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WO1999019402A1 - Polymeres a cristaux liquides thermotropiques utilises comme stabilisants dans les polyesters thermoplastiques - Google Patents

Polymeres a cristaux liquides thermotropiques utilises comme stabilisants dans les polyesters thermoplastiques Download PDF

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Publication number
WO1999019402A1
WO1999019402A1 PCT/US1998/020284 US9820284W WO9919402A1 WO 1999019402 A1 WO1999019402 A1 WO 1999019402A1 US 9820284 W US9820284 W US 9820284W WO 9919402 A1 WO9919402 A1 WO 9919402A1
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Prior art keywords
polymer
composition
poly
tlcp
polyester
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PCT/US1998/020284
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English (en)
Inventor
Bruce Edwin Wilson
Clinton Cherry
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Eastman Chemical Co
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Eastman Chemical Co
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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

Definitions

  • This invention relates generally to polyester resins, to the use of thermotropic liquid crystalline polymers to improve the properties of such resins, and to polyester resins containing such thermoplastic liquid crystalline polymers.
  • the resins are processed in a manner that subjects the resins to potentially damaging mechanical shear and/or heat.
  • Process steps that cause such shear and heat include, for example, extrusion, compounding and molding.
  • the molecular weight of a polyester is often reduced. It is generally desirable to minimize the molecular weight loss during these processing operations, however, in order to provide optimum mechanical properties in the final articles. Narious techniques are known in the art for minimizing this molecular weight loss, although none has yet been totally satisfactory.
  • This invention concerns the use of thermotropic liquid crystalline polymers ("TLCPs”) to minimize the reduction of molecular weight in polyesters during processing.
  • TLCPs thermotropic liquid crystalline polymers
  • the use of TLCPs to reduce the viscosity of polyesters is known in the art, as described in Cogswell et al. in U.S. Patents 4,433,083 and 4,386,174, and by La Mantia in Thermotropic Liquid Crystal Polymer Blends. Technomic Publishing Co. (1993).
  • the rheology of polyester/TLCP blends is complex, with numerous examples of significant negative deviations from linear mixing rules. As reported by Cogswell, for example, blends of miscible polyesters and TLCP can have viscosities substantially lower than either component individually.
  • TLCPs that comprise aromatic hydroxyl residues are added to polyesters before the polyesters are processed in order to minimize the molecular weight loss that occurs during the processing.
  • a TLCP and polyester are chosen that are at least partly immiscible.
  • the addition of TLCP to the polyester before processing minimizes the amount of polyester molecular weight loss during processing, when compared to the polyester molecular weight loss that occurs when the polyester is processed without TLCP.
  • the addition of TLCP even increases the viscosity of the polyester, in further contrast to the teachings of Cogswell et al.
  • this invention in one aspect, relates to a composition
  • a composition comprising at least 50 parts by weight of a first polymer, the first polymer being a thermoplastic polyester; and less than or equal to 50 parts by weight of a second polymer that is a TLCP; wherein: the second polymer comprises at least one monomeric aromatic hydroxyl residue; the first polymer and the second polymer have an overlapping melt processing temperature range; the first polymer and the second polymer are immiscible or partly immiscible when mixed within the overlapping temperature range; and the first polymer and the second polymer are provided in such quantities that the molecular weight of the first polymer in the composition after shear or heat processing is greater than the molecular weight of the first polymer alone after shear or heat processing.
  • the invention in another aspect relates to a composition
  • a composition comprising at least
  • the first polymer being a thermoplastic polyester; and less than or equal to 50 parts by weight of a second polymer that is a TLCP; wherein: the second polymer comprises at least one monomeric aromatic hydroxyl residue; the first polymer and the second polymer have an overlapping melt processing temperature range; the first polymer and the second polymer are present in a weight ratio of at least 10:1 ; and the first polymer and the second polymer are provided in such quantities that the molecular weight of the first polymer in the composition after shear or heat processing is greater than the molecular weight of the first polymer alone after shear or heat processing.
