AU708261B2 - Compatibilized LCP blends - Google Patents

Description

V

axIILn D'J GRiiikS IFFIkTH HACH( FELB 83/06/99 12:35 Pq S/18 COMPazibilized LCP Bleads FIELD OF THE D-NF>TTO0N cy-sm.UIne pcivyre-s(L5 s and oolvethvtc-e U-ehlhar an ai. Jeast one czmpzdi~ii:, B ACK GR 0UND High Pefrnan: tiasdcs are- in w4ides-zre,-d use'- inmn i dts and th~ere- is much ineetLtdevejooing 1"eW olasidcs WhicL arm. -oorlicnd and r~ycable, azs we-1 as hihpfrrac.Tebei~~adaxigor israng polymers is a cosz te4;crve way to product newk hj.ig oe:frt.nc plsC. hchme the$-- Polvmer blends ccn~ajnjn te.rrno-pc C~ hverttn .incrrzstng- att ition in tt e-'C.-ntifc and te--.icatcz Lim e T'he o ~hich peo~n~thermocLastc fleyibd polymers which have beit bit-ided with ThCP's include polvt-ddes, polyaxnides, poly(etherUilfone)

(PES),

poly~eh-mLe poiyeaherktn polyCari~nat (pC), PQ1Y(6ihY1S1Ae terphthlatej (PET), poly(mthyleft naphthalate)

(PEN),

polypheriylen aulfide (PPS), and palyarylatehermnozooic LCPs ze a re laively new class of hi gh pef-,ormnanjc= 20 Coyei maeid wj4cgj cum,~ COir~le the adatAe off meltpc tsabr CC and outsiandi.rg mec'nanicz-1 properdes. Because of the~ir rigid backcbone structurfe with flexiole smactr groups, cornmetciafly aveiable therrroa-opic LCPs have fir highe- tensile strtnath and flexural moduli t~han conventionali .polym=rs. However, h-nouooic LC~s art in many c:1es difificult to rprcess wir~iouc s &eid-, uiomeic and ve-y costly as cornioa,- with conven-Ionzi1 olyme:5 when used alonie.

BleridLrg the=Anotrooic L-C?s with orche polymers has been. shownl ro LrflD ove proctssa'oi icy ofute other! polym -rs, rtidculazly LC~s base-d on wholly axornatc chaim- stzm-2ncs, Fre--nebndiwjhconveidomal therrno-lastic oolymers red--uces costs, because less of the very costly LCP is ustd. Also, beea--use thenor-opjc LCPs form anr ordered Dphzsc in the melt 03/06 '99 THU 12:36 [TX/RX NO 8054] Z~005 WO 96/00752 PCT/US95/08358 -2- (hence, the name thermotropic), they have shear viscosities far lower than other polymers 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 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, 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 rigid structure has been reported.

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 Groeninckx, 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 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 or more, the LCP phase was reported to show a well-developed microfibrillar 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, 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 Polymer Processing Society Summer Meeting, Amherst, Massachusetts, August 16-17, 1989, Paper 10F. See, also Williams, Proceedings of WO 96/00752 PCT/US95/08358 -3- 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, 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 compromise of properties and economies of the individual components. It is well known that the 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 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 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 exceeding those of the average of the original ingredients. The types of interaction or "chemical bonding" between the components can include, for example, one or more of the following mechanisms: ionic; covalent; molecular interpenetration; hydrogen bonding; or associative.

Successful compatibilization by one or more of these interactions gives rise to interfacial adhesion to provide the formation of cohesive multiphase compatibilized alloys with useful properties. To achieve compatibilization a number of strategies have emerged.

WO 96/00752 PCT/US95/08358 -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 compatibilized blend.

In another approach, polymers having nucleophilic functional groups are interacted with compatibilizers containing hydrogen to form hydrogen bonding. Ionomers have also served as compatibilizers. In some cases, ionic or strong physicochemical interactions are generated across the interface, which in turn enhances compatibilization.

