~ ~lim~thznnl. Kodar'~9 or Eastarm A150 is one plc:r~ d con~ ;ially available PCTA for use in the present invention. Preferred comlllelcially available PETs include a PET
homopolymer produced from dimethyl terephth~lz~te and ethylene glyçol 10 such as Kodapak~ or F~t~p~k~ 7352; a PET copolymer comprising terephth~lic acid, isotel~l h~lalic acid and ethylene glycol such as Shell's Traytuff~ 8006; and a CPET such as Shell's T~ayLurr CPET.
Suitable thermotropic LCPs for use in the present invention include wholly and partially aromatic polyesters and co-polyesters such as those lS disclosed in U.S. Patent Nos. 3,991,014, 4,067,852, 4,083,829, 4,130,545, 4,161,470, 4,318,842, and 4,468,364. Plt;fe.led thermotropic ~CPs include wholly or partially aromatic polyesters or copolyesters. Particularly ~lerell~d copolyesters include XYDAR~, VECTRA~ and ZENITE~ (E.I.
duPont de Nemours). Other pl~relled thermotropic liquid crystal polymers 20 include SUMIKASUPER~ and EKONOL~ (Sulllik~lllo Chemi~l), DuPont HXTU, RODRUN'~9 (Unitika) and GRANLAR~ (~r~n-lm~,nt) Vectra~ A950, sold by ('~ nese Research Corporation, Summit, New Jersey is one ~lerelled wholly aromatic copolyester. This polymer has been reported to consist es~enti~lly of about 25-27 percent of 6-oxy-2-25 naphthoyl moieties and about 73-7~ percent of p-oxybenzoyl moieties, as described in example 4 of U.S. Patent No. 4,468,364 and in G. W.
(~alllnr1~nn et al., "Anisotropic Polymers, Their Synthesis and Properties", .lillLed from Procee~lin~ of the Robert A. Welch Co~ l-ces on SUBSTITUTE SHEET (RULE 26) CA 0224l860 l998-06-26 W O 97/24403 PCT~US95/17114 Ch~mic~l Research, XXVI Synthetic Polymers, November 15-17, ~982, ~ouston, Texas, pp. 247-291 (see especially pp. 263-265).
Another particularly ~r~r~led thermotropic LCP is ZENITE~. This polymer has been reported to consist of hydroxy-benzoic acid/phenyl 5 hydroquinone/dimethyl-napthylene dicarboxylate units.
In form~ ting the composition of the alloys of the present invention a number of variables jnrlll~lin~, the properties of the polymers to be blended, ~lu~eliies of the compatibilizers, and the amount and ratio of the components, are taken into consideration. These variables are tailored and 10 o~ d in accordance with the present tç~chin~ to provide alloys to meet a particular end use specification. For example, if high gas barrier properties are desired, then polymers having high individual gas barrier properties are preferably selecte~l The amount of c(~...~~ il>ilizer is adjusted to provide intermolecular 15 bonding among the components of the alloy to enh~nre properties and at the same time, to avoid the formation of a quasi- or pseudo-cross linlced network which is not readily processable.
The compatibilizers for use in the present invention are either rniscible with each of the LCP and the thermoplastic aromatic polyester 20 through, e.g., covalent, ionic, molecular inter-pen~tr~tinn~ hydrogen bonding or associative interactions as mentioned above, or have interactive miscibility when the LCP and thermoplastic aromatic polyester are present in a common phase. In other words, the functional groups of the comp~tihilizer, LCP, and thermoplastic aromatic polyester for use in the 25 alloys are also rh~mic~lly compatible. For example, if the LCP to be alloyed with thermoplastic aromatic polyester has an ~liph~tic type of polyester functionality, such as acrylate or methacrylate, or an aromatic functionality, such as a benzoate or phth~l~t~ ester linkage, then ~ref~,led SuBsTlTuTE SHEET (RULE 26~
W O 97/24403 PCTrUS9S/17114 compatibilizers will have a functionality, such as a polyester functional group or a maleic anhydride functional group, that is capable of reacting with the polyester group.
C~-mp~tihilizers for use in the present invention are also processable in the melting and processing range of thermoplastic aromatic polyester and the LCP and exhibit l~ elaLul~ stability at the int~ ied processing temperature. By temperature stability is meant that a component of the alloy es~enti~lly retains its ch~ l functionality and, hence, its interfacial interaction with the other components of the alloy with which it interacts. If one of the components were not th~ lly stable, it is possible that the compatibilization achieved could fail on subsequent proces~in~.
Preferred alloys of the present invention comprise at least one thermotropic LCP, thermoplastic aromatic polyester, and at least one compatibilizer. Particularly plerelred embo~ ; include two or more compatibilizers, wherein at least one colll~aLibilizer interacts with the LCP
and at least one interacts with the thermoplastic aromatic polyester. The ratios of compatibilizers to each other and in the total composition are adjusted to achieve alloys having the desired pL~ Lies as is shown in the examples which follow.
The following compatibilizers are particularly ~ ed in the practice of the present invention wherein components of the alloy comprise thermoplastic aromatic polyesters and wholly aromatic esters and copolyesters liquid crystal polymers, such as VECTRA~ and XYDAR~:
i. Copolyester elastomers such as HYTREL~
HTR-6108 from DuPont;
ii. Ethylene maelic arlhydride copolymers including HDPE grafted with maleic anhydride, such as Polybond~ 3009 from BP Chlomir~
S~J~ 111 ~JTE SHEET (RULE 26) W O 97/24403 PCT~US95/17114 and a linear low density polyethylene-maleic anhydride graft such as Fusabond~ E-MB-226D
from DuPont of C~n~
iii. Ethylene-methyl acrylate copolymers, such as S SP 2205~ and SP3306~ from Chevron Chemi-~l Co~ lly;
iv. Ethylene-methyl acrylate copolymers grafted with maleic anhydride, such as DS~ 1328/60 from Chevron Chemi~ :ll Colllpal-y and Fusabond~ A MG-175D from DuPont (~n~
v. Ethylene-methyl acrylate copolymer, such as Lotader~ 2400, Lotader~ 3410 and Lotader~
5~00 from Elf Atocll~rn;
vi. E~ylene-methyl-methacrylic acid terpolymers (ethylene-methyl acrylate-acrylic acid terpolymers) such as Escor'l9 ATX-320, EscoP
ATX-325, and EscoP XV-1104 from Exxon Chemi~l; and vii. Acrylic rubber such as VAMACTM G1 from DuPont.
