[go: up one dir, main page]

WO1996000752A1 - Melanges de polymeres a cristaux liquides compatibilises - Google Patents

Melanges de polymeres a cristaux liquides compatibilises Download PDF

Info

Publication number
WO1996000752A1
WO1996000752A1 PCT/US1995/008358 US9508358W WO9600752A1 WO 1996000752 A1 WO1996000752 A1 WO 1996000752A1 US 9508358 W US9508358 W US 9508358W WO 9600752 A1 WO9600752 A1 WO 9600752A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
alloy
lcp
accordance
maleic anhydride
Prior art date
Application number
PCT/US1995/008358
Other languages
English (en)
Inventor
Laszlo J. Bonis
Peter S. Schuler
Ashok M. Adur
Original Assignee
Foster-Miller, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foster-Miller, Inc. filed Critical Foster-Miller, Inc.
Priority to NZ289669A priority Critical patent/NZ289669A/en
Priority to EP95925455A priority patent/EP0767815A4/fr
Priority to AU29583/95A priority patent/AU708261B2/en
Priority to JP8503478A priority patent/JPH10502398A/ja
Publication of WO1996000752A1 publication Critical patent/WO1996000752A1/fr

Links

Classifications

    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O

Definitions

  • the present invention provides alloys comprising thermotropic liquid crystalline polymers (LCPs) and polyethylene terephthate (PET) and at least one compatibilizer.
  • LCPs thermotropic liquid crystalline polymers
  • PET polyethylene terephthate
  • 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 existing polymers is a cost effective way to produce new high performance plastics which meet these criteria.
  • thermoplastic flexible polymers which have been blended with TLCPs include polyimides, polyamides, poly(ethersulfone) (PES), poly(etherimide) (PEI), polyetherketone (PEEK), polycarbonate (PC), poly(ethylene terphthlate) (PET), poly (ethylene naphthalate), polyphenylene sulfide (PPS), and polyarylate.
  • thermotropic LCPs are a relatively new class of high performance polymeric 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 process without specialized equipment and very costly as compared with conventional polymers when used alone.
  • 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 thermoplastic polymers reduces costs, because less of the very costly LCP is 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 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.
  • thermotropic LCP melt viscosity of PET.
  • LCP 10% loading
  • thermotropic LCPs in blends to provide "reinforcement," especially where the LCP has a very rigid structure
  • XYDAR ® Poly(oxybenzoyl-co-bisphenyl terephthalate), Amoco, and NECTRA ® Poly(oxybenzoyl-co-oxynaphthoyl), Hoechst-Celanese
  • XYDAR ® Poly(oxybenzoyl-co-bisphenyl terephthalate), Amoco, and NECTRA ® Poly(oxybenzoyl-co-oxynaphthoyl), Hoechst-Celanese
  • Crevecoeur, G. and Groeninckx, G., Polymer Eng. Science, 3_ ⁇ , 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 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.
  • 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 inter- penetration; hydrogen bonding; or associative.
  • 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.
  • polymers having nucleophilic functional groups are interacted with compatibilizers containing hydrogen to form hydrogen bonding.
  • Ionomers have also served as compatibilizers.
  • 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, i.e., 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.
  • the present invention provides alloys comprising a thermotropic LCP, PET, and at least one compatibilizer.
  • two compatibilizers are present.
  • Preferred compatibilizers include copolyester elastomers; ethylene- unsaturated ester copolymers, such as ethylene-maleic anhydride copolymers; copolymers of 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-methyl acrylate copolymers; copolymers of ethylene and a carboxylic acid or acid derivative, such as ethylene-methyl acrylate-maleic anhydride terpolymers; terpolymers of ethylene, unsaturated ester and a carboxylic acid or acid derivative, such as ethylene-methyl-methacrylic acid terpolymers; and acrylic elastomers, such as acrylic rubbers.
  • a particularly preferred copolyester elastomer is HYTRELTM HTR-6108; ethylene-maleic anhydride copolymer is PolybondTM3009; ethylene-methyl acrylate copolymer is SP 2205TM; ethylene-methyl acrylate copolymer grafted with maleic anhydride is DS 1328/60TM; ethylene-methyl acrylate-maleic anhydride terpolymer is LotaderTM 2400; ethylene-methyl-methacrylic acid terpolymer is EscorTM ATX-320, EscorTM ATX-325 or EscorTM XV-11.04; and acrylic rubber is VamacTM Gl.