  • the invention in another aspect relates to a method for lessening the shear or heat induced reduction in molecular weight of a thermoplastic polyester, comprising: admixing at least 50 parts by weight of a first polymer with less than or equal to 50 parts by weight of a second polymer, the first polymer being a thermoplastic polyester, and the second polymer being a TLCP, to obtain a polyester/TLCP mixture, and subjecting the polyester/TLCP mixture to heat or shear, wherein the second polymer comprises at least one monomeric aromatic hydroxyl residue; the first polymer and the second polymer have an overlapping melt processing temperature range; the first polymer and the second polymer are immiscible or partly immiscible when mixed within the overlapping temperature range; and the first polymer and the second polymer are provided in such quantities that the molecular weight of the first polymer in the composition after shear or heat processing is greater than the molecular weight of the first polymer alone after shear or heat processing.
  • the invention in another aspect relates to a method for lessening the shear or heat induced reduction in molecular weight of a thermoplastic polyester, comprising: admixing at least 50 parts by weight of a first polymer with less than or equal to 50 parts by weight of a second polymer, the first polymer being a thermoplastic polyester, and the second polymer being a TLCP, to obtain a polyester TLCP mixture, and subjecting the polyester/TLCP mixture to at least 1500 s "1 units of shear, wherein: the second polymer comprises at least one monomeric aromatic hydroxyl residue; the first polymer and the second polymer have an overlapping melt processing temperature range; and the first polymer and the second polymer are provided in such quantities that the molecular weight of the first polymer in the composition after shear or heat processing is greater than the molecular weight of the first polymer alone after shear or heat processing.
  • X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
  • a residue of a chemical species refers to the moiety that is the reaction product of the chemical species in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether the moiety is actually obtained from the chemical species.
  • an ethylene glycol residue in a polyester refers to one or more -OCH 2 CH 2 O- units in the polyester, regardless of whether ethylene glycol was used to prepare the polyester.
  • a sebacic acid residue in a polyester refers to one or more - CO(CH 2 ) g CO- moieties in the polyester, regardless of whether the residue is obtained by reacting sebacic acid or an ester thereof to obtain the polyester.
  • Ranges are often expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that a more preferred range is typically from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value is typically more preferred.
  • an effective amount of a compound as provided herein is meant such amount as is capable of performing the function of the compound for which an effective amount is expressed.
  • the exact amount required will vary from process to process, depending on a host of recognizable variables such as the compounds employed and the processing conditions observed. Thus, it is not possible to specify an exact "effective amount.” However, an appropriate effective amount may be determined by one of ordinary skill in the art using only routine experimentation.
  • polymer and “resin” are used interchangeably herein, and each term is meant to include any of various substances made by chemical synthesis, especially those used in the making of plastics, any compound formed by polyemerization, and any of two or more polymeric compounds.
  • modified is often used herein to describe polymers and means that a particular monomeric unit that would typically make up the pure polymer has been replaced by another monomeric unit that shares a common polymerization capacity with the replaced monomeric unit. Thus, for example, it is possible to substitute diol residues for glycol in poly(ethylene glycol), in which case the poly(ethylene glycol) will be "modified” with the diol.
  • the poly(ethylene glycol) is modified with a mole percentage of the diol, then such a mole percentage is based upon the total number of moles of glycol that would be present in the pure polymer but for the modification.
  • the diol and glycol residues are present in equimolar amounts.
  • TLCP is the abbreviated term for "thermotropic liquid crystalline polymer", as distinct from lytropic liquid crystalline polymer.
  • Liquid crystalline polymers are well known in the art and are characterized by being capable of maintaining a high degree of intermolecular order in a liquid state, even in the absence of anisotropic shear forces, and by exhibiting a behavior pattern characteristic of a crystalline liquid.
  • Thermotropic LCP's such as Vectra, give rise to this ordered system in the molten state, while lyotropic LCP's such as Kevlar, give rise to this ordered system in solution.
  • TLCP nematic, smectic, or cholesteric
  • TLCP's are reviewed, for example, in F.P. LaMantia, Thermotropic Liquid Crystalline Blends. Technomic Publishing Co. (1993). The disclosure of this publication is hereby incorporated by reference as if fully set forth herein.
