NZ289669A - Alloy containing thermotropic liquid crystalline polymer, polyethylene terephthate and a compatibilizer - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £89669 New Zealand No 289669 International No PCT/US95/08358 TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION Priority dates 23 06 1994, Complete Specification Filed 28 06 1995 Classification (6) C08L67/02 Publication date 2£Apn!1999 Journal No 143? NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention Compatibilized LCP blends Name, address and nationality of applicant(s) as in international application form FOSTER-MILLER, INC , 350 Second Avenue, Waltham, Massachusetts 02254, United States of America "WO 96/00752 P CT/U S95/08358 Compatibilized LCP Blends FIELD OF THE INVENTION The present invention provides alloys comprising thermotropic liquid crystalline polymers (LCPs) and polyethylene terephthalate (PET) and at least one compaubikzer BACKGROUND High performance plastics are in widespread use in many industries and there is much interest in developing new plastics which are economical and recyclable, as well as high performance The blending and alloying of 10 existing polymers is a cost effective way to produce new high performance plastics which meet these criteria Polymer blends containing thermotropic LCPs have received increasing attention in the scientific and technical literature The range of high performance thermoplasuc flexible polymers which have been blended 15 with TLCPs include polyimides, polyamides, poly(e<-hersulfone) (PES), poly(ethenmide) (PEI), polyetherketone (PEEK), polycarbonate (PC), polyethylene terphthalate) (PET), polyethylene naphthaIate)(PEN), polypheny! ene sulfide (PPS), and polyarylate Thermotropic LCPs are a relatively new class of high performance 20 polymenc materials which combine the advantages of melt processability and outstanding mechanical properties Because of their rigid backbone structure with flexible spacer groups, commercially available thermotropic LCPs have far higher tensile strength and flexural moduli than conventional polymers However, thermotropic LCPs are in many cases difficult to 25 process without specialized equipment and very costly as compared with 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 Furthermore, blending with conventional 30 thermoplastic polymers reduces costs, because less of the very costly LCP is used Also, because thermotropic LCPs form an ordered phase m the melt INTELLECTUAL PROPERTY OFFICE OF NZ - FEB 1S99 RECEIVED 2 - (hence, the name thermotropic), they have shear viscosities far lower than other polymtrs and thus, have potential importance as a processing aid in mixtures with other polymers by reducing the melt viscosity of the mixture Thermotropic LCP in blends with PET have been reported to act as 5 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'Bnen and Crosby (O'Brien, 10 G S and Crosby, J M , Proceedings of COMPALLOY '91 Conference.

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 "reinforcement," especially where the LCP has a very ngid structure has been reported 15 XYDAR® (Poly(oxybenzoyl-co-bisphenyl terephthalate), Amoco, and VECTRA® Poly(oxybenzoyl-co-oxynaphthoyl), Hoechst-Celanese, are thermotropic LCPs which have been much studied as blend components Crevecoeur, G and Groemnckx, G , Polymer Eng Science, 2Q, 532 (1990), reported that a thermotropic LCP can be used at 5-30% levels in 20 polystyrene so that the LCP forms a disperse phase In a 75.25 Polystyrene/VECTRA® A950 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 microfibrillar morphology and to display a substantial increase in elastic modulus 25 over a compression or injection-molded sample The use of LCPs in blends with thermoplastic polymers, e.g., PC and PET, to achieve improved mechanical properties over those of the thermoplastic polymer alone was reported in 1989 See, Bonis, L J., "Multilayer Thermoplastics Advance Composites By Coextrusion", The 30 Polymer Processing Society Summer Meeting, Amherst, Massachusetts, August 16-17, 1989, Paper 10F See, also Williams, D J., Proceedings of WO 96/00752 PCT/US95/08358 COMPALLOY '91 Conference. January 30 - February 1, 1991, pp 393-408 which describes potential applications for thermotropic liquid crystal polyester blends Polymer molding compositions containing polycarbonates, 5 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 m U.S Patent No. 5,262,473, compatible blenas of the polyester and polycarbonate may be used Other blends are disclosed m, for example, U S. Patent Nos 10 5,070,157 and 5,156,785 A blend is a physical mixture of two or more components which typically offers a compromise of properties and economies of the individual components It is well known that the nature and properties of the interface of components m a blend frequently exert a limiting effect on the bulk 15 properties of a multi-phase blend material. In fact, the physical and mechanical properties of a blend are very often inferior to the mathematical average of the properties of the original components Blend components can be miscible or immiscible in their beha\ior toward each other Alloys are different from blends Although they are also composed 20 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 m turn, creates new properties different from those of the original components and often exceeding those of the average of the original ingredients The types of interaction or 25 "chemical bonding" between the components can include, for example, one or more of the following mechanisms- ionic; covalent; molecular mter-penetration; hydrogen bonding; or associative.

Successful compatibilization by one or more of these interactions gives rise to interfacial adhesion to provide the format'on of cohesive multi-30 phase compatibilized alloys with useful properties To achieve compatibilization a number of strategies have emerged 4 - In one approach, suitable block or graft copolymers are introduced to serve as macromolecular emulsifiers providing covalent bonds that traverse and fortify the blend interface Block and graft copolymers may be generated in-situ through reactive extrusion and blending to generate a 5 compatibilized blend.