The alloys of the present invention can be extruded to form various articles of m:~mlf~ re such as films and tubes useful, e.g., in food pack~ging, electronic circuit sllbstr~tPs and structural applications. The 25 films can be therrnoformed to provide, e.g., trays, blow molded to, e.g., form containers, and otherwise processed by known methods. In some embo-limPnts, articles of m~mlf~ctnre COlll~liSillg the alloys of the present invention are provided with a thin coating of, e.g., glass, metal or another 51u~5 ~ 1 1 UTE SHEET ~RULE 26) W O 97/24403 PCTrUS95/17114 polymer both to protect the article and to provide suitable means to affix labels and the like.
To illustrate the i~ oved properties of the alloys of the present invention, various alloys were prepared as taught herein and extruded to 5 form films having improved tensile strength, tensile modulus and/or oxygen barrier properties over films extruded from thermoplastic arornatic polyester or LCP and thermoplastic aromatic polyester blends without compatibilizers.
In some films, tensile strength was increased by up to more than 2 times and tensile mmlnlllc was increased up to more than 3 times over that of the blend without cnmp~tihilizer. In many in~nrPc, values above 10,000 psi and tensile strength and/or above 500,000 psi and tensile modulus were obtained.
Films extruded from alloys CO~ ;Sil~g thermoplastic aromatic polyesters in~ rlin~ PCTA and PET homopolymers, a wholly aromatic 15 copolyester LCP, and a co.~ Libilizer selected from a copolyester elastomer; a copolyester elastomer and an ethylene ester copolymer grafted with maleic anhydride; or an ethylene-methyl acrylate-mPfh~crylic acid terpolymer.
Films extruded from alloys c~ ing therrnoplastic aromatic 20 polyester, and an anhydride-grafted ethylene-methyl acrylate copolymer, thermotropic LCP wholly aromatic copolyester and a ethylene ester copolymer grafted with maleic anhydride showed improved mf~rh~nir~l properties.
Films extruded ~rom three component alloys colll~lisi~g 25 thermoplastic aromatic polyester, wholly aromatic copolyester and an ethylene-methyl-methacrylic acid terpolymer, e.g., Escor~ ATX-320 or -325, had superior mPch~nir~ vpel~ies. Also, three component blends con~li~ g thermoplastic aromatic polyester, wholly aromatic copolyester SUBSTITUTE SHEET (RULE 26~
W O 97/24403 PCTrUS9Stl7114 and a copolyester elastomer such as HYTRELTM HTR-6108 were extruded to produce films having superior m~ch~nif~l ~rop~:llieS.
A number of films extruded from the alloys of the present invention yielded low oxygen permeation values, ranging from about 18 to 30, well below the 36 to 40 cc-mil/lOin~-24 hours-l atm expected for Kodar~ or Eastar~ A150 and in another case ranging from about 8 to 22, well below the about 28 cc-mil/lOin2-24 hours-latm expected for Kodapaka9 or F~ct~p~kTM 7352.
Films extruded from alloys CO~ liSillg PCTA such as Kodar'~9 or EastarlM A150, a wholly aromatic copolyester LCP and a copolyester elastomer such as HYTRELTU HTR-6108 had excellent barrier properties.
Also, films extruded from alloys com~ g thermoplastic aromatic polyester, a copolyester elastomer, such as HYTRELTU HTR-6108, a wholly aromatic copolyester, and ethylene maleic anhydride copolymer, such as Polybond~ 3009, had excellent oxygen barrier p~ ellies, e.g., from about 21 to 23 cc-mil/lOin2-24 hours-l atm. Excellent barrier l)L~pelLies were also obtained with films extruded from alloys c~,lllprising KodapakZ9 or F~t~r~k~ 7352, VECTRAsU A-950 and Escor~9 ATX-325 or HYTREL~
HTR-6108. One preferred alloy comprised Kodapak'~9 or F~tS~r~k~ 7352 at about 87%, HYTRELTM HTR-6108 at about 3~'o, and VECTRA~A-950 at about 10%. Another pl~lled alloy comprised Kl-d~r~k'l9 or F.~t~p~k~ 7352 at between about 88-89%, Escor'lDATX-325 at about 2 to 4%, and VECTRA~ A-950 at 10%. See Table Q. The over 3 times improvement in barrier equal to over 3 times reduction in permeability was unexpected.
2~ The o~linlulll amount of compatibilitizer to obtain the desired reduction in permeability will vary depending upon run conditions but such opLilllulll amounts are readily determined by the skilled artisan in view of the present te~rhin~ .
SUBSTITUTE SHEET ~RULE 26) CA 0224l860 l998-06-26 Optional components well known to the skilled artisan may be added to alloys of the present invention provided that ~ey do not i~ LÇ~l~ with formation or with the desired final properties of an alloy. Such additives includes ~lllers and pigments, lubricants, mold release agents, plasticizers, 5 ultraviolet stabilizers and so forth.
~ n the methods of the present invention, co...~ ilizers are used either alone or in various combinations with LCP and thermoplastic aromatic polyester to achieve the desired results. They are also used in single step and sequential compatibilization methods as described below.
The following methods have been found to provide alloys having improved properties which can be used, e.g., to provide films having improved ~n~pe~lies over films of LCP and thermoplastic aromatic polyester blends. These methods include:
i. LCP, thermoplastic aromatic polyester 1~ and at least one compatibilizer are mixed and melt blended to form an alloy;
ii. LCP, thermoplastic aromatic polyester and a portion of the total compatibilizer to be used are mixed and melt blended, the rem~in~ler of the comp~tihilizer is added at a later time and further melt blended;
iii. LCP, thermoplastic aromatic polyester and a first compatibilizer are mixed and melt blended. A second compatibilizer is added to the melt blend at a later time and further melt blended;
SU~ I ~ I UTE SHEET (RULE 2 W O 97t24403 PCT~US95117114 iv. LCP and thermoplastic aromatic polyester are mixed and melt blended and at least one compatibilizer is added at a later time to the melt blend and furt'ner melt blended;
v. Thermoplastic aromatic polyester is melted under applol liate conditions in an extruder and at a later time LCP and at least one con~ ibilizer are added to the thermoplastic aromatic polyester and further melt blended;
vi. Thermoplastic aromatic polyester and a first compatibilizer are melt blended and at a later time LCP and a second comp~tihilizer are added to the melt blend and further mixed and melt blended;
vii. Thermoplastic aromatic polyester and LCP are mixed and melt blended and two compatibilizers are added to the melt blended and further melt blended; and viii. Thermoplastic aromatic polyester, LCP
and t~,vo compatibilizers are mixed and simlllt,.n~ously melt blended.