  • PET-HB is the abbreviated term for poly(ethylene terephthalate-co-p- hydroxybenzoate), meaning a copolymer of p-hydroxybenzoyl and oxyethyleneoxyterephthaloyl residues. Such polymers may be prepared by modifying poly (ethylene terephthalate) to contain the p-hydroxybenzoate residues.
  • melt processing range refers to the temperature range between which the polymer begins to flow and where the thermal degradation results in unacceptable loss of properties.
  • copolyesters includes copolyesters.
  • inherent viscosity of TLCPs is measured at 25 C using 0.5 wt.% polymer in pentafluorophenol.
  • the inherent viscosity of polyesters is measured using 0.5 wt.% polyester in 60/40 phenol/tetrachloroethane at 25 C.
  • the invention relates to a composition
  • a composition comprising at least 50 parts by weight of a first polymer, the first polymer being a thermoplastic polyester; and less than or equal to 50 parts by weight of a second polymer that is a TLCP; wherein: the second polymer comprises at least one monomeric aromatic hydroxyl residue; the first polymer and the second polymer have an overlapping melt processing temperature range; the first polymer and the second polymer are immiscible or partly immiscible when mixed within the overlapping temperature range; and the first polymer and the second polymer are provided in such quantities that the molecular weight of the first polymer in the composition after shear or heat processing is greater than the molecular weight of the first polymer alone after shear or heat processing.
  • the composition is preferably in the form of an inhomogeneous solid phase blend.
  • the polyester and TLCP are chosen in amounts so that the viscosity of the polyester without the TLCP is less than the viscosity of a composition containing both the polyester and the TLCP.
  • the melt viscosity of the polyester/TLCP mixture measured at 1000 s "1 or higher, is 5% or more higher than the melt viscosity of the first polymer.
  • the invention in another aspect relates to a composition
  • a composition comprising at least
  • the first polymer being a thermoplastic polyester; and less than or equal to 50 parts by weight of a second polymer that is a TLCP; wherein: the second polymer comprises at least one monomeric aromatic hydroxyl residue; the first polymer and the second polymer have an overlapping melt processing temperature range; the first polymer and the second polymer are present in a weight ratio of at least 10:1 ; and the first polymer and the second polymer are provided in such quantities that the molecular weight of the first polymer in the composition after shear or heat processing is greater than the molecular weight of the first polymer alone after shear or heat processing.
  • the invention provides a method for lessening the shear or heat induced reduction in molecular weight of a thermoplastic polyester, comprising: admixing at least 50 parts by weight of a first polymer with less than or equal to 50 parts by weight of a second polymer, the first polymer being a thermoplastic polyester, and the second polymer being a TLCP, to obtain a polyester/TLCP mixture, and subjecting the polyester/TLCP mixture to heat or shear, wherein the second polymer comprises at least one monomeric aromatic hydroxyl residue; the first polymer and the second polymer have an overlapping melt processing temperature range; the first polymer and the second polymer are immiscible or partly immiscible when mixed within the overlapping temperature range; and the first polymer and the second polymer are provided in such quantities that the molecular weight of the first polymer in the composition after shear or heat processing is greater than the molecular weight of the first polymer alone after shear or heat processing.
  • the invention in still another aspect relates to a method for lessening the shear or heat induced reduction in molecular weight of a thermoplastic polyester, comprising: admixing at least 50 parts by weight of a first polymer with less than or equal to 50 parts by weight of a second polymer, the first polymer being a thermoplastic polyester, and the second polymer being a TLCP, to obtain a polyester/TLCP mixture, and subjecting the polyester/TLCP mixture to at least 1500 s "1 units of shear, wherein: the second polymer comprises at least one monomeric aromatic hydroxyl residue; the first polymer and the second polymer have an overlapping melt processing temperature range; and the first polymer and the second polymer are provided in such quantities that the molecular weight of the first polymer in the composition after shear or heat processing is greater than the molecular weight of the first polymer alone after shear or heat processing. Because the process lessens the reduction in polyester molecular weight, compositions obtained by the process often have improved physical properties such as modulus and elong
  • the invention is particularly suitable for application to extrusion processes, wherein the shear induced reduction in molecular weight is applied by extrusion.