Compatibilization can also result from the addition of a similar functional group using the "like attract like" theory, such as the use of chlorinated polyethylene to compatibilizer polyvinyl chloride with polyethylene. This has been referred 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 primary blend components, those components intended to be compatibilized. The compatibilizing effects of the mutually miscible component may result from its presumed tendency to become enriched in 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 with a singular 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, thereby, to provide LCP/PET alloys having properties which can be tailored to meet end-use specifications are being sought.

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.

Preferred compatibilizers include copolyester elastomers; ethylene-unsaturated ester copolymers, such as ethylene-methyl acrylate copolymers; copolymers of 10 ethylene and a carboxylic acid or acid derivative, such as ethylene-methyl acrylate copolymers; polyolefins or ethylene-unsaturated ester copolymers grafted with functional monomers, such as ethylene-maleic anhydride copolymers; copolymers or terpolymers of ethylene and a carboxylic acid or acid derivative, such as ethylenemethyl acrylate-maleic anhydride terpolymers; terpolymers of ethylene, unsaturated ester and a carboxylic acid or acid derivative, such as ethylenemethyl acrylate-acrylic acid terpolymers; and acrylic 20 elastomers, such as acrylic rubbers. A particularly preferred copolyester elastomer is HYTRELTM HTR-6108; ethylene-maleic anhydride copolymer is Polybond3009; ethylene-methyl acrylate copolymer is SP 2205TM; ethylene-methyl acrylate copolymer grafted with maleic anydride is DS1328/60TM; ethylene-methyl acrylate-maleic anhydride terpolymer is LotaderTM 2400; ethylene-methyl acrylate-acrylic acid terpolymer is EscorTN ATX-320, EscorTmATX-325 or EscorrMXV-11.04; and acrylic rubber is VamacT" Gl.

H:\Simeona\Keep\29583.95.doc 28/05/99 5A Preferred thermotropic LCPs include wholly or partially aromatic polyesters or copolyesters.

A

particularly preferred copolyester is XYDART7m or VECTRATm.

Other preferred thermotropic liquid crystal polymers include SUMIKOSUPER® and EKONOLTW (Sumitomo Chemical), DuPont HXTm and DuPont ZENITETW I. duPont de Nemours), RODRUN® (Unitika) and GRANLARTW (Grandmont).

Preferred LCPs for use in the present invention 10 include any such resins With a melt temperature in the range of 250 to 320'C. Particularly preferred LCPs have a melt temperature in the range of 250 to 280 0

C.

one preferred alloy in accordance with the present invention .r 00* WO 96/00752 PCTIUS95/08358 -6comprises 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 comprises PET, a wholly aromatic LCP copolyester and an ethylene-maleic anhydride 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 anhydride compatibilizer, such as

DS

T 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 copolyester elastomer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl acrylate-maleic anhydride terpolymer, ethylene-methyl-methacrylic 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 ethylene-maleic anhydride copolymer compatibilizer. Exemplary ethylenemethyl acrylate-acrylic acid terpolymers include Escor" ATX-320, Escor

T

ATX-325, or Escor XV-11.04 and an exemplary ethylene-maleic anhydride copolymer is Polybond" 3009.

In other preferred PET/LCP alloys, the LCP comprises a wholly aromatic copolyester and the compatibilizers are an ethylene-methyl acrylate copolymer and/or an ethylene-maleic anhydride copolymer. An exemplary ethylene-methyl acrylate copolymer is SP 2205" and an exemplary ethylenemaleic anhydride copolymer is Polybond" 3009.

Another preferred LCP/PET alloy of the present invention comprises a wholly aromatic LCP copolyester and an ethylene-methyl acrylate copolymer grafted with maleic anhydride and an ethylene-maleic anhydride WO 96/00752 PCT/US95/08358 -7copolymer compatibilizer. Yet another preferred alloy comprises PET, wholly aromatic LCP copolyester, and copolyester elastomer such as

HYTREL

T HTR 6108 and an ethylene-maleic anhydride copolymer such as Polybond T 3009.