25 By controlling the order in which ~e components of the alloys are mixed and melt blended the properties of the alloy are controlled to enable the production of articles of m~mlf~-~t~lre, e.g., films, which have improved properties over the plup~l~ies of a similar article of m~m~f~ct~lre composed SUBSTITUTE SHEET (RULE 26) W O 97/24403 PCT~US95/17114 solely of thermoplastic aromatic polyester or of LCP and thermoplastic aromatic polyester.
In the production of films from the alloys described above, the meld blend is extruded, e.g., through a slot die, a circular, counter-rotating die, or a circular rotating trimodal die.
In alloys cont~ining two compatibilizers, sequential compatibilization according to methods (iii) and (vi) above are pler~l,ed pl~a.dLion methods.
It was unexpectedly discovered that these unique methods of combining two or more compatibilizers, provided alloys having irnproved properties.
While not wishing to be bound by theory, it is believed that in this novel process, two compatibilizers interact sequentially to provide the desired compatibilization and in some cases also interact with each other. In the case of thermoplastic aromatic polyester-LCP blends of the present invention, the interaction is between the thermoplastic aromatic polyester and a first comp~tihilizer, and the LCP int~r~ts with a second comr~tihilizer. The products of these two interactions, then seq~nti~lly react with one another to form an alloy.
The methods of the present invention provide a great deal of flexibility to achieve the desired compatibilization through the wide array of possibilities for the compatibilizers to interact with the major colllponellL~ of the alloy, which is the object of the co,-,p~lihilization. The methods of the present invention provide an innovative yet efficient way to achieve the desired end results.
In one ~ rell~d embodiment of the present invention, Chevron DSTU
1328/60, an a-ll~ydlide-grafted ethylene-methyl acrylate copolymer, was melt blended with thermoplastic aromat;c polyester and then Polybond~
3009, and VECTRA~ A-950 were added to the mixture and further melt blended to produce alloys which were extruded to produce films having SUBSTITUTE SHEFT (RULE 26~
W 097/24403 PCTrUS95/17il4 greatly improved mP-~h~nic~l properties. For example, a tensile strength of 14,800 psi was obtained in one i~llm extruded from an alloy made by feeding 5% of the Chevron DS~ 1328/60 in the hopper with the thermoplastic aromatic polyester, and then by feeding 2% Polybond~ 3009 S with the LCP VECTRA~ A-950 into the vent feed port.
In another preferred embo~limf~nt~ Escor~9 ATX-325, an ethylene-methyl-mPth~crylic acid terpolymer, was melt blended with thermoplastic aromatic polyester and then Polybondn' 3009 and VectraTM A950 were added to the mixture and further melt blended. A tensile m~ lhlC value of 1.09 10 million psi was obtained in a film extruded from an alloy made by feeding ~% of Exxon ATXTY 320 in the hopper with the PAT, and then feeding 2%
Polybond~ 3009 with the LCP VECTRA~ A-950 into the vent feed port.
Accol.lhlgly, it can be seen that films produced from the alloys of the present invention have surprisingly improved plu~llies over films of 15 LCP and PAT blends or of PAT alone.
Conventional extrusion e~lui~ ellt was used to produce the alloys of the present invention and to extrude films from these alloys. Mixing and melt blending of components to form the alloys of the present invention is carried out using conventional single or double screw extruders. It is 20 pl~fellc:d that the extruder system has not less than 25/l L/D ratio.
Extrusion conditions such as processing tempeldLul~ s, rotation speed of the screw, feed rate and through put were optimized for the particular alloy by taking into consideration the pl~")elLies of the polymers being melt blended to form the alloy, including res~llting viscosity of the melt blend. Typically, 25 higher shear screw configurations were found to give better dispersions of the LCP and better compatibilization remlting in alloys that could be used to produce films having improved properties. Typical L~ Lules SuBsTlTuTE SHEET (RULE 26~
W O 97/24403 PCTrUS95/17114 employed for the processing were 525 to 620~F. The rotation rate of the screw was, typically between 50 to 300 rpm.
The alloy components are ~Iu~iately conditioned, e.g., dried and then fed to the extNder using convPntio~l methods. For example, the S components can be melt blended and extruded to form pellets. The pellets can then be extruded or injection molded to form the desired article of m~mlf~ lre. ~ ;vely, the dry components can be blended, fed into the extruder, and extruded, e.g., to a film directly.
The rnasterblending or masterb~tching technique in which typically, a 10 blend of two components is processed into pellets to form the "masterblend"
can also be used. The masterblend can be run through an extruder a second time with additional components added in accordance with the tP~rhin~c of the present invention. This is a convenient method of m~mlf~rtllre, because an inventory of masterblend material can be made and then combined with 15 dirrel~llL components as desired. One advantage to the masterblending process is that small and very controlled amounts of additional components can be added to the l,la~L~ lend. For example, if the llla~L~.l,atch has 10%
LCP, the ma~LelbaLcll can be passed through the extruder again with, for example, 10% of the masterbatch and 90% of the other polymers, providing 20 a masterbatch that is 1 ~o in LCP.
Through ma~L~lb~ hinp, controlled low concentration of a component in the alloy can be obtained; and ~ itiQn~l mixing and ~h~ring through multi-passes in the extruder can be achieved, if desired.
Masterbaching also provides advantages when working with a 25 component having a low melt temperature, such as the compatibilizer Fusabond~9 A MG-175D which has a melt temperature of about 45~C. It can be added over time at the vent feed with the LCP. However, in one pl~Lred method of the present invention the LCP and low melt SUBSTITUTE SHEET ~RULE 26~
W O 97/24403 PCTrUS95/17114 temperature compatibilizer are masterb~trhPc~, thus allowing greater control over the processing of this low melt temperature component which is also present at a low conr~ntr~tion.
The present invention will be fur~er illustrated with reference to the S following example which is inten-le(l to aid in the underst~n(iin~ of the present invention, but which is not to be construed as a limitation thereof.
E~LE
The alloy components should be appioL~liately treated, e.g., dried, before processing as would be readily apparent to the skilled artisan.
The work described in the following exarnple was carried out using a conventional 25 mm or 40 mm co-rotating, non-hl~ p~ twin screw extruder m~nnf~rtllred by Berstorff Corporation. Mixing and knP~(1ing elemPnt~ for the screw configuration were varied according to conventional wisdom to achieve the desired degree of mixing.