  • the process has further particular application to processes in which the composition is subjected to over about 250 s "1 units of shear.
  • the invention may preferably be employed in processes in which the composition is subjected to over about 1000 s '1 units of shear, even more preferably to processes in which the composition is subjected to over about 1500 s "1 units of shear, and still even more preferably to processes in which the composition is subjected to over about 2500 s "1 units of shear.
  • a preferred range in which to practice the invention is from about 500 to about 25,000 s "1 units of shear, and an even more preferred range is from about 3,000 to about 9,000 s "1 units of shear and a still even further preferred range is from about 4,000 to about 10,000 s "1 units of shear.
  • a particular advantage from the process of the present invention is the reduction in shear-induced damage to molecular weight of the polyesters in thermoplastic polymers.
  • the molecular weight loss of the polyester is preferably reduced on average by 5% or more, when compared to polyesters processed conventionally, and even more preferably, the loss in molecular weight is reduced on average by 10% or more, when measured by GPC.
  • the first and second polymers preferably should be chosen so that they are immiscible or partly immiscible in an effective amount to reduce the shear induced reduction in molecular weight that otherwise would occur during processing of the first polymer in the absence of the TLCP.
  • the polymers are compatible, and may be used in the compositions of the present invention, if they evidence any effective amount of immiscibility.
  • the miscibility and potential compatibility of polymers is discussed in M.M. Coleman et al., Specific Interactions and the Miscibility of Polymers. Technomic Publishing, Lancaster, Pennsylvania, Chapter 2 (1991), the disclosure of which is hereby incorporated by reference as if fully set forth herein.
  • the effective amount of miscibility of the polymers can, in many instances, be expressed numerically by measuring or identifying the difference between the solubility parameters for the polymers.
  • Polymers that have solubility parameters that differ by about 0.3 (J/cm 3 ) 05 and greater are generally immiscible, and are particularly suitable for practicing the present invention.
  • the difference in solubility parameters of the first polymer and second polymer is greater than about 0.5 (J/cm 3 ) 05 , in another embodiment the difference in solubility parameters of the first polymer and second polymer is greater than about 0.7 (J/cm 3 ) 05 , in yet another embodiment the difference in solubility parameters of the first polymer and second polymer is greater than about 1.0 (J/cm 3 ) 0 5 , in still another embodiment the difference in solubility parameters of the first polymer and second polymer is greater than about 1.3 (J/cm 3 ) 05 , and in a still even further embodiment the difference in solubility parameters of the first polymer and second polymer is greater than about 1.6 (J/cm 3 ) 0 5 .
  • the composition of the present invention may comprise the first and second polymers at any ratio, although it is generally preferred that the first and second polymers be present in the composition in effective amounts to reduce the shear induced reduction in molecular weight that otherwise would occur during processing of the first polymer in the absence of the TLCP.
  • the polymers should also be present in an effective amount to prevent brittle failure problems in the final product due to the immiscibility of the polymers.
  • the first and second polymers may preferably be present in effective amounts in which the weight ratio of second polymer to first polymer is less than 1 :10, and greater than 1 :49. Even more preferably, the weight ratio of second polymer to first polymer is from about 1 :14 to about 1 :25, and most preferably the ratio is about 1 :19.
  • compositions comprise from about 20 to about 99.5 percent by weight of the first polymer, and from about 0.1 to about 50 percent by weight of the second polymer. Even more preferred compositions comprise from about 1 to about 20 percent by weight of the second polymer.
  • the first and second polymers be melt processable, and that the melt processing range for each of the first and second polymers overlap.
  • the melt processing ranges overlap by at least 5 C, more preferably the ranges overlap by at least 10 C, more preferably at least 20 C, and most preferably the ranges overlap by from about 20 C to about 30 C.