In another approach, polymers having nucleophihc functional groups are interacted with compatibilizers containing hydrogen to form hydrogen bonding. Ionome.s have also served as compatibilizers In some cases, ionic or strong physicochemical interactions are generated across the 10 interface, which in turn enhances compatibilization Compatibilization car. also result from the addition of a similar functional group using the "like attract like" theory, such as the use of chlonnated polyethylene to compatibilizer polyvinyl chloride with polyethylene This has been referred to as "associative" bonding. 15 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 primary blend components, l e , those components intended to be compatibilized. The compatibilizmg effects of tne mutually miscible component may result from its presumed tendency to 20 become enriched m the vicinity of the blend interface Alloying provides a tool to lower the cost of high performance resins while at the same time retaining many of the desirable properties and/or providing improved properties such as increased processability The most successful alloying procedures result in a controlled and stable morphology 25 with a sing alar thermodynamic profile However, even when alloying is not "complete" in the multi-component system useful compositions can result At present, there is no known direct compatibility between LCPs and PET Accordingly, approaches to compatibilize LCPs with PET and, 30 thereby, to piovide LCP/PET alloys having properties which can be tailored to meet end-use specifications are being «ought PCT/TJ S95/08358 SUMMARY OF THE INVENTION The present invention provides alloys comprising a thermotropic LCP, PET, and at least one compatibilizer In one preferred embodiment, two compatibilizers are present 5 Preferred compatibilizers include copolyester elastomers ethylene- unsaturated ester copolymers, such as ethylene-methyl acrylate copolymers, copolymers of ethylene and a carboxyuc acid or acid derivative, such as ethylene-methyl acrylate copolymers; polyoleflns or ethylene-unsaturated ester copolymers grafted with functional monomers, 10 such as ethylene-maleic anhydnde copolymers, copolymers or terpolymers of ethylene and a carboxyhc acid or acid derivative, such as ethylene-methj 1 acrylate-maleic anhydnde terpolymers, terpolymers of ethylene, unsaturated ester and a carboxylic acid or acid derivative, such as ethylene-methyl acrylate-ac'Mic acid terpolymers, and acrylic elastomers, such as acrylic rubbers A particulary ^ preferred copolyester elastomer is HYTREL™ HTR-6108, ethylene-maleic anhydnde copolymer is Polybond™3009, ethylene-methyl acrylate copolymer is SP 2205™, ethylene-methyl acrylate copolymer grafted with maleic anhydnde is DS1328/60™, ethylene-methyl acrylate-maleic anhydnde terpolymer is Lotader™ 2400, ethylene-methyl acrylate-acrylic acid terpolymer is Escor ™ ATX-320, Escor™ ATX-325 or Escor™ XV-11 04, and acrylic rubber is Vamac™ G1 Preferred thermotropic LCPs include wholly or partially aromatic polyesters or copolyesters. A particularly preferred copolyester is XYDAR™ or VECTRA'0' Other preferred thermotropic liquid crystal 25 polymers include SUMIKOSUPER® and EKONOL™ (Sumitomo Chemical), DuPont HX™ and DuPont ZEN lib"' (E I duPont de Nemours), RODRUN® (Umtika) and GRANLAR™ (Grandmont).

Preferred LCPs for use in the present invention include any such resins with a melt temperature in the range of 250 to 320°C. Particularly 30 preferred LCPs have a melt temperature m the range of 250 to 280°C One preferred alloy m accordance with the present invention INTELLECTUAL PROPERTY OFFICE OF N2 - FEB 1999 RPPFIX/PH PCTYUS95/08358 compnses PET, a wholly aromatic LCP copolyester and an ethylene-methyl acrylate-acrylic acid terpolymer compatibilizer, for example, Escor™ ATX-320, Escor™ ATX-325, or Escor™ XV-11.04 Another preferred alloy compnses PET, a wholly aromatic LCP 5 copolyester and an ethylene-maleic anhydnde copolymer compatibilizer such as Polybond™ 3009 Yet another preferred alloy in accordance with this invention comprises PET, a wholly aromatic LCP copolyester and an ethylene-methyl acrylate copolymer grafted with maleic anhydnde compatibilizer, such as 10 DS™ 1328/60, or a copolyester elastomer such as HYTREL™ HTR 6108 Alloys comprising PET, LCP and at least two compatibilizers are particularly preferred in the practice of the present invention The compatibilizers are preferably selected from a copolyestei elastomer, ethylene-maleic anhydnde copolymer, ethylene-methyl acrylate copolymer, 15 ethylene-methyl acrylate copolymer, ethylene-methyl acrylate-maleic anhydnde terpolymer, ethylene-methyl-methacryhc acid terpolymer or acrylic rubber Preferred two compatibilizer alloys include PET, a wholly aromatic LCP copolyester, an ethylene-methyl acrylate-acrylic acid terpolymer and an 20 ethylene-maleic anhydnde copolymer compatibilizer Exemplary ethylene-methyl acrylate-acrylic acid terpolymers include Escor™ ATX-320, Escor™ ATX-325, or Escor™ XV-11.04 and an exemplary ethylene-maleic anhy-inde copolymer is Polybond™ 3009.