The ethylene-methyl acrylate copolymer grafted with maleic anhydride, DS" 1328/60, and the ethylene-maleic anhydride copolymer, Polybond™ 3009 are particularly preferred when the LCP is VECTRA

T

Also preferred when the LCP is VECTRA T is the compatibilizer, Polybond T 3009 and a second compatibilizer, Escor" ATX-320, Escor" ATX-325, DS1328/60", Escor" XV-11.04, or HYTREL6108.

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 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 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 comprising 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/100in.

2 It was unexpectedly found that when PET/LCP alloys were formed by adding suitable compatibilizers in accordance with the teachings of the present invention, improved mechanical properties and/or lower gas permeation (barrier) numbers were WO 96/00752 PCT/US95/08358 -8obtained.

The present invention also provides methods of preparing the alloys described above. These methods include: i. LCP, PET and at least one compatibilizer are mixed and melt blended to form an alloy; ii. 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; iii. 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 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 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 and simultaneously melt blended.

~1~1 WO 96/00752 PCT/US95/08358 -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.

The alloys of the present invention comprise 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 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, from about 78 to about 86 weight percent PET, and from about 5 to about 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 ordinary skill in the art. Suitable PET is also available commercially from a number of vendors, including KODAR" A150, KODAR T 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 in the present invention include wholly aromatic co-polyester. Vectra T M A950, sold by Celanese Research Corporation, Summit, New Jersey is one such wholly aromatic copolyester. This polymer has been reported to

II~

WO 96/00752 PCT/US95/08358 consist essentially of about 25-27 percent of 6-oxy-2-naphthoyl moieties and about 73-75 percent of p-oxybenzoyl moieties, as described in example 4 of U.S. Patent No. 4,468,364 and in G. W. Calundann et al., "Anisotropic Polymers, Their Synthesis and Properties", reprinted from Proceedings of 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 thermotropic LCPs include wholly or partially aromatic polyesters or copolyesters. A particularly preferred copolyester is

XYDAR

T or VECTRA

T

Other preferred thermotropic liquid crystal polymers include SUMIKOSUPER® and EKONOL (Sumitomo Chemical), DuPont HX" and DuPont ZENITE" duPont de Nemours), RODRUN® (Unitika) and GRANLAR" (Grandmont).

In formulating the composition of the alloys of the present invention 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 barrier properties are desired, then polymers having high individual gas barrier 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 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, covalent, ionic, molecular inter-penetration, hydrogen bonding or associative interactions as mentioned above, or have interactive miscibility when the LCP and PET are 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 1 WO 96/00752 PCT/US95/08358 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 phthalate ester linkage, then preferred 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.

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 temperature stability is meant that a component of the alloy essentially retains its chemical functionality and, hence, its interfacial 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.