E~ilms were extruded from a slot die, approximately 8 inches wide with die gap of approximately 0.010 to 0.020 inches. Also, a counter-rotating die or circular trimordal die ~see, U.S. Patents 4,975,312 and 5,288,529) can be used to extrude films coll~lisillg one or more alloys of the present invention. Since the degree of llni~xi~l orient~ti~ n produced in the extruded film has an impact on the properties, films having similar extrusion conditions were cOlll~al~d in the work cli~r~c~e~ below.
A universal testing m~rhin~ was used for testing the tensile properties based on ASTM standard tests, e.g., ASTM #0882.
The LCP used was Vectra~ A-950 from Hoechst-Cel~n~se Corporation. A PCTA copolymer purchased from F~ctm~n Chemiral~
under the tr~(len~m~ Kodar'9 or Eastar~ A150 was used in the following work. Also used was a PET homopolymer purchased from F~tm~n SlJ~ JTE SHEET (RULE 26) W O 97/24403 PCTrUS95/17114 l~hPmir~l under the tr~den~m~ Kodapak~ or F~t~r~k~ 7352 and a CPET
purchased from Shell under the tr~ n~m~ Traytuf~ CPET. The compatibilizers used included: HYTRELTM HTR-6108; PolybondTY 3009; and Fusabond~ E-MB-226D; SP 2205TU and 3306TM; DSsM 1328/60 and S Fusabond39 A Mal75D; Lotader~ 240~); Escor'l9 ATX-320, Escor~9 ATX-325, and; Escor39 XV-1104; and Vamac~ G1.
The run conditions and results are shown in Tables I-VII. In the Tables, the thermoplastic aromatic polyesters used are inr1ie~terl as follows:
Kodar'l9 or Eastar~ A150 as "A150," or Kodar'l9 or Eastar~ 9921 as "9921,"
or Kodapak~9 or F~t~r~krM 7352 as "7352" and Shell's TraytuffrM CPFT as "CPET." The VECTRA~ LCP is in~ tt-d as "A950." "Ten Yld St."
intli(~t~s Tensile Yield Streng~; and "Ten. Mod. " in-lir~t~s Tensile Modulus Values. In ~e Tables, compatibilizers listed are itl~.ntifi~cl as ~ollows: HYTl~ELTU HTR-6108 as Hytrel 6108; Polybond~ 3009 as "BP3009"; SP 2205TU as "SP2205"; DS~ 1328/60 as "Chev DS"; Lotader~
2400 as "Lotader 2400"; Escor~9 ATX-320, ATX-325 and XVl104s "ATX320", "ATX325" and "XVllO4" respectively, and Fusabond~9 E-MB-226D as "Fusabond226".
SUBSTITUTE SHEET (RULE 26) W O 97/24403 PCTrUS95/17114 TABLE A
LCP, themoplastic aromatic polyester and at least one compatibilizer are mixed and melt blended to forrn an alloy.
s RUN # HOPPER ~ ;D TEN YLD TEN MOD OX-ST MD(Kpsi)MD(Kpsi) BARRlER
6299-7 85.7%A150+9.5%A950 10.6 800 27.2 +4.8%ATX320 6299-9 85.7%A150+9.5%A950 9.7 810 +4.8%ATX325 6299-10 8S.7%A150+9.5%A950 9.1 570 25.3 +4.8 %Chevron 8249-9 95%8006+4%A9507.1 209 +4%Hy~rel6108 TABLE B
LCP, thermoplastic aromatic polyester and a portion of ~e total compatibilizer to be used are mixed and melt blended, the rem~in~ler of the compatibilizer is added at a later time and further melt blended.
R~ ~ HOPPER FEED VENT FEED TEN YLDTEN MOD OX-ST MD MD BAR
(Kpsi) (Kpsi) RIER
6249-3 85.7%A150+ 2.4%ATX325 10.0 421 25.5 9.5 %A950 + 2.4 %ATX325 6249-7 85.7%A150+ 2.4%BP3009 12.9 460 26.8 9.S %A950 +2.4%BP3009 8319-2 91 %8006+2% 1 %Fusabond226D6.9 320 Hyt}el6108 +7%A950 9085~ 86%7352+1% 10%A950+ 7.19 263 8.4 Hytrel6108 2%F~ )n~1'7~6D
2~i SUBSTITUTE SHEET (RULE 263 W O 97/24403 PCT~US95/17114 TABLE C
LCP, thermoplastic aromatic polyester and a first compatibili~er are mixed and melt blended. A second S comp~tt~lilizer is added to the melt blend at a later time and further melt blended.
RUN # HOPPER FEED VENT FEED TEN YLD TEN MOD
ST MD(Kpsi) MD(Kpsi) 6249-8 85.7%Al50+ 2.4%Lotader7.2 233 9.5 %A950 2400 +2.4%ATX325 TABLE D
LCP and thermoplastic aromatic polyester are mixed and melt blended and at least one compatibilizer is added at a later time to the melt blend and further melt blended.
RUN # HOPPER FEED VENT TEN YLD TEN OX-FElEDST MOD BARRIER
MD(Kpsi) MD(Kpsi) 6299-14 85.7%Al50+ 7.8% 9.1 530 26.6 9.5 %A950 ATX320 TABLE E
Thermoplastic aromatic polyester is melted under ~I ~r~ ial~
conditions in an extruder and at a later time LCP and at least one compatibilizer are added to the PET and further melt blended.
RUN # HOPPER FEED VENT FEED TEN YLD TEN
ST MOD
MD(Kpsi)MD(Kpsi) 6309-12 85.7%Al50 9.7%A950 7.1 460 +4.8 %ATX325 8249-4 94%8006 4%A950 7.16 233 +0.75 %SP2260 S~ TE SHEET(RULE 26) TABLE F
Thermoplastic aromatic polyester and a first compatibilizer are melt blended and at a later time LCP and a second cnmr~tibilizer are added to the melt blend and further mixed and melt blended.
RUN #HOPPER FEEDVENT FEED TEN YLD TEN OX-ST MOD RARR~.R
MD(Kpsi)MD(Kpsi) 7019-789%A150 9.3%A950 12.7 810 29.6 +4.7%ATX320 +2%BP3009 7069-889%A150 9.3 %A950 11.2 960 25.7 +4.7% +2%BP3009 ChevronDS
7069-989%A150 9.3%A950 9.6 740 +4.7%XV11.04 +2%BP3009 7069-1089%Al50 9.3 %A950 9.3 850 20.3 +4.7% +2%BP3009 Hyt~el6108 7079-189%A150 9.3%A950 14.8 840 29.8 +4.7% +2%BP3009 ChevronDS
8259-3939ta8006 4%A950 7.73 278 +2%Hytrel6108 + 1 %
Fusabond TABLE G
Thermoplastic aromatic polyester & LCP are mixed and melt blended and two compatibilizers are added to the melt blended and further melt blended.