In other preferred PET/LCP alloys, the LCP compnses a wholly 25 aromatic copolyester and the compatibilizers are an ethylene-methyl acrylate copolymer and/or an ethylene-maleic anhydnde copolymer An exemplary ethylene-methyl acrylate copolymer is SP 2205™ and an exemplary ethylene-maleic anhyande copolymer is Polybond™ 3009.

Another preferred LCP/PET alloy of the present invention compnses 30 a wholly aromatic LCP copolyester and an ethylene-methyl acrylate copolymer grafted with maleic anhydnde and an ethylene-maleic anhydnde copolymer compatibilizer Yet another preferred alloy compnses PET, wholly aromatic LCP copolyester, and copolyester elastomer such as HYTREL™" HTR 6108 and an ethylene-maleic anhydnde copolymer such as Polybond™ 3009 The ethylene-methyl acrylate copolymer grafted with mz&eic anhydnde, DS™ 1328/60, and the ethylene-maleic anhydnde copolymer, Polybond™ 3009 are particularly preferred when the LCP is VECTRA™ Also preferred when the LCP is VECTRA™ is the compatibilizer, Polybond™ 3009 and a second compatibilizer, Escor™ ATX-32Q, Escor™ 10 ATX-325, DS 1328/60™, Escor™ XV-11 04, or HYTREL™6108 The properties of the LCP and PET, as well as desired properties of the resulting alloy, are all taken into consideration in selecting suitable compatibilizers for use in the present invention The properties of the PET/LCP alloys of the present invention are adjusted by adjusting the 15 amount of compatibilizer and, in some preferred embodiments, by the manner in which the components are combined 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 of the composition as low as possible while achieving 20 the desired effect Hence, in the present alloys the LCPs are used as the disperse phase, whereas PET is used as the predominant or bulk phase When no compatibilization exists between PET and LCP, such as when no compatibilizer is present, the mechanical properties of the resulting blend are low For example, in films extruded from blends compnsing 25 10% LCP / 90% PET (KODAR™ A-150) a machine direction (MD) tensile strength of only about 6,000 psi and MD tensile modulus of only about 300,000 psi are obtained Furthermore, the oxygen barrier properties are poor, for example, around 35 to 40 cc/lOOin 2 It was unexpectedly found that when PET/LCP alloys were formed by adding suitable compatibilizers 30 in accordance with the teachings of the present invention, improved mechanical properties and/or lower gas permeation (barner) numbers were obtained Ths present invention also provides methods of prepanng the alloys described above These methods include 1 LCP. PET and at least one compatibilizer are 5 mixed and melt blended to form an alloy, 11. LCP, PET and a portion of the total compatibilizer to be used are mixed and melt blended, the remainder of the compatibilizer is added at a later time and further melt blended; 10 ni LCP, PET 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, iv LCP and PET are mixed and melt blended and 15 at least one compatibilizer is added at a later time to the melt blend and further melt blended, v. PET is melted under appropriate corditions in an extruder and at a later time LCP and at least 20 one compatibilizer are added to the PET and further melt blended, vi PET and a first compatibilizer are melt blended and at a later time LCP and a second compatibilizer are added to the melt blend and further mixed and melt blended, vii PET and LCP are mixed and melt blended and two compatibilizers are added to the melt blended and further melt blended, and viii. PET, LCP and two compatibilizers are mixed 30 and simultaneously melt blended PCT/US95/0S358 9 - DETAILED DESCRIPTION OF THE INVENTION The LCP/PET alloys of the present invention are formed by use of at least one compatibilizer. In one preferred embodiment, two compatibilizers are used to form the alloys 5 The alloys of the present invention compnse from about 0.5 to about weight percent thermotropic liquid crystalline polymer, from about 40 to about 90 weight percent PET, and from about 1 to about 50 weight percent compatibilizer The liquid crystalline polymer is preferably present in amounts from 10 about 5 to about 10 weight percent, PET 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 preferred embodiment, the compositions of the present invention contain from about 9 to about 12 weight percent LCP, 15 from about 78 to about 86 weight percent PET, and from about 5 to about 10 weight percent compatibilizer Suitable PET for use in the present invention is prepared by the reaction of either terephthalic acid or dimethyl terephthalate with ethylene glycol Other methods of making suitable PET are known to one of 20 ordinary skill in the art Suitable PET is also available commercially from a number of vendors, including KODAR™ A150, KODAR™ 9921, and Eastman 13339 from Eastman Chemical and CPET™ from Goodyear. KODAR™ A150 is one preferred commercially available PET for use in the present invention.