Preferred alloys of the present invention comprise 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 PET. The ratios of compatibilizers to each other and in the total 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 comprise PET and wholly aromatic esters and copolyesters liquid crystal polymers, such as VECTRA T and XYDAR": i. Copolyester elastomers such as HYTREL HTR-6108 from DuPont; ii. Ethylene-maleic anhydride copolymers (HDPE grafted with maleic anhydride), such as Polybond" 3009 from BP Chemicals; iii. Ethylene-methyl acrylate copolymers, such as WO 96/00752 PCT/US95/08358 12- SP 2205 from Chevron; iv. Ethylene-methyl acrylate copolymers grafted with maleic anhydride, such as DS 1328/60 from Chevron; v. Ethylene-methyl acrylate-maleic anhydride 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 various articles of manufacture such as films and tubes useful, in food packaging, electronic circuit substrates and structural applications. The films can be thermoformed to provide, trays, blow molded to, e.g., form containers, and otherwise processed by known methods. In some embodiments, articles of manufacture comprising the alloys of the present invention are provided with a thin coating of, 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 invention, various alloys were prepared as taught herein and extruded to form films having improved tensile strength, tensile modulus and/or oxygen barrier 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 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 Fax ent h4 61392438333 GRIFFITH HACH MELB Faxsen ht 61924833 tIFITHHAC MED 3/86/99 12:35 PN: 6/18 Filims exctrudied from thrae componen~t alloys cornpriainq PET, wholly aromatic cupolyestar and an athylezne-mathyl acry2late-acrylic acid teroymer, P27 OMZlv c ~Coooi''eSZ2 2zd a colvest,2 e1stOrne, SLuch as HZ T? F7R.OSLOR, We -:ZLtuc"e4 to *OrQ-duc-- Llrs havl. Su'.:L-oz Mech "~Czi -jrOe'4eS- AriL~mC or ~msL th aL~ovs ore Lrsn uvtnE~n .yield--" low o:-Ygrn ue--.71'2Zort values, C-'-irn fi-Cr about IS to 30, wCL[ o the 36 to 40o cc/ ICC&. e:'eC'ted fa. PEI, 151im Fhn =d ti aLloys comr s' 7. PETL, a wholly -xoina C cc-colvestze' LC? and a. copolveste: za-szorer suc.1 as ~yTRELT 6108 had C0o00lyeste:, and eu.hy-e.- -ma:eic anhydrd-zcoo-ie:, such a5 Polybocid7 3009 hzd excYUent oxge o er urn~s rom about 21 tc 23 *OdnicornoonenLs well !ciown wo t-he sd1 ardsari may be added rto aloyS of~ 6-e pr!Stnt Livnton provided that they do not Lriter7fex' wich formadon or withl Lhe d!Sir-.d 1'2- DOre--.ieS Of an alloy. Such,- Zddi-vels u!~avo~etszaoLUizers arc. So Forth".

e; C.e tn e o r inLL aou _i-unsW LPad PET to 'hei:e de~td ~sirs.Tnya:., 722o IS:-d In Singi' szzo anld sec-ue-nua! comm~a~odrl rn,-thods a5 dtsct-ibed loeow.

Thre roi~owirig innet-hcd5 have beti foun-d to orovidt ,U.oys havingr 03/06 '99 THU 12:36 [TX/RX NO 8054] IM006 WO 96/0( 752 PCT/US95/08358 14improved properties which can be used, to provide films having improved properties over films of LCP and PET blends. These methods include: i. LCP, PET and at least one compatibilizer are mixed and melt blended to form an alloy; ii. 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; iii. 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 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 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 WO 96/00752 PCT/US95/08358 15 added to the melt blended and further melt blended; and viii. PET, LCP and two compatibilizers are mixed and simultaneously melt blended.

By controlling the order in 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, films, which have improved properties over the properties of a similar article of manufacture composed solely of PET or of LCP and PET.

In the production of films from the alloys described above, the meld blend is extruded, through a slot die, a circular, counter-rotating die, or a circular rotating trimodal die.

In alloys containing two compatibilizers, sequential compatibilization according to methods (iii) 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 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.

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 end results.

In one preferred embodiment of the present invention, Chevron DS WO 96/00752 PCT/US95/08358 16- 1328/60, an anhydride-grafted ethylene-methyl acrylate copolymer, was melt blended with PET and then Polybond 3009, an ethylene-maleic anhydride copolymer, and VECTRA T A950 were added to the mixture and further melt blended to produce alloys which were extruded to produce 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

T A950 into the vent feed port.

In another preferred embodiment, Escor" ATX-325, an ethylenemethyl-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 T 320 in the hopper with the PET, and then feeding 2% Polybond 3009 with the LCP VECTRA

T

A950 into the vent feed port.