  • preferred thermoplastics for the first polymer of this invention, and preferred TLCPs for the second polymer each have a melting point from about 200 C to about 400 C, and more preferably from about 250 C to about 350 C.
  • the melting point of a TLCP may be lowered by adding side groups (e.g., replacing hydroquinone with phenylhydroquinone), reducing the aromatic content (e.g., replacing hydroquinone with ethylene glycol), or adding bends into the rigid sections (e.g., replacing hydroquinone with resorcinol). Care should be taken, however, not to substantially modify or replace the aromatic hydroxyl residues of the TLCP, or to affect the properties of the TLCP.
  • side groups e.g., replacing hydroquinone with phenylhydroquinone
  • reducing the aromatic content e.g., replacing hydroquinone with ethylene glycol
  • bends into the rigid sections e.g., replacing hydroquinone with resorcinol
  • the first polymer may preferably be formed from one or more aliphatic, aromatic, or alicyclic dibasic acids containing from about 2 to about 40 carbon atoms, and one or more aliphatic or alicyclic glycols containing from about 2 to about 40 carbon atoms.
  • the first polymer comprises poly(ethylene terephthalate) (PET); poly(tetramethylene terephthalate) (PBT); poly (1,4-cyclohexylenedimethylene terephthalate (PCT); poly(ethylene 2,6-naphthalenedicarboxylate) (PEN); poly(ethlene 1 ,4-cyclohexanedicarboxylate) ( PEC); a PET copolyester containing isophthalic acid residues; a PET copolyester containing 1,4-cyclohexane dimethanol residues; a PEN copolyester containing 1,4- cyclohexane dimethanol residues; a PEN copolyester containing terephthalic acid residues; a PEN copolyester containing 1,4-cyclohexane dimethanol residues; and/or a PET copolyester containing isophthalic acid residues.
  • PET poly(ethylene terephthalate)
  • PBT poly
  • the first polymer may also be advantageously modified with from about 0.1 to about 25 mole % of aliphatic dibasic acids containing from 2 to about 40 carbon atoms.
  • a particularly suitable first polymer comprises PEN formed from 2,6-, 2,7-, 1 ,4-, and or 1 ,5-naphthalenedicarboxylic acid.
  • the first polymer also preferably has an inherent viscosity of from about 0.4 to about 2.0 dl/g.
  • any TLCP which contains an aromatic hydroxyl residue, and which has a melt processing range that overlaps the processing range of the thermoplastic polyester used in the invention is operable.
  • the TLCP can thus be formed from monomers that contain aromatic hydroxyl functionalities, and from monomers that before reacting to form the TLCP are converted to contain an aromatic hydroxyl functionality.
  • Processes for preparing the TLCP are known in the art, and include those discussed by Jackson, et al., in U.S. Patent 4,169,933 (the disclosure of which is hereby incorporated by reference).
  • Particularly suitable TLCPs for the second polymer comprise residues of ethylene glycol, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-6-carboxyl-2-ol, hydroquinone, p-hydroxybenzoic acid, methylhydroquinone, phenylhydroquinone, naphthalene-6-carboxyl-2-amide, p-aminobenzoic acid, and/or isophthalic acid.
  • residues of terephthalic acid, naphthalene-2,6-dicarboxylic acid, hydroquinone, p-hydroxybenzoic acid or mixtures thereof are more preferred.
  • the second polymer is a poly(ethylene terephthalate) copolyester containing from about 50 to about 90 mole percent p-hydroxybenzoic acid residues (PET-HB).
  • PET-HB poly(ethylene terephthalate) copolyester
  • the second polymer is a PET- HB containing from about 60 to about 85 mole percent p-hydroxybenzoic acid residues.
  • the PET-HB copolyester may also be modified by up to 20 mole % with one or more dibasic acids comprising from 2 to 40 carbon atoms.
  • dibasic acids include succinic, glutaric, adipic, sebasic, 1 ,4- cyclohexanedicarboxylic, isophthalic, naphthalenedicarboxylic, trans-stilbene-4,4'- dicarboxylic, and dimer acid.