Suitable thermotropic LCPs for use in the present invention include wholly and partially aromatic polyesters and co-polyesters such as those 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 Preferred thermotropic LCPs for use m the present invention include wholly aromatic co-polyester Vectra™ 30 A950, sold by Celanese Research Corporation, Summit, New Jersey is one such wholly aromatic copolyester This polymer has been reported to consist essentially of about 25-27 percent of 6-oxy-2-naphthoyl moieties and about 73-75 percent of p-oxyben7oyl moieties, as descnbed in example 4 of U S Patent No 4,468,364 and in G. W Calundann et al., "Anisotropic Polymers, Their Synthsms and Properties", repnnted from Proceedings of 5 the Robert A Welch Conferences on Chemical Research, XXVI Synthetic Polymers, November 15-17, 1982, Houston, Texas, pp 247-291 (see especially pp 263-265) Preferred theraotropic LCPs include wholly or partially aromatic polyesters ci copolyesters A particularly preferred copolyester is 10 XYDAR™ oi VEC TRA™ Other preferred thermotropic liquid crystal polymers include SUMIKOSUPER® and EKONOL™ (Sumitomo Chemical), DuPont HX™ end DuPont ZENITE™ (E I. duPont de Nemours), RODRUN® (UnitiV-* j-1 GRANLAR™ (Grandmont) In formulating the composition of the alloys of the present invention 15 a number of variables including, the properties of the polymers to be blended, properties of the compatibilizers, and the amount and ratio of the components, are taken into consideration These variables are tailored and optimized in accordance with the present teachings to provide alloys to meet a particular end use specification For example, if high gas barner 20 properties are desired, then polymers having high individual gas barner properties are preferably selected The amount of compatibilizer is adjusted to provide intermolecular bonding among the components of the alloy to enhance properties and at the same time, to avoid the formation of a quasi- or pseudo-cross linked 25 network which is not readily processable The compatibilizers for use in the present invention are either miscible with each of the LCP and the PET through, e g., covalent, ionic, molecular inter-penetration, hydrogen bonding or associative interactions as mentioned above, or have interactive miscibility when the LCP and PET are 30 present in a common phase In other words, the functional groups of the compatibilizer, LCP, and PET for use in the alloys are also chemically - 11 compatible. For example, if the LCP to be alloyed with PET has an aliphatic type of polyester functionality, such as acrylate or methacrylate, or an aromatic functionality, such as a benzoate or Dhthalate ester linkage, then preferred compatibilizers will have a functionality, such as a polyester 5 functional group or a maleic anhydnde functional group, that is capable of reacting with the polyester group.

Compatibilizers for use in the present invention are also processable in the melting and processing range of PET and the LCP and exhibit temperature stability at the intended processing temperature By 10 temperature stability is meant that a component of the alloy essentially retains its chemical functionality and, hence, its mterfacial interaction with the other components of the alloy with which it interacts If one of the components were not thermally stable, it is possible that the compatibilization achieved could fail on subsequent processing. 15 Preferred alloys of the present invention compnse at least one thermotropic LCP, PET, and at least one compatibilizer Particularly preferred embodiments include two or more compatibilizers, wherein at least one compatibilizer interacts with the LCP and at least one interacts with the PF T. The ratios of compatibilizers to each other and in the total 20 composition are adjusted to achieve alloys having the desired properties as is shown in the examples which follow The following compatibilizers are particularly preferred in the practice of the present invention wherein components of the alloy compnse PET and wholly aromatic esters and copolyesters liquid crystal polymers, 25 such as VECTRA™ and XYDAR™. l. Copolyester elastomers such as HYTREL™ HTR-6108 from DuPont, li. Ethylene-maleic anhydnde copolymers (HDPE grafted with maleic anhydnde), such as 30 PolybondT" 3009 from BP Chemicals; in Ethylene-methyl acrylate copolymers, such as SP 2205 from Chevron, iv Ethylene-methyl acrylate copolymers grafted with maleic anhydnde, such as DS 1328/60 from Chevron, v Ethylene-methyl acrylate-maleic anhydnde terpolymers, such as Lotader™ 2400 from Atochem, vi Ethylene-methyl-methacrylic acid terpolymers (ethylene-methyl acrylate-acrylic acid terpolymers) such as Escor™ ATX-320, Escor™ ATX-325, and Escor™ XV-11.04; and vii Acrylic rubber such as VAMAC™ from DuPont The alloys of the present invention can be extruded to form vanous articles of manufacture such as films and tubes useful, e g , in food packaging, electronic circuit substrates and structural applications The films can be thermoformed to provide, e.g., trays, blow molded to, e.g , form containers, and otherwise processed by known methods. In some 20 embodiments, articles of manufacture compnsing the alloys of the present invention are provided with a thin coating of, e g , glass, metal or another polymer both to protect the article and to provide suitable means to affix labels and the like.