  • thermotropic LCPs include wholly or partially aromatic polyesters or copolyesters.
  • a particularly preferred copolyester is XYDARTM or VECTRATM.
  • Other preferred thermotropic liquid crystal polymers include SUMIKOSUPER ® and EKONOLTM (Sumitomo Chemical), DuPont HXTM and DuPont ZENTTETM (E.I. duPont de Nemours), RODRUN ® (Unitika) and GRANLARTM (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 preferred LCPs have a melt temperature in the range of 250 to 280°C.
  • One preferred alloy in accordance with the present invention comprises PET, a wholly aromatic LCP copolyester and an ethylene-methyl acrylate-acrylic acid terpolymer compatibilizer, for example, EscorTM ATX- 320, EscorTM ATX-325, or EscorTM XN-11.04.
  • Another preferred alloy comprises PET, a wholly aromatic LCP copolyester and an ethylene-maleic anhydride copolymer compatibilizer such as PolybondTM 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 DSTM 1328/60, or a copolyester elastomer such as HYTRELTM 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 ethylene- methyl acrylate-acrylic acid terpolymers include EscorTM ATX-320, EscorTM ATX-325, or EscorTM XN-11.04 and an exemplary ethylene-maleic anhydride copolymer is PolybondTM 3009.
  • 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 2205TM and an exemplary ethylene- maleic anhydride copolymer is PolybondTM 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 copolymer compatibilizer.
  • Yet another preferred alloy comprises PET, wholly aromatic LCP copolyester, and copolyester elastomer such as HYTRELTM HTR 6108 and an ethylene-maleic anhydride copolymer such as PolybondTM 3009.
  • the ethylene-methyl acrylate copolymer grafted with maleic anhydride, DSTM 1328/60, and the ethylene-maleic anhydride copolymer, PolybondTM 3009 are particularly preferred when the LCP is NECTRATM.
  • LCP is NECTRATM
  • compatibilizer PolybondTM 3009 and a second compatibilizer, EscorTM ATX-320, EscorTM ATX-325, DS1328/60TM, EscorTM XN-11.04, or HYTRELTM6108.
  • 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.
  • 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.
  • the LCPs are used as the disperse phase, whereas PET is used as the predominant or bulk phase.
  • 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.
  • 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
  • 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.
  • 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 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 ordinary skill in the art. Suitable PET is also available commercially from a number of vendors, including KODARTM A150, KODARTM 9921, and Eastman 13339 from Eastman Chemical and CPETTM from Goodyear. KODARTM A 150 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.
  • thermotropic LCPs for use in the present invention include wholly aromatic co-polyester.
  • NectraTM 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-oxybenzoyl moieties, as described in example 4 of U.S. Patent No. 4,468,364 and in G. W.
  • thermotropic LCPs include wholly or partially aromatic polyesters or copolyesters.
  • a particularly preferred copolyester is XYDARTM or VECTRATM.
  • Other preferred thermotropic liquid crystal polymers include SUMIKOSUPER ® and EKONOLTM (Sumitomo Chemical), DuPont HXTM and DuPont ZENTTETM (E.I. duPont de Nemours), RODRUN ® (Unitika) and GRANLARTM (Grandmont).
  • 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, 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 present in a common phase.
  • the functional groups of the compatibilizer, LCP, and PET for use in the alloys are also chemically compatible.
  • 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
  • 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.
  • 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.
  • 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 NECTRATM and XYDARTM: i. Copolyester elastomers such as HYTRELTM
  • Ethylene-maleic anhydride copolymers (HDPE grafted with maleic anhydride), such as PolybondTM 3009 from BP Chemicals; iii. Ethylene-methyl acrylate copolymers, such as 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 LotaderTM 2400 from
  • ethylene-methyl acrylate-acrylic acid terpolymers such as EscorTM ATX-320, EscorTM
  • the alloys of the present invention can be extruded to form various 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.
  • articles of manufacture comprising 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.
  • 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/100in. 2 expected for PET.
  • Films extruded from alloys comprising PET, a wholly aromatic copolyester LCP and a copolyester elastomer such as HYTRELTM 6108 had excellent barrier properties.