Accordingly, it can be seen that films produced from the alloys of the present invention have surprisingly improved properties over films of LCP and PET blends or of PET alone.

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 carried 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 smaller than 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 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 17- Typical temperatures employed for 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, dried and then fed to the extruder using conventional methodologies. For example, 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, to a film directly.

The masterblending or masterbatching technique in which typically, a 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 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 different components as desired. One advantage to the masterblending process is that small and very controlled amounts of additional components can be added to the masterblend. For example, if the masterbatch has LCP, the masterbatch can be passed through the extruder again with, for example, 10% of the masterbatch and 90% of the other polymers, providing a masterbatch that is 1 in LCP.

Through masterbatching, controlled low concentration of a component in the alloy can be obtained; and additional mixing and shearing through multi-passes in the extruder can be achieved, if desired.

The present invention will be further illustrated with reference to the following example which is intended to aid in 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, dried, before processing as would be readily apparent to the skilled artisan.

The work described in the following example was carried out using a WO 96/00752 PCT/US95/08358 18conventional 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 according to conventional wisdom to achieve the desired degree of mixing.

Films were extruded from a slot die, approximately 8 inches wide with die gap of approximately 0.010 to 0.020 inches. Also, a counterrotating die or circular trimordal 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 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, ASTM #0882.

The LCP used was Vectra" A-950 from Hoechst-Celanese Corporation. PET purchased from Eastman Chemicals under the tradename

KODAR

T 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 with maleic anhydride); SP 2205 from Chevron (ethylene-methyl acrylate copolymer); DS 1328/60 from Chevron (ethylene-methyl acrylate copolymer grafted with maleic anhydride); Lotader" 2400 from Atochem (ethylene-methyl acrylatemaleic anhydride 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" XV-11.04 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 "A150" or "9921" the VECTRA" LCP is indicated as "A950." "Ten Yld St." indicates Tensile Yield Strength; and "Ten. Mod." indicates Tensile Modulus Values. In the Tables, compatibilizers listed are identified as follows: HYTREL HTR-6108 as WO 96/00752 PTU9/85 PCTfUS95/08358 19 Ilytrel 6108; PolybondP" 3009 as "BP3009"; SP 2205T" as "SP2205"; DS 1328/60 as "Chev DS"; Lotade tm 2400 as "Lotader 2400"; Escor m ATh- 320, ATX-325 and XV11.04 as "ATX32O", "ATX325' and "XVl1.04" respectively.

TABLE A LCP, PET and at least one compatibilizer are mixed and melt blended to form an alloy RUN HOPPER FEED VENT FEED ITEN YLD jTEN MOD OX.

6299-7 85.7%A150+9. %A950+4.8%ATX320 j J 10.6 J 00 J 27.2 j 6299-9 85.7%A1SO+9.5%A950+4 .8%ATX325 j j 9.7 810 J 6299-10 85.7%A150+9.5%A95 0+4.8%Chievron 9.1 570 f 25.3 TABLE B 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 furhter melt blended.

tRUN I JHOPPER FEED JVENT FEED TE JL TN MOD jOX- MD(Kpst) IBARREER _I I_ 6249-3 85.7%A150+9.5%A950+2.4%ATX325 2.4%ATX325 10.0 421 24-7 .7%A 50+9.5 %A950+2.4 %BP3009 2.4%BP3009 f 12.9 460 26.8 WO 96/00752 PTU9I8S PCT/US95/08358 20 TABLE C 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.

RUN F HOPPER FEED JVENT FEED ITEN YLD TEN MOD oxf6249-8 85.7%A150+9.5%A95O+2.4 %ATX32S 2.4 %Lotadcr2400 7.2 233- 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.

R UN A HOPPER FEED IVENT FEED TEN YLD 1TEN MOD fOX- IST MD(Kpsi)_JMD(Kpsi) BARRIER f6299.14 85.7%A150+9.5%A950 7.8%ATX320 f 9.1 5310 J 26.6 TABLE E 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.