To illustrate the improved properties of the alloys of the present 25 invention, vanous alloys were prepared as taught herein and extruded to form films having improved tensile strength, tensile modulus and/or oxygen barner properties over films extruded from PET or LCP and PET blends without compatibilizers In some films, tensile strength was increased by up to more than 2 times and tensile modulus was increased up to more than 3 30 times over that of the blend without compatibilizer. In many instances, values above 10,000 psi and tensile strength and/or above 500,000 psi and PCT7US95/08358 *■4 - 13 tensile modulus were obtained Films extruded from alloys comprising PET, and an anhydnde-grafted ethylene-methyl acrylate copolymer, thermotropic LCP wholly aromatic copolyester and an ethylene-maleic anhydnde copolymer showed 5 great improved mechanical properties Films extruded from three component alloys comprising PET, wholly aromatic copolyester and an ethylene- methyl acrylate acrylic acid terpolymer, e.g , Escor™ ATX-320 or -325, had superior mechanical properties Also, three component blends comprising PET, wholly aromatic copolyester and a 10 copolyester elastomer such as HYTREL™ HTR-6108 were extruded to produce films having superior mechanical properties 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/lOOin 2 expected for PET 15 Films extruded from alloys comprising PET, a wholly aromatic copolyester LCP and a copolyester elastomer such as HYTREL™ 6108 had excellent barrier properties Also, films extruded from alloys comprising PET, a copolyester elastomer, such as HYTREL™ 6108, a wholly aromatic copolyester, and ethylene-maleic anhydnde copolymer, such as Polybond™ 20 3009 had excellent oxygen barner properties, e g , from about 21 to 23 cc/100in2 Optional components well known to the skilled artisan may be added to alloys of the present invention provided that they do not interfere with formation or with the desired final properties of an alloy Such additives 25 includes fillers and pigments, lubricants, mold release agents, plastersizers, ultraviolet stabilizers and so forth In the methods of the present invention, compatibilizers are used either alone or in vanous combinations with LCP and PET to achieve the desired results They are also used m single step and sequential 30 compatibilization methods as descnbed below The following methods have been found to provide alloys having INTELLECTUAL PROPERTY OFF OF NZ - FEB 1999 - 14 improved properties which can be used, e.g , to provide films having improved properties over films of LCP and PET blends These methods include 1 LCP, PET and at least one compatibilizer are mixed and melt blended to form an alloy, n LCP, PET and a portion of the total compatibilizer to be used are mixed and melt blended, the remainder of the 10 compatibilizer is added at a later time and further melt blended, m LCP, PET and a first compatibilizer are mixed and melt blended A second compatibilizer is added to the melt blend 15 at a later time and further melt blended, iv LCP and PET 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. PET is melted under appropriate conditions in an extruder and at a later time LCP and at least one compatibilizer are added to the PET and further melt blended, vi PET ind a first compatibilizer are melt blended and at a later time LCP and a second compatibilizer are added to the melt blend and further mixed and melt blended, vn PET and LCP are mixed and melt blended and two compatibilizers are 0 WO 96/00752 added to the melt blended and further melt blended, and vm PET, LCP and two compatibilizers are mixed and simultaneously melt blended By controlling the order m which the components of the alloys are mixed and melt blended the properties of the alloy are controlled to enable the production of articles of manufacture, e g , films, which have improved properties over the properties of a similar article of manufacture composed 10 solely of PET or of LCP and PET In the production of films from the alloys descnbed above, the meld blend is extruded, e.g , through a slot die, a circular, counter-rotating die, or a circular rotating tnmodal die In alloys containing two compatibilizers, sequential compatibilization 15 according to methods (in) and (vi) above are preferred preparation methods It was unexpectedly discovered that these unique methods of combining two or more compatibilizers, provided alloys having improved 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 20 compatibilization and in some cases also interact with each other In the case of PET-LCP blends of the present invention, the interaction is between the PET and a first compatibilizer, and the LCP interacts with a second compatibilizer. The products of these two interactions, then sequentially react with one another to form an alloy 25 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 components of the alloy, which is the object of the compatibilization. The method of the present invention is an innovative yet efficient way to achieve the desired 30 end results In one preferred embodiment of the present invention, Chevron DS 1328/60, an anhydride-grafted ethylene-methyl acrylate copolymer, was melt blended with PET and then Polybond™ 3009, an ethylene-maleic anhydnde copolymer, and VECTRA™ A950 were added to the mixture and further melt blended to produce alloys which were extruded to produce 5 films having greatly improved mechanical properties For example, a tensile strength of 14,800 psi was obtained in one film extruded from an alloy made by feeding 5% of the Chevron DS 1328/60 in the hopper with the PET, and then by feeding 2 % Polybond™ 3009 with the LCP VECTRA™ A950 into the vent feed port 10 In another preferred embodiment, Escor™ ATX-325, an ethylene- methyl-methacrylic acid terpolymer, was melt blended with PET and then Polybond™ 3009 and Vectra™ A950 were added to the mixture and further melt blended A tensile modulus value of 1 09 million psi was obtained in a film extruded from an alloy made by feeding 5 % of Exxon ATX™ 320 in 15 the hopper with the PET, and then feeding 2% Polybond™ 3009 with the LCP VECTRA™ A950 into the vent feed port Accordingly, it can be seen that films produced from the alloys of the present invention have surpnsmgly improved properties over films of LCP and PET blends or of PET alone 20 Conventional extrusion equipment 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 earned out using conventional single or double screw extruders. It is preferred that the extruder system has not less than 25/1 L/D ratio and not 25 smaller than 2" Extrusion conditions such as processing temperatures, rotation speed of the screw, feed rate and through put were optimized for the particular alloy by taking into consideration the properties of the polymers being melt blended to form the alloy, including resulting viscosity of the melt blend. Typically, higher shear screw configurations were found 30 to give better dispersions of the LCP and better compatibilization resulting in alloys that could be used to produce films having improved properties • WO 96/00752 PCT/US95/08358 Typical temperatures employed fo/ the processing were 525 to 580°F. The rotation rate of the screw was, typically between 50 to 200 rpm The alloy components are appropriately conditioned, e g , dried and then fed to the extruder using conventional methodologies. For example, 5 the 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 manufacture Alternatively, the dry components can be blended in a hopper and extruded, e.g , to a film directly The masterblendmg or masterbatchmg technique in which typically, a 10 blend of two components is processed mto 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 teachings of the present invention This is a convenient method of manufacture, because an inventory of masterblend material can be made and then combined with 15 different components as desired One advantage to the masterblendmg process is that small and very controlled amounts of additional components can be added to the masterblend For example, if the masterbatch has 10% LCP, the masterbatch can be passed through the extruder again with, for example, 10% of tne masterbatch and 90% of the other polymers, providing 20 a masterbatch that is 1 % in LCP Through masterbatchmg, controlled low concentration of a component in the alloy can be obtained, and additional mixing and shearing through multi-passes m the extruder can be achieved, if desired The present invention will be further illustrated with reference to the 25 following example which is intended to aid m the understanding of the present invention, but which is not to be construed as a limitation thereof EXAMPLE The alloy components should be appropriately treated, e g., dried, 30 before processing as would be readily apparent to the skilled artisan.