RUN #HOPPER VENT FEED TEN YLD TEN OX-FEED ST MOD l~ARRTF,R
MD(Kpsl)MD(Kpsi) 7069-685.7%A1502.4%Hyt}el6108 6.2 420 26.3 +9.5%A950 +2.4%BP3009 SuBsTlTuTE SHEFT (RULE 26 W O 97/24403 PCT~US95/17114 TABLE H
Thermoplastic arom~tic polyester, LCP and two S compa~ibilizers are mixed and .~iml-lt~nPously melt blended in an extruder and extruded through a slot die.
RUN # HOPPER FEED TEN YLD T~N MOD OX-ST ~DD~Kpsi) BARRUER
h1D(Kpsi) 7169-3 80%A150+10%A950 7.9 370 25.3 +~.5%Hytrel6108+~.5%BP3009 TABLE J
Thermoplastic aromatic polyester, LCP and two co~ )aLil)ilizers are mixed and ~imlllt~nPously melt blended and extruded through a circular, counter-rotating die.
RUN # HOPPER FEED TEN YLD TEN MOD
ST ~DD(Kpsi) ~DD(Kpsi) 1199~3 83%A150+10%A950+5%ATX320 6.2 440 +2%BP3009 H99-4 81%A150+10%A950+5%SP2205 5.9 370 +4 %BP3009 1199-5 81%A150+10%A950+5%SP2205 7.2 440 +4%Hysrel6108 SUBSTITUTE S~IEET (RULE 26 W O g7/24403 PCTrUS95117114 TABLE K
Thermoplastic aromatic polyester and a first co~ a~ibilizer are S melt blended and, at a later time, LCP and a second comp~tihlizer are added to the melt and fur~er mixed and melt blended and extruded using a circular rotating trimodal die.
RUN # HOPPER FEED VENT FEED TEN YLD TEN
ST MOD
MD(Kpsi) MD(Kpsi) 3249-2 83.6%A150 10%A950+2%BP3009 9.0 290 + 4.4 %ATX320 3249-5 83.6%A150 10%A950+2%BP3009 6.5 220 +4.4%ChevronDS
TABLE L
Control thermoplastic aloll~Lic polyester RUN # HOPPER FEEDTEN YLD TEN OX-ST MOD RARV~R
MD(Kpsi)MD(Kpsi) 6249-1 100%A150 5.5 162 5269-0 100%A150 5.4 190 5119-0 100%A150 5.8 169 4239-1 100%A150 6.2 176 31.5 6299-1 100%A150 5.2 320 7069-1 100%A150 5.3 320 29.9 3189-1 100%A150 6.2 200 SlJ3~ 111 ulTE SHEET (RULE 26 TABLE M
Control thermoplastic aromatic polyester & LCP, No Com?atibilizer RUN #HOPPER FEED l~:N YLD TEN OX-ST MOD B,~RRni.R
MD(Kpsi)MD(Kpsi) 3189-2 90%A150+10%A950 6.9 290 3189-5 90%A150+10%A950 5.5 210 22.7 3189-9 90%A150+ 10%A950 5.8 231 6249-2 90%A150+ 10%A950 7.4 251 7069-2 90%A150+10%A950 6.1 420 24.9 7019-5 90%A150+10%A950 6.1 440 TABLE N - Ma~ lJa~ch RUN # HOPPER FEED VENT TEN YLD TEN OX-FEED ST MOD BARR
MD~Kpsi) ~DD(Kpsi ) 8129-1 83%A150 10%A950 8.0 550 20.6 +5%Hytrel6108 +2%BP3009 8129-5 78%A150 10%A950 7.8 230 19.6 +10%Hytrel6108 +2%BP3009 8129-10 83%A150 10%A950 5.6 430 22.1 +5%Hytrel6108 +2%BP3009 8129-16 78%A150 10%A950 5.9 420 18.5 + 10%Hytrel6108 +2%Hytrel6108 8129-17 78%A150 10%A950 5.8 430 18.4 + 10%Hytrel6108 +2%Hytrel6108 8129-18 78%A150 10%A950 7.4 600 19.5 + 10%Hytrel6108 +2%BP3009 8129-19 78%A150 10%A950 7.6 710 18.0 + 10%Hytrel6108 +2%BP3009 8289-5 94~o7352 1 %A950 7.37 268 +2%Hytrel6108 +3 %Fusabond SuBsTlTuTE SHEET (RULE 26 W O 97/24403 PCTrUS95/17114 TABLE O
In some runs, LCP, thermoplastic aromatic polyester and one S co~ libilizer are added to the hopper feed and melt blended to form an alloy. In other runs, thermoplastic aromatic polyester and one comr~tihilzer are added to the hopper feed and LCP and Fusabond 226 are added at the vent feed and melt blended to form an alloy.
0 RIJN # HOPPER ~ED VENT FEEDTEN YLD TEN
ST MD MOD
~Kpsi~MD(Kpsi) 9259-1 100%A150 - 5.5 180 9259-2 90%A150+10%A950 - 7.3 560 9259-3 85%A150+10%A950 - 8.7 740 + 5 %ATX325 9269-1 100%7352 - 5.8 250 9269-2 90%7352+10%A950 - 6.2 290 9269-3 85%7352+10%A950 - 7.0 290 +5 %ATX325 9269-4 88%7352+10%A950 - 6.7 300 +2%Escor325 9269-5 86%7352+ 10%A950 - 7.3 300 +4%Escor325 9269-6 86%7352 10%A950 7.3 320 +2%Escor325 +2%Fusabond226 9269-7 84%7352 10%A950 7.2 310 +4%Escor325 +2%Fusabond226 9269-8 86%7352 10%A950 7.2 310 +2%Hytrel6108 +2%Fusabond226 9269-9 84%7352 10%A950 6.5 260 +4%Hytrel6108 +2%Fusabond226 9269-lOA 85 %7352 10 %A950 6.7 280 +4%Hytrel6108 + 1 %Fltr ~hont~ 6 SUBSTITUTE SHEET (RULE 21;~
W O 97t24403 PCT~US95/17114 TABLE O - cont'd RUN # HOPPER Fl~;ED VENT FEED TEN YLD TE;N
ST MD MOD
(Kpsi)MD(Kpsi) 5 9269-lOB85%7352 10%A950 7.0 340 +4%Hytrel6108 +1%r~ 6 9269-11 82%7352 10%A950 7.0 320 +5%Hytrel6108 +3%F~ h-n~ 6 9269-1286%7352+10%A950 - 6.4 310 +4%Hytrel6108 9269-1387%7352+10%A950 - 7.3 340 +3 %Hytrel6108 9269-1488%7352+ 10%A950 - 6.9 330 +2%Hyt~el6108 109269-1589%7352+10%A950 - 7.3 320 + 1 %Hytrel6108 TABLE P
LCP, thermoplastic aromatic polyester and comp~tihilizer are added to the hopper feed and melt blended to form an alloy.