RUN# HOPPER FEED VENT FEED) TEN YLD jTEN MOD JOX- IST MD(Kpsi) -MD(Kps) -BARRIER 6309-12 85.7%A150 9.7%A950+4.8%A'rX325 J 7.1 460- WO 96/00752 WO 9600752PCTIUS95/08358 21 TABLE F 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.

RUN HOPPER FEED IVENT FEED STEND YLD TEN MOD OX.

7019-7 89%AI50+4.7%ATX32O 9.3%A950+2%BP3009 12.7 J 810 J 29.6 [7069-8 J89%A150+4.7%ChcvronDS [9.3%A950+2%BP3009 11.2 J 960 T 25.7 7069-9 89%A150+4.7%XVII.04 [9.3%A950+2%BP3009 9.6 J 740 E7069-110 89%A150+4.7%Hytre6108 9.3%A950+2%BP3009 93850 20.3 70E79-1 ]89%A150+4.7%ChevronDS 9.3%A950+2qBP3009 14.8 840 29.8 TABLE G PET LCP are mixed and melt blended and two compatibilizers are added to the melt blended and further melt blended.

RUN HOPPER FEED VENT FEED TEN YLD ITEN MOD JOx- I IST MD(Kpsi) MD(Kpsi) BARRIER 7069-6 85.7%A150+9.5%A950 I2.4%HytreI6108+2.4%BP3009 J 6.2 420 J 26.3 TABLE H PET, LCP and two compatibilizers are mixed and simultaneously melt blended in an extruder and extruded through a slot die.

RUN#JHOPPER FEED TE STMD(p TEN OD) [0RI 7169-3 J80%A150+ 10%A950+7.5 %Hytre]6108 +2.5 %BP3009 f 7.9 370 25.3 I_ I__ SUBSTITUTE SHEET (RULE 26) WO 96/00752 PCTIUS95/08358 22 TABLE J PET, LCP and two compatibilizers are mixed and simultaneously melt blended and extruded through a circular, counter-rotating die.

RJN IOPPER FEED VENTI TEN YLD ITEN MOD IOX- JFEED- ST MD(Kpsi) MD(Kpsi)_jBARRIER_ [1199-3 3%A150+10q6A950+5%ATX320+2%BP3009jj- 6.2 440 [11994 [81%A150+10%6A950+5%SP2205+4%BP309 1 5.9 J 370 1995 8 %A150+10%A950+5%SP2205+4%Hytrrl6lO8 L.i 7.2 J 40 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 and further mixed and melt blended and extruded using a circular rotating trimodal die.

RUN#]_HOPPER FEED) VENT TEN TNMOD jOX' j 3249-2 J83.6%A150+4.4%ATX320 J10%A950+2%6BP3009 f 9.0 290 3249-5 J83.6%4A150+4.4%ChevronDS J10%A950+2%BP3009 f 6.5 220 SUBSTITUTE SHEET (RULE 26) WO 96/00752 PCTIUS95/08358 -23 TABLE L Control PET RUN I HOPPER FEED VENT FEED TEN YD TEN MOD OX- ST MD(Kp!) MD(Kps!) BARRIER 6249-1 100%A1SO 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%A15f 5.2 320 7069-1 100%A150 5.3 320 29.9 3189-1 100%A150 6.2 200 TABLE M Control PET LCP, No Compatibilizer RUN 1 HOPPER FEED VENT FEED TEN YLD TEN MOD OX- ST MD(Kpei) MD(Kpsi) BARRIER 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 I 6.1 420 24.9 7019.5 90%A150+10%A950 6.1 440 24 TA1BLE N Masterbatch RUN I RU ~HOPP2

F=

VMiT F= TEN YLD Tmi MOD 0X_

S

S.