  • films extruded from alloys comprising PET, a copolyester elastomer, such as HYTRELTM 6108, a wholly aromatic copolyester, and ethylene-maleic anhydride copolymer, such as PolybondTM 3009 had excellent oxygen barrier properties, e.g., from about 21 to 23 cc/100in 2 .
  • additives 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.
  • additives includes fillers and pigments, lubricants, mold release agents, plaster sizers, ultraviolet stabilizers and so forth.
  • compatibilizers are used either alone or in various combinations with LCP and PET to achieve the desired results. They are also used in single step and sequential compatibilization methods as described below.
  • 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.
  • 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 solely of PET or of LCP and PET.
  • the meld blend is extruded, e.g., through a slot die, a circular, counter-rotating die, or a circular rotating trimodal die.
  • 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.
  • Chevron DS 1328/60 an anhydride-grafted ethylene-methyl acrylate copolymer
  • PolybondTM 3009 an ethylene-maleic anhydride copolymer
  • NECTRATM A950 were added to the mixture and further melt blended to produce alloys which were extruded to produce films having greatly improved mechanical properties.
  • 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% PolybondTM 3009 with the LCP NECTRATM A950 into the vent feed port.
  • EscorTM ATX-325 an ethylene- methyl-methacrylic acid terpolymer
  • PolybondTM 3009 and VectraTM 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 ATXTM 320 in the hopper with the PET, and then feeding 2% PolybondTM 3009 with the LCP NECTRATM A950 into the vent feed port.
  • 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 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.
  • the alloy components are appropriately conditioned, e.g., dried and then fed to the extruder using conventional methodologies.
  • 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.
  • the dry components can be blended in a hopper and extruded, e.g., 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 10% 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.
  • alloy components should be appropriately treated, e.g., dried, before processing as would be readily apparent to the skilled artisan.
  • the LCP used was VectraTM A-950 from Hoechst-Celanese Corporation. PET purchased from Eastman Chemicals under the tradename KODARTM A 150 was used in the following work.
  • the compatibilizers used included: HytrelTM HTR-6108 from DuPont (Copolyester elastomer); PolybondTM 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); LotaderTM 2400 from Atochem (ethylene-methyl acrylate- maleic anhydride terpolymer); EscorTM ATX-320 from Exxon Chemicals (ethylene-methyl acrylate acrylic acid terpolymer); EscorTM ATX-325 from Exxon Chemicals (ethylene-methyl acrylate-acrylic acid terpolymer); EscorTM XN-11.04 from Exxon
  • compatibilizers listed are identified as follows: HYTRELTM HTR-6108 as Hytrel 6108; PolybondTM 3009 as “BP3009”; SP 2205TM as “SP2205”; DS 1328/60 as “Chev DS”; LotaderTM 2400 as “Lotader 2400”; EscorTM ATX- 320, ATX-325 and XV11.04 as “ATX320", “ATX325" and “XV11.04" respectively.
  • LCP, PET and at least one compatibilizer are mixed and melt blended to form an alloy
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • PET & LCP are mixed and melt blended and two compatibilizers are added to the melt blended and further melt blended.
  • PET, LCP and two compatibilizers are mixed and simultaneously melt blended in an extruder and extruded through a slot die.
  • PET, LCP and two compatibilizers are mixed and simultaneously melt blended and extruded through a circular, counter-rotating die.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne des alliages comprenant au moins un polymère à cristaux liquides thermotrope, du polyéthylène-téréphthalate et au moins un compatibilisant, ainsi que des procédés de production de tels alliages.
PCT/US1995/008358 1994-06-28 1995-06-28 Melanges de polymeres a cristaux liquides compatibilises WO1996000752A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
NZ289669A NZ289669A (en) 1994-06-28 1995-06-28 Alloy containing thermotropic liquid crystalline polymer, polyethylene terephthate and a compatibilizer
EP95925455A EP0767815A4 (fr) 1994-06-28 1995-06-28 Melanges de polymeres a cristaux liquides compatibilises
AU29583/95A AU708261B2 (en) 1994-06-28 1995-06-28 Compatibilized LCP blends
JP8503478A JPH10502398A (ja) 1994-06-28 1995-06-28 相溶化ｌｃｐブレンド