20 RUN # HOPPER FEED TEN YLD TEN MOD
ST MD (Kpsi) MD (Kpsi) 04059-1 90%CPET+10%950 10 610 04059-2 86~h%CPET+10%A950+31h%ATX320 11 640 04059-3 85 %CPET + 10 %A950 + 5 %ATX32011.7 620 S~J~a 1 l l UTE SHEET (RULE 26) TABLE Q
s LCP, thermoplastic aromatic polyester and cc ...p;1lihilizer are added to the hopper feed and melt blended to form an alloy RUN # HOPPER FEED OXYGEN-pF,Rl~lAR~ ,lTY
cc-milllOOin2-d ,.' 11169-1 100%7352 28 9269-3 85 %7352 + 5 %ATX325 + 10 %A950 9 92694 88%7352+2%ATX325+10%A9S0 9 9269-S 86%7352+4%ATX325+10%A9S0 9 9269-12 86%7352+4%Hytrel6108+109t0A9S0 21 9269-13 87%7352+3%Hyt~el6108+ 10%A950 8 9269-14 88%7352+2%Hytrel6108+10%A950 20 9269-15 89%7352+1%Hytrel+10%A95022 The present invention has been described in detail inr~ ing the p,~;re,led embotlim~nt~ thereof. EIowever, it would be a~pl~.;idled that those 2~ skilled in the art, upon c~m~ider~tion of the present disclosure, may ~ke modifif ~tinns and/or improvements on this invention and still be within the scope and spirit of ~is invention as set for~ in the following claims.
SUBSTITUTE SHEET (RULE 26~
Claims (44)
1. An alloy comprising at least one thermotropic liquid crystalline polymer (LCP), at least one thermoplastic aromatic polyester and at least one compatibilizer, wherein the compatibilizer comprises:
(i) a copolyester elastomer;
(ii) an ethylene ester copolymer;
(iii) a copolymer of ethylene and a carboxylic acid or acid derivative;
(iv) ethylene ester copolymers grafted with at least one functional monomer;
(v) an ethylene copolymer-acrylic acid terpolymer;
(vi) terpolymers of ethylene, unsaturated ester and a carboxylic acid or acid derivative; and (vii) an acrylic elastomer.
(i) a copolyester elastomer;
(ii) an ethylene ester copolymer;
(iii) a copolymer of ethylene and a carboxylic acid or acid derivative;
(iv) ethylene ester copolymers grafted with at least one functional monomer;
(v) an ethylene copolymer-acrylic acid terpolymer;
(vi) terpolymers of ethylene, unsaturated ester and a carboxylic acid or acid derivative; and (vii) an acrylic elastomer.
2. An alloy in accordance with claim 1 wherein:
(i) the copolyester elastomer comprises HYTREL TH HTR-6108.
(ii) the ethylene ester copolymer comprises an ethylene-methyl acrylate copolymer;
(iii) the copolymer of ethylene and a carboxylic acid or acid derivative comprises an ethylene-maleic anhydride copolymer;
(iv) the ethylene ester copolymer comprises an ethylene-methyl acrylate copolymer grafted with maleic anhydride;
(v) the ethylene copolymer-acrylic acid terpolymer comprises an ethylene-methyl acrylate-maleic anhydride terpolymer;
(vi) the terpolymer of ethylene, unsaturated ester and a carboxylic acid or acidderivative comprises an ethylene-methyl acrylate-methacrylic acid terpolymer;
and (vii) the acrylic elastomer comprises an acrylic rubber.
(i) the copolyester elastomer comprises HYTREL TH HTR-6108.
(ii) the ethylene ester copolymer comprises an ethylene-methyl acrylate copolymer;
(iii) the copolymer of ethylene and a carboxylic acid or acid derivative comprises an ethylene-maleic anhydride copolymer;
(iv) the ethylene ester copolymer comprises an ethylene-methyl acrylate copolymer grafted with maleic anhydride;
(v) the ethylene copolymer-acrylic acid terpolymer comprises an ethylene-methyl acrylate-maleic anhydride terpolymer;
(vi) the terpolymer of ethylene, unsaturated ester and a carboxylic acid or acidderivative comprises an ethylene-methyl acrylate-methacrylic acid terpolymer;
and (vii) the acrylic elastomer comprises an acrylic rubber.
3. An alloy in accordance with claim 2 wherein:
(i) the ethylene-methyl acrylate copolymer comprises SP 2205TM or 3306TM;
(ii) the ethylene-maleic anhydride copolymer comprises PolybondTM 3009 or Fusabond~ E-MB-226D;
(iii) the ethylene-methyl acrylate copolymer grafted with maleic anhydride comprises DSTM 1328/60 or Fusabond~ A MG-175D;
(iv) the ethylene-methyl acrylate-maleic anhydride terpolymer cmprises LotaderTM 2400, LotaderTM 3410, and LotaderTM 5500 from Elf Atochem;
(v) the ethylene-methyl acrylate-methacrylic acid terpolymer comprises Escor~
ATX-320, Escot~ ATX-325 or Escor~ XV-1104; and (vi) the acrylic rubber comprises Vamac~ G1
(i) the ethylene-methyl acrylate copolymer comprises SP 2205TM or 3306TM;
(ii) the ethylene-maleic anhydride copolymer comprises PolybondTM 3009 or Fusabond~ E-MB-226D;
(iii) the ethylene-methyl acrylate copolymer grafted with maleic anhydride comprises DSTM 1328/60 or Fusabond~ A MG-175D;
(iv) the ethylene-methyl acrylate-maleic anhydride terpolymer cmprises LotaderTM 2400, LotaderTM 3410, and LotaderTM 5500 from Elf Atochem;
(v) the ethylene-methyl acrylate-methacrylic acid terpolymer comprises Escor~
ATX-320, Escot~ ATX-325 or Escor~ XV-1104; and (vi) the acrylic rubber comprises Vamac~ G1
4. An alloy in accordance with claim 1, wherein the copolyester elastomer comprises HyTRELTM HTR-6108.
5. An alloy in accordance with claim 1, wherein the thermotropic LCP comprises awholly aromatic polyester or copolyester.