S

*5

S

S

S S

S

S

S S

S

S

S

S MKp.) jNMl(K*) jBARRMR f 129-1 13l%A150+.5%Hy=MId08 10%A950+~2%BP3009 .0J 17 5 T 06 3129-5 j 7 8%A1SO+10%HtJC1I03 10SA950+2%Bp300g 7. 32-10 33%A150-.5%Hyux-610$ 10%A950-+2%BP3009 J 5.6 430=.

r3129L-16 7 8%A1SO+10%HyarJ6I0SO I IOA950+2%HyTmL~jos 5.9 42 18.5___ 3129-17 73 %AISO+ I0%Hyrxci103 10l%A950-2%{ytv-1 1 5.8 430 10 [3129-18 7I 7 %A 150+10%Hytrci6I08 10SA9S0+2%B30 7.4 60 1.

312.9-19 78 7 %A1S0+10%Hiytei6IO8 10%A950+2%BP3009 7.6 710 18.0 The present invention has been described in detail including the preferred embodiments thereof. However, it would be appreciated that those silled in the art, upon consideration of the present disclosure, may make modifications and/or improvemnents on this invention and still be 20 within the scope and spirit of this invention as set forth in the following claims.

Throughout this specification and the claims, the words "comprise", "comprises" and "comprising" are used in a nonexclusive sense.

Claims (9)

1. An alloy comprising at least one thermotropic liquid crystalline polymer (LCP), polyethylene terephthaJlate (PET) and at least one compatibilizer, wherein the compatibilizer comprises: a copolyester elastomer; (ii) an ethylene-unsaturated eater copolymner grafted with at least one functional monomer; or (iii) an acrylic elastomer.

2. An alloy in accordance with claim 1, wherein the copolyeoter elastomer is HYTRET2' HTR-610B; 15 (ii) the ethylene-unsaturated eater copolymer grafted with at least one functional monomer is an ethylenie-methyl acrylate copolymer grafted with maleic anhydride; and (iii) the acrylic elastomer is an acrylic ru~bber.

3. An alloy in accordance with claim 2, wherein 0(i) the ethylene-methyl acrylate copolymer grafted with mialeic anhydride ia VS1328/6O"'; and (ii) the acrylic ruzbber in Vamac TM G1.

4. An alyiacodnewith claim 1, wherein the thermotropic LCP compriges wholly or partially aromatic 0 polyesters or Co~olyesters and blends thereof. S. An alloy in accordance with claim 4, wherein the copolyeater is a biphenyl-based aromatic copolyeater or a naphthalene-baoed aromatic copolyester. 3,S 03/06 '99 THU 12:36 [TX/RX NO 80541 Qj007 Fax sent bu 61392438333 GRIFFITH HACK MELBF 03/06/99 12:35 Pq: 8/18 26 An alloy in accordance with claim 1. wherein the LCP in wholly aromatic copolyester and the compatibilizer is a copolyester elastomer.

7. An alloy in accordance with claim 1, wherein at least two compatibilizers are present.

8. An alloy comprising at least one thermotropic liquid crystalline polymer (LCP), wherein the LCP comprises wholly or partially aromatic polyesters or copolyesters and blends thereof, polyethylene terephthalate (PET) and at least two compatibilizers, wherein the compatibilizers are selected from a Copolyeater elastomer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate copolymer, i: 15 ethylene-methyl acrylate copolymer grafted with maleic anhydride, ethylene-methyl aczylate-maleic anhydride terpolymer, ethylene-methyl acrylate-acrylic acid *terpolymer or acrylic rubber.