The work descnbed in the following example was earned out using a • WO 96/00752 PCT/US95/08358 conventional 25 mm or 40 mm co-rotating, non-intermeshing twin screw extruder manufactured by Berstorff Corporation Mixing and kneading elements for the screw configuration were varied accoroing to conventional wisdom to achieve the desired degree of mixing 5 Films 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 tnmordal die (see, U.S Patents 4,975,312 and 5,288,529) can be used to extrude films comprising one or more alloys of the present invention Since the degree of uniaxial orientation produced in 10 the extruded film has an impact on the properties, films having similar extrusion conditions were compared in the work discussed below A universal testing machine was used for testing the tensile properties based on ASTM standard tests, e g , ASTM #0882.

The LCP used was Vectra™ A-950 from Hoecnst-Celanese 15 Corporation. PET purchased from Eastman Chemicals under the tradename KODAR™ A150 was used in the following work The compatibilizers used included Hytrel™ HTR-6108 from DuPont (Copolyester elastomer), Polybond™ 3009 from BP Chemicals (HDPE grafted v-ith maleic anhydride), SP 2205 from Chevron (ethylene-methyl acrylate copolymer), 20 DS 1328/60 from Chevron (ethylene-methyl acrylate copolymer grafted with maleic anhydnde), Lotader™ 2400 from Atochem (ethylene-methyl acrylate-maleic anhydnde terpolymer), Escor™ ATX-320 from Exxon Chemicals (ethylene-methyl acrylate acrylic acid terpolymer), Escor™ ATX-325 from Exxon Chemicals (ethylene-methyl acrylate-acrylic acid terpolymer), Escor™ 25 XV-11 (k from Exxon Chemicals (ethylene-methyl acrylate-acrylic acid terpolymer), and Vamac™ G1 Acrylic rubber from DuPont The run conditions and results are shown in Tables I-VII In the Tables, the PET used is indicated as "A 150" or "9921" the VECTRA™ LCP is indicated as "A950 " "Ten Yld St " indicates Tensile Yield Strength, and 30 "Ten. Mod " indicates Tensile Modulus Values In the Tables, compatibilizers listed are identified as follows HYTREL™ HTR-6108 as Hytrel 6108; Polybond™ 3009 as HBP3009"; SP 2205™ as "SP2205", DS 1328/60 as "Chev DS", Lotader™ 2400 as "Lotader 2400", Escor™ ATX-320, ATX-325 and XVI1 04 as "ATX320", "ATX325M and "XVI 1.04" respectively.

TABLE A LCP, PET and at least one compatibilizer are mixed and melt blended to form an alloy RUN# HOPPER FEED VENT FEED TEN YLD ST MD(Kp«i) TEN MOD MD(Kpai) OX- BARRIER 6299-7 85 7RA150+9 5SA950+4 8SATX320 - 6 800 272 6299-9 85 7WA150+9 596A950+4 896ATX325 - 9 7 810 - 6299-10 85 7SEA150+9 5*A950+4 8*ClevroD - 9 I 570 3 TABLE B LCP, PET and a portion of the total compatibilizer to be used 25 are mixed and melt blended, the remainder of the compatibilizer is adaed at a later time and furhter melt blended RUN I HOPPER FEED VENT FEED TEN YLD ST MDCKpsi) TEN MOD MDCKpsi) OX- BARRIER 6249-3 85 7WA150+9 5SA950+2 45EATX325 2 4 # ATX325 0 421 255 6249-7 85 7WA150+9 5 *A950+2 4 *BP3009 2 456BP3009 12 9 460 26 8 TABLE C LCP, PET and a first compatibilizer are mixed and melt 5 blended. A second compatibilizer is added to the melt blend at a later tame and further melt blended RUN t HOPPER FEED VENT FEED TEN YLD STMD(KpoI) TEN MOD MB(Rpal) ox BARRIER 6249 8 85 7%A15O+9.5*A9S0+2 45SATX325 2 4%LoUda2400 72 233 TABLE D LCP and PET 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 FEED TEN YLD ST MDCKpst) TEN MOD MD(Kpsi) OX- BARRIER 6299 14 85 7S6AI50+9 5%A9V) 7 8*ATX320 9 1 530 26 6 TABLE E PET is melted under appropnate 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 t HOPPER FEED VENT FEED TEN YLD ST MD(KpsI) TEN MOD MDCKpu) OX- BARRIER 6309-12 85 7%A150 9 7 % A950+4 8 56ATX325 71 460 TABLE F PET and a first compatibilizer are melt blended and at a later 5 time LCP and a second compatibilizer are added to the melt blend and further mixed and melt blended RUN # HOPPER FEED VENT FEED TEN VXD ST MDftCpai) TEN MOD MD(Kpii) OX- BARRIER 7019-7 8996A150+4 7SATX320 9 3*A950+2%BP3009 127 810 29 6 7069-8 8996A150+4 7%ChevrooDS 9 3%A950+2%BP3009 112 960 257 7089 9 89*A150+4 7*XV11 04 9 3SA950+2SBP3009 96 740 7069 10 8996A150+4 7*HytreI6108 9 3 %A950+2 96 BP3009 93 850 1 7079 1 8996A150+4 7%ChevrooDS 9 3%A950+2%BP3009 14 8 840 29 8 TABLE G PET &. LCP are mixed and melt blended and two 20 compatibilizers are added to the melt blended and further melt blended RUN # HOPPER FEED VENT FEED TEN YLD ST MD(Kpst) TEN MOD MDfKpsi) OX- BARRIER 7069-6 8J7SA150+9 S96A950 2 4%HytrcI6108+2 4SBP3009 6 2 420 26 1 TABLE H PET, LCP and two compatibilizers are mixed and simultaneously melt blended in an extruder and extruded through a slot die RUN# HOPPER FEED TEN YLD ST MD(Kp*i) TEN MOD MDCKpil) OX- BARRIER 7169 3 80S6A150+10*A950+7 5#Hytrel6108+2 596BP3009 79 370 3 40 SUBSTITUTE SHEET (RULE 26) TABLE J PET, LCP and two compatibilizers are mixed and simultaneously melt blended and extruded through a circular, counter-rotating die.