6. An alloy in accordance with claim 1, wherein the thermotropic LCP comprises apartially aromatic polyester or copolyester.
7. An alloy in accordance with claim 5, wherein the wholly aromatic polyester orcopolyester comprises 6-oxy-2-naphthoyl and p-oxybenzoyl moieties.
8. An alloy in accordance with claim 7, wherein the wholly aromatic polyester orcopolyester comprises Vectra~ A-950.
9. An alloy in accordance with claim 5, wherein the wholly aromatic polyester orcopolyester comprises hydroxy benzoic acid/phenyl hydroquinone/dimethyl-napthylene dicarboxylate units.
10. An alloy in accordance with claim 9, wherein the wholly aromatic polyester or copolyester comprises ZENITETM.
11. An alloy in accordance with claim 5, wherein the wholly aromatic polyester or copolyester is XYDARTM, VECTRATM, SUMIKASUPER~, EKONALTM, HXTM, ZENITETM, RODRUN~ or GRANLARTM.
12. An alloy in accordance with claim 5, wherein the compatibilizer comprises a copolymer elastomer.
13. An alloy in accordance with claim 12, wherein the copolymer elastomer comprises HYTRELTM HTR-6108.
14. An alloy in accordance with claim 13, wherein the thermoplastic polyester is PCTA.
or a PET homopolymer.
or a PET homopolymer.
15. An alloy in accordance with claim 14, wherein the PCTA is Kodapak~ or EstapakTM
A150 and the PET homopolymer is Kodapak~ or EstapakTM 7352.
A150 and the PET homopolymer is Kodapak~ or EstapakTM 7352.
16. An alloy in accordance with claim 5, wherein the barrier properties of the alloy are from 1 to 3 times better than the barrier properties of the thermoplastic aromatic polyester.
17. An alloy in accordance with claims 1 or 2, whelein at least two compatibilizers are present.
18. An alloy in accordance with claim 17, wherein the LCP comprises a wholly aromatic copolyester and the compatibilizers comprise an ethylene-methyl acrylate-acrylic acid terpolymer and an ethylene-maleic anhydride coploymer.
19. An alloy in accordance with claim 18, wherein the ethylene-methyl acrylate-acrylic acid terpolymer comprises EscorTM ATX-320, EscorTM ATX-325, or EscorTM XV-1104 and the ethylene-maleic anhydride comprises PolybondTM 3009 or Fusabond~ E-MB-226D.
20. An alloy in accordance with claim 19, wherein the thermpolastic aromatic polyester comprises a PCTA copolymer.
21. An alloy in accordance with claim 20, wherein the PCTA copolymer comprises Kodar~ or Eastar~ A150.
22. An alloy in accordance with claim 17, wherein the LCP comprises a wholly aromatic copolyester and the compatibilizers comprise an ethylene-methyl acrylate copolymer grafted with maleic anhydride and an ethylene-maleic anhydride coploymer.
23. An alloy in accordance with claim 22, wherein the ethylene-methyl acrylate copolymer grafted with maleic anhydride comprises DSTM 1328/60 or Fusabond~ A MG-175D
and the ethylene-maleic anhydride coploymer comprises PolybondTM 3009 or Fusabond~
E-MB-226D.
and the ethylene-maleic anhydride coploymer comprises PolybondTM 3009 or Fusabond~
E-MB-226D.
24. An alloy in accordance with claim 17, wherein the LCP comprises a wholly aromatic copolyester and the compatibilizers conmprise a copolyester elastomer and an ethylene-maleic anhydride coploymer.
25. An alloy in accordance with claim 24, wherein the copolyester elastomer comprises HYTRELTM HTR-6108 and the ethylene-maleic anhydride coploymer comprises PolybondTM
3009 or Fusabond~ E-MB-226D.
3009 or Fusabond~ E-MB-226D.
26. An alloy in accordance with claim 17, wherein tne LCP copolyester comprises 6-oxy-2-naphthoyl and p-oxybenzoyl moieties and the compatibilizers comprise an ethylene-ethylene-methyl acrylate copolymer grafted with maleic anydride and an ethylene-maleic anhydride coploymer.
27. An alloy in accordance with claim 26, wherein the copolyester comprises VectraTM
A-950 and the ethylene-methyl acrylate copolymer grafted with maleic anhydride comprises DSTM 1328/60 or FusabondR A MG-175D and the ethylene-maleic anhydride coploymer comprises PolybondTM 3009 or FusabondR E-MB-226D.
A-950 and the ethylene-methyl acrylate copolymer grafted with maleic anhydride comprises DSTM 1328/60 or FusabondR A MG-175D and the ethylene-maleic anhydride coploymer comprises PolybondTM 3009 or FusabondR E-MB-226D.
28. An alloy in accordance with claim 17, wherein the LCP wholly aromatic copolyester comprises 6-oxy-2-naphthoyl and p-oxybenzoyl moieties and the compatibilizers comprise a copolyester elastomer and an ethylene-maleic anhydride copolymer.
29. An alloy in accordance with claim 28, wherein the LCP wholly aromatic copolyester comprises Vectra A-950 and the copolyester elastomer comprises HYTRELTM HTR 6108 and the ethylene-maleic anhydride copolymer comprises PolybondTM 3009 or FusabondR
E-MB-226D.
E-MB-226D.
30. An alloy in accordance with claim 17, wherein the LCP wholly aromatic copolyester comprises 6-oxy-2-naphthoyl and p-oxybenzoyl moieties and the compatibilizers comprise an ethylene-methyl acrylate-acrylic acid terpolymer and an ethylene-maleic anhydride copolymer.
31. An alloy in accordance with claim 28, wherein the LCP wholly aromatic copolyester comprises Vectra A-950 and the ethylene-methyl acrylate-acrylic acid terpolymer comprises EscorTM ATX-320, EscorTM ATX-325, EscorTM XV-1104, or HYTRELTM HTR 6108 and the ethylene-maleic anhydride copolymer comprises PolybondTM 3009 or FusabondR E-MB-226D.