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US26760394A 1994-06-28 1994-06-28
US08/267,603 1994-06-28

Publications (1)

Publication Number Publication Date
WO1996000752A1 true WO1996000752A1 (fr) 1996-01-11

Family

ID=23019476

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/008358 WO1996000752A1 (fr) 1994-06-28 1995-06-28 Melanges de polymeres a cristaux liquides compatibilises

Country Status (6)

Country Link
EP (1) EP0767815A4 (fr)
JP (1) JPH10502398A (fr)
AU (1) AU708261B2 (fr)
CA (1) CA2194171A1 (fr)
NZ (1) NZ289669A (fr)
WO (1) WO1996000752A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999012585A3 (fr) * 1997-09-10 1999-05-27 Scimed Life Systems Inc Ballonnet de dilatation de catheter fabrique dans un homopolymere ou copolymere aleatoire a base de pen
WO1999012586A3 (fr) * 1997-09-10 1999-06-03 Scimed Life Systems Inc Ballonnets obtenus au moyen de melanges de polymeres cristallins liquides
US6013373A (en) * 1997-10-20 2000-01-11 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymer and polypropylene
US6015524A (en) * 1997-10-20 2000-01-18 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymers and polyethylene
US6042902A (en) * 1997-10-20 2000-03-28 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymers and poly(ethylene terephthalate) or polycarbonate
US6284333B1 (en) 1997-09-10 2001-09-04 Scimed Life Systems, Inc. Medical devices made from polymer blends containing low melting temperature liquid crystal polymers
US6312772B1 (en) 1997-10-20 2001-11-06 Hoechst Celanese Corporation Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-polyester thermoplastic polymer
EP1176102A2 (fr) 2000-07-25 2002-01-30 Ticona LLC Disque d'étanchéité asymétrique ayant une haute imperméabilité aux gaz ainsi qu'une fermeture
US6426128B1 (en) 1998-01-06 2002-07-30 Hna Holdings, Inc. Co-processable multi-layer laminates for forming high strength, haze-free, transparent articles and methods of producing same
US6660182B2 (en) 2000-09-01 2003-12-09 Ticona Llc Blends of stretchable liquid crystal polymers with thermoplastics
US6730377B2 (en) 2002-01-23 2004-05-04 Scimed Life Systems, Inc. Balloons made from liquid crystal polymer blends
WO2004104100A1 (fr) * 2003-05-15 2004-12-02 E.I. Dupont De Nemours And Company Compositions de polyester a cristallisation rapide
WO2004104099A3 (fr) * 2003-05-15 2005-04-28 Du Pont Composition de polyester
WO2005040257A1 (fr) * 2003-10-21 2005-05-06 E.I. Dupont De Nemours And Company Films, rubans, fibres et textiles non tisses en polyester orientes modifies par copolymeres ethyleniques
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
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
CN103980673A (zh) * 2014-04-09 2014-08-13 昆山狼盟精密电子有限公司 抗氧化耐腐蚀汽车连接器绝缘体及其制备方法
JP2017522442A (ja) * 2014-07-14 2017-08-10 ヴァーテラス ホールディングス エルエルシー オレフィン−無水マレイン酸コポリマーを用いたエンジニアリングプラスチックの改質