  • Preferred dibasic acids are terephthalic acid, naphthalene-2,6-dicarboxylic acid, hydroquinone, and p-hydroxybenzoic acid as disclosed by Jackson, et al., in U.S. Patent 4,169,933 (the disclosure of which is hereby incorporated by reference).
  • the PET-HB can similarly be modified with up to 20 mole % of one or more glycols containing from 2 to about 12 carbon atoms.
  • Preferred modifying glycols include propylene glycol, 1,3-propanediol, 1,4- butanediol, 1 ,6-hexanediol, neopentyl glycol, 2,2,4,4-tetramethyl-l,3- cyclobutanediol, and 1,4-cyclohexane dimethanol.
  • the inherent viscosity of the TLCP is a further consideration in the selection of preferred second polymers.
  • a preferred second polymer is PET-HB having an inherent viscosity of from about 0.3 to about 10.0 dl/g.
  • An even more preferred second polymer is PET-HB having an inherent viscosity of from about 0.5 to about 3.5 dl/g.
  • Beneficial results are obtained using either pellet blends or melt blends of the TLCP and of the thermoplastic polyesters.
  • the melt blends may be made in any conventional melt blending apparatus such as single or twin screw extruders, Brabender plastographs, and the like.
  • Beneficial results are also obtained when the TLCP is used as one component in a polymeric formulation.
  • various other polymers are blended with the TLCP prior to blending with the thermoplastic.
  • compositions of this invention may optionally comprise one or more additives which lend to the composition desirable qualities such as, for example, flame retardants, glass fibers, carbon fibers, fibrous reinforcing materials, inert fillers, reinforcing agents, pigments, dyes, colorants, stabilizers, antioxidants, plasticizers, epoxides, nucleators, and processing aids.
  • Preferred fillers and reinforcing agents include glass fibers, glass beads, mica, and polymeric fibers, including preformed or in-situ TLCP fibers or fibrils.
  • the composition comprises from about 20 to about 98.9% by wt. of the first polymer, from about 0.1 to about 50% by wt. of the second polymer, and from about 1 to about 70 wt. % of the one or more additive components.
  • Compositions comprising from about 15 to about 40 wt. % of the one or more additive components are more preferred.
  • compositions of the present invention optionally can be used during the manufacture of various products, and can also be incorporated into final products.
  • the composition can be a raw material that is further processed before a final product is prepared, and the compositions can be present as the final article.
  • the composition can, for example, be incorporated into shaped articles, including extruded shaped articles and molded shaped articles.
  • Particularly suitable products that can be obtained from the present invention include molded parts, film sheeting, and fibers.
  • the compounds and components of the invention may be readily synthesized and prepared using techniques generally known to synthetic organic or polymer chemists. Suitable experimental methods for making and deriving the first and second polymers are described, for example, in the references cited in this document, the disclosures of which being hereby incorporated by this reference for their general teachings and for their synthesis teachings. Methods for making specific and preferred compositions of the present invention are described in detail in examples set forth below.
  • thermotropic liquid crystalline polymer prepared from 1 part chloroterephthalic acid, 3 parts naphthalene-2,6- dicarboxylic acid, 40 parts hydroquinone, and 60 parts p-hydroxybenzoic acid.
  • thermotropic liquid crystalline polymer prepared from 1 part dimethyl tr ⁇ --stilbene- 4,4'-dicarboxylate, 0.9 parts butane- 1 ,4-diol, and 0.1 parts ethylene glycol. This pellet blend was processed under conditions identical to Example 1.

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  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé qui permet d'atténuer la diminution, induite par le cisaillement ou par la chaleur, du poids moléculaire d'un polyester thermoplastique, ainsi que des compositions utilisées dans et obtenues par ledit procédé. Selon ce dernier, on mélange au moins 50 parties en poids d'un premier polymère avec une quantité inférieure ou égale à 50 parties en poids d'un second polymère, le premier polymère étant un polyester thermoplastique et le second un polymère à cristaux liquides thermotropiques (TLCP), de façon à obtenir un mélange polyester/TLCP; puis on soumet ledit mélange à la chaleur ou au cisaillement. Le second polymère renferme au moins un résidu hydroxyle aromatique monomère; le premier et le second polymère ont des plages de température de fusion qui se chevauchent; ils sont immiscibles ou partiellement immiscibles quand ils sont mélangés à une température située à l'intérieur de la partie chevauchante desdites plages de température; et leurs quantités sont telles que le poids moléculaire du premier polymère compris dans la composition, après traitement par la chaleur ou par cisaillement, est supérieur à celui du premier polymère seul après ledit traitement.