32. An alloy in accordance with claim 5, wherein the thermoplastic aromatic polyester is a PET homopolymer or copolymer, PBT, PETG, PCTA copolymers, APET, CPET, PCPT
or PBN.
or PBN.
33. An alloy in accordance with claim 17, wherein the thermoplastic aromatic polyester is a PET homopolymer or copolymer, PBT, PETG, PCTA copolymers, APET, CPET, PCPT
or PBN.
or PBN.
34. An alloy in accordance with claim 32, wherein the PET homopolymer is Kodapak~ or EstapakTM A150, the PCTA copolymer is Kodapak~ or EstapakTM 7352, and the CPET is TraytuffTM.
35. An alloy in accordance with claim 33, wherein the PET homopolymer is Kodapak~ or EstapakTM A150, the PCTA copolymer is Kodapak~ or EstapakTM 7352, and the CPET is TraytuffTM.
35. An alloy in accordance with claim 33, wherein the PET homopolymer is Kodapak~ or EstapakTM A150, the PCTA copolymer is Kodapak~ or EstapakTM 7352, and the CPET is TraytuffTM.
35. An alloy in accordance with claim 17, wherein the wholly aromatic polyester of copolyester is XYDARTM, VECTRATM, SUMIKASUPER~, EKONALTM, HXTM, ZENITETM,
36. An alloy in accordance with claim 5, wherein the wholly aromatic LCP is VectraTM
A950 and the compatiblizer is Escor ATX325 or HYTREL.
A950 and the compatiblizer is Escor ATX325 or HYTREL.
37. A method of producing an alloy comprising at least one thermotropic LCP, PET and at least one compatibilizer, wherein the method comprises melt blending the LCP, PET and compatibilizer to form an alloy.
38. A method in accordance with claim 36, wherein the method comprises melt blending LCP, PET and a portion of a compatibilizer to form a first melt blend, and adding the remainder of the compatibilizer to the first melt blend and further melt blending to form an alloy.
39. A method of producing an alloy comprising at least one thermotropic LCP, PET and a first and second compatibilizer, wherein the method comprises melt blending PET and the first compatibilizer to form a first melt blend, adding LCP and second compatibilizer to the first melt blend, and further melt blending to form an alloy.
40. A method in accordance with claim 39, wherein the method comprises melt blending LCP, PET and the first compatibilizer to form a melt blend, adding the second compatibilizer to the melt blend, and further melt blending to form an alloy.
41. An article of manufacture comprising an alloy according to claims 1 or 2.
42. An article of manufacture according to claim 41, wherein the article comprises a film, a sheet, a tube, or a container.
43. An article of manufacture according to claim 41, wherein the article is provided with a coating comprising glass, metal or polymer.
44. An alloy in accordance with claim 17, wherein the barrier properties of the alloy are from 1 to 3 times better than the barrier properties of the thermoplastic aromatic polyester.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU46502/96A AU4650296A (en) | 1995-12-28 | 1995-12-28 | Compatibilized lcp blends |
| PCT/US1995/017114 WO1997024403A1 (en) | 1995-12-28 | 1995-12-28 | Compatibilized lcp blends |
| EP95944454A EP0869993A1 (en) | 1995-12-28 | 1995-12-28 | Compatibilized lcp blends |
| CA002241860A CA2241860A1 (en) | 1995-12-28 | 1995-12-28 | Compatibilized lcp blends |
| FI981483A FI981483A (en) | 1995-12-28 | 1998-06-26 | LCP blends made blendable |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1995/017114 WO1997024403A1 (en) | 1995-12-28 | 1995-12-28 | Compatibilized lcp blends |
| CA002241860A CA2241860A1 (en) | 1995-12-28 | 1995-12-28 | Compatibilized lcp blends |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2241860A1 true CA2241860A1 (en) | 1997-07-10 |
Family
ID=25680330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002241860A Abandoned CA2241860A1 (en) | 1995-12-28 | 1995-12-28 | Compatibilized lcp blends |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0869993A1 (en) |
| AU (1) | AU4650296A (en) |
| CA (1) | CA2241860A1 (en) |
| WO (1) | WO1997024403A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU9081198A (en) * | 1997-09-05 | 1999-03-29 | Acome Societe Cooperative De Travailleurs | Optical fibre cable of compact composite structure |
| US7101597B2 (en) | 1997-09-10 | 2006-09-05 | Boston Scientific Scimed, Inc. | Medical devices made from polymer blends containing low melting temperature liquid crystal polymers |
| US6242063B1 (en) | 1997-09-10 | 2001-06-05 | Scimed Life Systems, Inc. | Balloons made from liquid crystal polymer blends |
| US6905743B1 (en) | 1999-02-25 | 2005-06-14 | Boston Scientific Scimed, Inc. | Dimensionally stable balloons |
| US6977103B2 (en) | 1999-10-25 | 2005-12-20 | Boston Scientific Scimed, Inc. | Dimensionally stable balloons |
| WO2002020698A1 (en) * | 2000-09-01 | 2002-03-14 | Ticona Llc | Blends of stretchable liquid crystal polymers with thermoplastics |
| US6733520B2 (en) | 2000-09-22 | 2004-05-11 | Scimed Life Systems, Inc. | Sandwich striped sleeve for stent delivery |
| US7169418B2 (en) * | 2001-06-04 | 2007-01-30 | The Procter And Gamble Company | Packaging system to provide fresh packed coffee |
| US6730377B2 (en) | 2002-01-23 | 2004-05-04 | Scimed Life Systems, Inc. | Balloons made from liquid crystal polymer blends |
| TWI636127B (en) | 2015-06-25 | 2018-09-21 | 財團法人工業技術研究院 | Liquid crystal polymer composite film |
| CN109456524B (en) * | 2018-10-22 | 2021-03-23 | 佳易容聚合物(上海)有限公司 | High-barrier PE/LCP/PET resin composition and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4172859A (en) * | 1975-05-23 | 1979-10-30 | E. I. Du Pont De Nemours And Company | Tough thermoplastic polyester compositions |
-
1995
- 1995-12-28 EP EP95944454A patent/EP0869993A1/en not_active Withdrawn
- 1995-12-28 CA CA002241860A patent/CA2241860A1/en not_active Abandoned
- 1995-12-28 AU AU46502/96A patent/AU4650296A/en not_active Abandoned
- 1995-12-28 WO PCT/US1995/017114 patent/WO1997024403A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997024403A1 (en) | 1997-07-10 |
| EP0869993A1 (en) | 1998-10-14 |
| AU4650296A (en) | 1997-07-28 |
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