RUN# HOPPER FEED VENT FEED TEN YLD ST MDflipal) TEN MOD MD(Kpsl) ox- BARRJER 1199-3 83%A150+10*A950 + 5*ATX320+ 2*BP3009 - 62 440 1199-4 81 * A150+10SA9J0+5 %SP2205 +4 #BP3009 - 9 370 1199-J 81%A150+10*A950 +5*SP2205 +4*Hytrel6108 - 7 2 440 - TABLE K PET and a first compatibilizer are melt blended and, at a later time, LCP and a second compatiblizer are added to the melt 25 and further mixed and melt blended and extruded using a circular rotating tnmodal die RUN# HOPPER FEED VENT TEN YLD ST MDfKpsi) TEN MOD MD(Hpsi) OX- BARRIER 3249-2 83 6SJA150+4 4J6ATX320 %A950+2%BP3009 90 290 - 3249-5 83 6%A15C+4 4#ChevroaDS *A950+2%BP3009 65 220 - SUBSTITUTE SHEET (RULE 26) TABLE L - Control PET RUN t HOPPER FEED VENT FEED TEN YLD ST MD(Kp»i) TEN MOD MD(Kp>!) OX- BARRIER 1 6249-1 100VA150 - 55 162 - 5249-0 100*A150 - 54 190 - 5119-0 100SA150 - 58 169 - 4239-1 100*A150 - 62 176 31.5 6299-1 100*A150 - 52 320 - 7069-1 100*A150 - 5J 320 29 9 3189-1 100*A150 - 62 200 - TABLE M - Control PET & LCP, No Compatibilizer RUN # HOPPER FEED VENT FEED TEN YLD ST MD(Rpsi) TEN MOD MD(KptI) OX- BARRIER 3189-2 90*A150+10*A950 - 6 9 290 - 3189-5 90*A150+10*A950 - 5 210 22 7 3189 9 90*A150+10*A950 - 8 231 - 6249-2 90*A150+I0*A950 - 74 251 - 7069-2 90*A150+10*A950 - 6 1 420 24 9 7019 5 90*A150+10#A950 - 6 1 440 - TABLE M - Masterbatch RUN# HOPPER JFQS VENT FEED TEN YLD ST MD(Kpai) TEN MOD MD(Kpoi) ox- BARJUER 1 8129-1 83*A150+5*HytnJ6108 *A950+2*BP3009 8 0 550 6 8129-5 7S8AI50+10*Hytrcl610S SO*A95O+2*BP3O09 78 230 196 8129-10 83«A150+5SHytrcH108 *A950+2*BP3009 6 430 22 1 8129-16 78*A150+10*Hytjrl6108 #A950+2*Hytrel6108 9 420 18 5 8129-17 78*A150+10«Hytrcl6108 *A950+2*Hytrc]6108 8 430 18 4 8129-18 7SXA150+10*Hytrel6108 *A950+2*BP3009 74 600 19 5 8129-19 78*A150+10*Hytrcl6108 #A950+ 2*BP3009 7 6 710 18 0 _ . 1 The present invention has been descnbed in detail including the preferred embodiments thereof However, it would be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention and still be 20 within the scope and spirit of this invention as set forth in the following claims

Claims (1)