PCT/US1998/020284 1997-10-10 1998-09-28 Polymeres a cristaux liquides thermotropiques utilises comme stabilisants dans les polyesters thermoplastiques Ceased WO1999019402A1 (fr)

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US6201697P 1997-10-10 1997-10-10
US60/062,016 1997-10-10
US12165298A 1998-07-23 1998-07-23
US09/121,652 1998-07-23

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Cited By (6)

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CN101891938A (zh) * 2010-07-16 2010-11-24 金发科技股份有限公司 一种非圆形横截面玻璃纤维增强液晶聚合物材料及其制备方法
CN102918116A (zh) * 2010-05-28 2013-02-06 Lg化学株式会社 用于熔融工艺的树脂共混物，树脂粒和使用它们制备树脂制品的方法
US10655002B2 (en) 2010-10-14 2020-05-19 Lg Chem, Ltd. Resin blend for melting process
CN111548612A (zh) * 2020-06-16 2020-08-18 深圳华力兴新材料股份有限公司 一种5g天线振子基材用pct/tlcp树脂组合物及其制备方法和应用
US10964971B2 (en) 2017-12-19 2021-03-30 Samsung Electronics Co., Ltd. Battery casing and battery including the same

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US7169880B2 (en) 2003-12-04 2007-01-30 Eastman Chemical Company Shaped articles from cycloaliphatic polyester compositions
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CN102918116B (zh) * 2010-05-28 2016-04-13 Lg化学株式会社 用于熔融工艺的树脂共混物，树脂粒和使用它们制备树脂制品的方法
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EP2578642A4 (fr) * 2010-05-28 2013-11-27 Lg Chemical Ltd Mélange de résines destiné à être transformé à l'état fondu, pastille et procédé pour la production d'articles en résine moulés les utilisant
EP2578640A4 (fr) * 2010-05-28 2014-01-08 Lg Chemical Ltd Mélange de résines et pastilles destinés à être transformés à l'état fondu et procédé de production pour des articles en résine moulés les utilisant
US9243134B2 (en) 2010-05-28 2016-01-26 Lg Chem, Ltd. Core-shell resin pellet having melt viscosity difference between the core resin and the shell resin
US9296888B2 (en) 2010-05-28 2016-03-29 Lg Chem, Ltd. Resin blend
US10035902B2 (en) 2010-05-28 2018-07-31 Lg Chem, Ltd. Resin blend
CN102918116A (zh) * 2010-05-28 2013-02-06 Lg化学株式会社 用于熔融工艺的树脂共混物，树脂粒和使用它们制备树脂制品的方法
CN101891938A (zh) * 2010-07-16 2010-11-24 金发科技股份有限公司 一种非圆形横截面玻璃纤维增强液晶聚合物材料及其制备方法
US10655002B2 (en) 2010-10-14 2020-05-19 Lg Chem, Ltd. Resin blend for melting process
US10655003B2 (en) 2010-10-14 2020-05-19 Lg Chem, Ltd. Resin blend for melting process
US10964971B2 (en) 2017-12-19 2021-03-30 Samsung Electronics Co., Ltd. Battery casing and battery including the same
CN111548612A (zh) * 2020-06-16 2020-08-18 深圳华力兴新材料股份有限公司 一种5g天线振子基材用pct/tlcp树脂组合物及其制备方法和应用
CN111548612B (zh) * 2020-06-16 2022-12-02 深圳华力兴新材料股份有限公司 一种5g天线振子基材用pct/tlcp树脂组合物及其制备方法和应用

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