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1117122C (zh) * 1998-05-18 2003-08-06 四川联合大学 聚乙烯/聚对苯二甲酸乙二醇酯合金型单层阻隔包装材料
JP2002080730A (ja) * 2000-07-03 2002-03-19 Daicel Chem Ind Ltd 熱可塑性樹脂組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4845169A (en) * 1986-12-12 1989-07-04 General Motors Corporation High impact polyethylene terephthalate polyblends
EP0369734A2 (fr) * 1988-11-14 1990-05-23 Amoco Corporation Propriétés thermiques d'un polytéréphtalate d'alkylène sans perte significative des propriétés physiques à basse température
WO1993024574A1 (fr) * 1992-05-29 1993-12-09 Neste Oy Melanges polymeres a cristaux liquides, leur procede de preparation et produits fabriques a partir desdits melanges

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3106616B2 (ja) * 1991-11-18 2000-11-06 東レ株式会社 高衝撃ポリエステル組成物
JP3111598B2 (ja) * 1992-02-28 2000-11-27 東レ株式会社 熱可塑性樹脂組成物
EP0566149B1 (fr) * 1992-04-17 2004-11-17 Mazda Motor Corporation Composition composite de moulage et procédé de préparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4845169A (en) * 1986-12-12 1989-07-04 General Motors Corporation High impact polyethylene terephthalate polyblends
EP0369734A2 (fr) * 1988-11-14 1990-05-23 Amoco Corporation Propriétés thermiques d'un polytéréphtalate d'alkylène sans perte significative des propriétés physiques à basse température
WO1993024574A1 (fr) * 1992-05-29 1993-12-09 Neste Oy Melanges polymeres a cristaux liquides, leur procede de preparation et produits fabriques a partir desdits melanges

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0767815A4 *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6358227B1 (en) 1997-09-10 2002-03-19 Scimed Life Systems, Inc. Dilatation catheter balloon made from pen based homopolymer or random copolymer
US6866649B2 (en) 1997-09-10 2005-03-15 Boston Scientific Scimed, Inc. Dilation catheter balloon made from pen based homopolymer or random copolymer
WO1999012585A3 (fr) * 1997-09-10 1999-05-27 Scimed Life Systems Inc Ballonnet de dilatation de catheter fabrique dans un homopolymere ou copolymere aleatoire a base de pen
US6585688B2 (en) 1997-09-10 2003-07-01 Scimed Life Systems, Inc. Dilatation catheter balloon made from PEN based homopolymer or random copolymer
US6284333B1 (en) 1997-09-10 2001-09-04 Scimed Life Systems, 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
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
US7026026B2 (en) 1997-09-10 2006-04-11 Boston Scientific Scimed, Inc. Balloons made from liquid crystal polymer blends
WO1999012586A3 (fr) * 1997-09-10 1999-06-03 Scimed Life Systems Inc Ballonnets obtenus au moyen de melanges de polymeres cristallins liquides
US6042902A (en) * 1997-10-20 2000-03-28 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymers and poly(ethylene terephthalate) or polycarbonate
US6015524A (en) * 1997-10-20 2000-01-18 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymers and polyethylene
US6312772B1 (en) 1997-10-20 2001-11-06 Hoechst Celanese Corporation Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-polyester thermoplastic polymer
US6013373A (en) * 1997-10-20 2000-01-11 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymer and polypropylene
US6426128B1 (en) 1998-01-06 2002-07-30 Hna Holdings, Inc. Co-processable multi-layer laminates for forming high strength, haze-free, transparent articles and methods of producing same
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
EP1176102A2 (fr) 2000-07-25 2002-01-30 Ticona LLC Disque d'étanchéité asymétrique ayant une haute imperméabilité aux gaz ainsi qu'une fermeture
US6660182B2 (en) 2000-09-01 2003-12-09 Ticona Llc Blends of stretchable liquid crystal polymers with thermoplastics
US6730377B2 (en) 2002-01-23 2004-05-04 Scimed Life Systems, Inc. Balloons made from liquid crystal polymer blends
WO2004104100A1 (fr) * 2003-05-15 2004-12-02 E.I. Dupont De Nemours And Company Compositions de polyester a cristallisation rapide
WO2004104099A3 (fr) * 2003-05-15 2005-04-28 Du Pont Composition de polyester
WO2005040257A1 (fr) * 2003-10-21 2005-05-06 E.I. Dupont De Nemours And Company Films, rubans, fibres et textiles non tisses en polyester orientes modifies par copolymeres ethyleniques
US7943699B2 (en) 2003-10-21 2011-05-17 E. I. Du Pont De Nemours And Company Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles
CN103980673A (zh) * 2014-04-09 2014-08-13 昆山狼盟精密电子有限公司 抗氧化耐腐蚀汽车连接器绝缘体及其制备方法
CN103980673B (zh) * 2014-04-09 2016-06-08 苏州功业肆点零智能科技有限公司 抗氧化耐腐蚀汽车连接器绝缘体及其制备方法
JP2017522442A (ja) * 2014-07-14 2017-08-10 ヴァーテラス ホールディングス エルエルシー オレフィン−無水マレイン酸コポリマーを用いたエンジニアリングプラスチックの改質