WHAT WE CLAIM IS -25- 28 9669 1 An alloy comprising at least one thermotropic liquid crystalline polymer (LCP), polyethylene terephthalate (PET) and at least one compatibilizer, wherein the compatibilizer is (i) a copolyester elastomer, (11) an ethylene-unsaturated ester copolymer grafted with at least one functional monomer, or (in) an acrylic elastomer 2 An alloy comprising at least one thermotropic liquid crystalline polymer (LCP), polyethylene terephthalate (PET) and at least one compatibilizer, wherein the LCP compnses wholly or partially aromatic polyesters or copolyesters and blends thereof and the compatibilizer is (i) a copolyester elastomer, (11) an ethylene-unsaturated ester copolymer grafted with at least one functional monomer, or (in) an acrylic elastomer 3 An alloy in accordance with claim 2, wherein (I) the ethylene-unsaturated ester copolymer grafted with at least one functional monomer is an ethylene-methyl acrylate copolymer grafted w.th maleic anhydnde, or (II) the acrylic elastomer is an acrylic rubber 4 An alloy compnsing at least one thermotropic liquid crystalline polymers (LCP), wherein the LCP compnses wholly or partially aromatic polyesters or copolyesters and blends thereof, polyethylene terephthalate (PET) and at least one compatibilizer, wherein the compatibilizer is (I) an ethylene-methyl acrylate-maleic anhydnde terpolymer, (II) an ethylene-methyl acrylate-acrylic acid terpolymer, or (in) an ethylene-methyl acrylate copolymer grafted with maleic anhydnde INTELLECTUAL PROPERTY OFFICC OF NZ 1 1 MAR 1999 VEO -26- 28 Pp 5 An alloy m accordance vVitli claim 2 or 4, wherein the copolyester is a bisphenol-based aromatic copolyester cr a naphthalene-based aromatic copolyester 6 An alloy in accordance with claim 2, wherein the LCP is wholly aromatic copolyester and the compatibilizer is a copolyester elastomer 7 An alloy in accordance with claim 2, wherein at least two compatibilizers are present 8 An alloy comprising at least one thermotropic liquid crystalline polymer (LCP), polyethylene terephthalate (PET) and at least two compatibilizers, wherein the LCP compnses wholly or partially aromatic polyesters or copolyesters and blends thereof and the compatibilizers are selected from a copolyester elastomer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl acrylate copolymer grafted with maleic anhydnde, ethylene-methyl acrylate-rnaleic anhydnde terpolymer, ethylene-methyl acrylate-acrylic acid terpolymer and acrylic rubber 9 An alloy in accordance with claim 8, wherein the LCP is a wholly aromatic copolyester and the compatibilizers are an ethylene-methyl acrylate-acrylic acid terpolymer and an ethylene-maleic anhydnde copolymer 10 An alloy m accordance with claim 8, wherein the LCP is a wholly aromatic copolyester and the compatibilizers are an ethylene-methyl acrylate copolymer and an ethylene-maleic anhydnde copolymer 11 An alloy in accordance with claim 8, wherein the LCP is a wholly aromatic copolyester and the compatibilizers are an ethylene-methyl acrylate copolymer grafted with maleic anhydnde and an ethylene-maleic anhydnde copolymer Intellectual p£or^n i ufhoP of n z 1 1 MAR 1999 RECEIVED 283660 12 An alloy in accordance with claim 8, wherein ihe LCP is a wholly aromatic copolyester and the compatibilizers are a copolyester elastomer and an ethylene-maleic anhydnde copolymer 13 An alloy compnsmg at least one thermotropic LCP, PET and at least one compatibilizer, wherein the compatibilizer is an ethylene-methyl acrylate copolymer 14 An alloy in accordance with claim 13, wherein the ethylene-unsaturated ester copolymer is an ethylene-methyl acrylate copolymer 15 A method of producing an alloy compnsing at least one thermotropic LCP, PET, and at least one compatibilizer compnsing a copolyester elastomer, wherein the LCP compnses wholly or partially aromatic polyesters and copolyesters and blends thereof and the method compnses melt blending the LCP, PET and compatibilizer to form an alloy 16 A method m accordance with claim 15, wherein the method compnses 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 17 A method of producing an alloy compnsing at least one thermotropic LCP, PET and a first and second compatibilizer, wherein the method compnses melt blending PET and the first compatibilizer to form a first melt blend, adding LCP and the second compatibilizer to the first melt blend, and further melt blending to form an alloy 18 A method of producing an alloy compnsing at least one thermotropic LCP, PET and a first and second compatibilizer, wherein the method compnses melt blending LCP, PET and the first compatibilizer to form a melt blend, adding the second compatibilizer to tne melt blend, and further melt blending to form an alloy INTELLECTUAL PROPERTY OFFICF OF NZ 1 1 MAR 1399 RECEIVED -28- 289669 19 An article of manufacture comprising an alloy according to any one of claims I to 14 20 An article of manufacture according to claim 19, wherein the article compnses a film, a sheet, a tube, or a con amer 21 An article of manufacture according to claim 19, wherein the article is provided with a coating compnsing glass, metal or polymer 22 An article according to claim 19, 20 or 21, substantially as herein descnbed 23 A method according to any one of claims 15 to 18, substantially as herein descnbed 24 An alloy whenever produced according to the method of any one of claims 15 to 18 and 23 25 An alloy according to any one of claims

1-14, substantially as herein descnbed (JF6 1 IMTrLLrcru, I T'lPERTY OFFICE ui 1 1 MAR 1999 RECEIVED