9. An alloy in accordance with claim 8, wherein the LCP is a wholly aromatic copoJyester and the compatibilizers are an ethylene-methyl acrylate-acrylic acid terpolymer and an ethylene-maleic anhydride copolymer. 25 10. An alloy in accordance with claim 9, wherein the ethylene-methyl adrylate-acrylic acid terpolymer is Escoru ATX-320, Escor' ATX-325, or Escor TM XV11.04 and the ethylene-maleic anhydride copolymer is PolybondTN 3009. H\sifona\~ecp\295R] l)do2 3/O6j/99 03/06 '99 THU 12:36 [TX/RX NO 8054] Z008 Fax sent bq 61392438333 GRIFFITH HACH MELB Faxsen bj 63943833GRIFIH HCI MED 3/06/99 12:35 Pq: 9/18

27- 11. An alloy in accordance with claim 8, wherein the LCP is a wholly aromatic copolyster and the couipatibilizers are an ethylene-methyl acrylate copolymer S and an ethylene-maleic anhydride copolymer. 12. An alloy in accordance with claim 9, wherein the ethylene-methyl acrylate copolymer is SP 2205T and the ethylene-maleic anhydride copolymer ia Polybond~m 3009. 'c 13. An alloy in accordance with claim 8, wherein the *LCP is a wholly aromatic copolysster and the 9 compatibilizers are an ethylene-methyl aczylate copolymer grafted with maleic anhydride and an eizhylene-maleic 15 anhydride copolymer.

914. An alloy in accordance with claim 13, wherein the ethylene-methyl acrylate copolymer grafted wit~h maleic anhydride in PST' 1328/60 and the othylene-maleic anihydride copolymer is PolybondT' 3009. 9 915. An alloy in accordance with claim 8, wherein the LCP is a wholly aromatic copolyester and the compatibilizers are a copolyester elaotomer and an 25 ethylene-uialeio anhydride copolymer. 16. An alloy in accordance with claim 15, wherein the copolyester elastomer is MYTREL~x HTR 6108 and the ethylene-maleic an~hydride copolymer is PolybondTft 3009. 17. An alloy in accordance with claim 5, having at least two qompatibilizers, wherein one compatibilizer is Polybond T K 3009 and one compatibilizer is EscorT4 ATX- 320, Egcor T ATX-325, PS1 3 28/6TL, EgCorTE XVll04, or HYTRELT"6108. H:Sm n .1.\99 95 n .3/06/99 03/06 '99 THU 12:36 [TX/RX NO 8054] Qj009 Fax sent by 61392438333 GRIFFITH HACH MELB 83/86/99 12:35 Pq: 18/18 28 18. A method of producing an alloy comprising at least one thermotropic LCP, wherein the LCP comprises wholly or partially aromatic polyesters and copolyesters and blends thereof, PET, and at least one compatibilizer comprising a copolyester elastomer, wherein the method comprises melt blending the LCP, PET and compatibilizer to form an alloy. 19. A method in accordance with claim 18, 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. 20. A method of producing an alloy comprising at least one thermotropic LCP, PET and a first and second S" compatibilizer, 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. S S a S* 21. An article of manufacture comprising an alloy according to claim 1 or 24. S. S" 22. An article of manufacture according to claim 21, wherein the article comprises a film, a sheet, a tube, or a *container. w 23. An article of manufacture according to claim 21, wherein the article is provided with a coating comprising glass, metal or polymer. -03/06 '99 THU 12:36 [TX/RX NO 8054] Z010 Fax sent bq 61392438333 GRIFFITH HACH MELB 83/86/99 12:35 Pq: 11/18 29 24- An alloy comprising at least one thermotropic LCP, PET and at least one compatibilizer, wherein the compatibilizer is an ethylene-unsaturated ester copolymer. An alloy in accordance with claim 24, wherein the ethylene-unsaturated ester copolymer is an ethylene-methyl acrylate copolymer, 26. An alloy in accordance with claim 24, wherein the ethylene-methyl acrylate copolymer is SP 2205'. 4 9 94 a 9 Se *e 4 4. 9 4 4 9* Dated this 3rd day of June 1999 FOSTER-MILLER. INC. 9* *9 9 4*,e By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia 9 H:\Simeona\Keep\295B3 95.dac 3/06/.9 03/06 '99 THU 12:36 [TX/RX NO 8054] [011