Also Published As

Publication number Publication date
EP0767815A1 (fr) 1997-04-16
AU2958395A (en) 1996-01-25
AU708261B2 (en) 1999-07-29
NZ289669A (en) 1999-04-29
CA2194171A1 (fr) 1996-01-11
JPH10502398A (ja) 1998-03-03
EP0767815A4 (fr) 1998-05-13

Similar Documents

Publication Publication Date Title
WO1996000752A1 (fr) Melanges de polymeres a cristaux liquides compatibilises
US5300572A (en) Moldable polyester resin compositions and molded articles formed of the same
US6221962B1 (en) Liquid crystal polymer blends, process for the preparation thereof and products manufactured from the blends
US5260380A (en) Self-reinforced composite and process for preparing same
CA2162319A1 (fr) Melanges de polymeres comprenant un polymere halogene, compatibilises par un polyester aliphatique greffe
WO1997024403A1 (fr) Melanges de polymeres a cristaux liquides (lcp) rendus compatibles
Baccouch et al. Experimental investigation of the effects of a compatibilizing agent on the properties of a recycled poly (ethylene terephthalate)/polypropylene blend
WO2001070887A1 (fr) Composition de resine thermoplastique
EP0595931B1 (fr) Melanges de polymeres
EP0796296B1 (fr) Melanges d'ether de polyphenylene et leur procede de production
US20030153684A1 (en) Polyester composition
US5281668A (en) Thermoplastic resin composition
JP4624499B2 (ja) 耐衝撃性ポリエステルの射出成形品
JPS6332098B2 (fr)
EP0448749B1 (fr) Mélanges thermoplastiques contenant un terpolymère de l'éthylène et son procédé de préparation
US20030105231A1 (en) Polyester composition
JP2000502737A (ja) 相溶化されたｌｃｐブレンド
JPH05105784A (ja) 熱可塑性樹脂組成物
JP2003238786A (ja) ポリエステル樹脂組成物及び該組成物から得られるフィルム
US5086113A (en) Thermoplastic blends of ABS containing ethylene terpolymers
JP3588384B2 (ja) ポリエステル樹脂の製造方法
JPH0570636A (ja) 熱可塑性樹脂組成物
JPH09143358A (ja) ポリカーボネート系樹脂組成物
JPH05202233A (ja) 熱可塑性樹脂組成物
Utracki Reasons for, benefits and problems of blending

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA FI JP KR MX NO NZ

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2194171

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 289669

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: 1995925455

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1995925455

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1995925455

Country of ref document: EP