Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
  • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
  • Y10T428/31797—Next to addition polymer from unsaturated monomers

Definitions

• This invention relates to stretchable anisotropic melt-forming polymers suitable for use in the production of a variety of shaped articles including films, fibers and blow-molded forms.
• This invention also relates to shaped articles made from such polymers, including multilayer laminates having at least one layer formed from such polymers.
• Anisotropic melt-forming polymers also known as liquid crystalline polymers or "LCPs", are well known in the art. Anisotropic melt-forming polymers exhibit a parallel ordering of molecular chains in the melt phase and are also termed "thermotropic" liquid crystalline polymers. Many of these materials are wholly aromatic in nature.
• Thermotropic polymers include aromatic copolyesters having recurring units derived from p-hydroxybenzoic acid, at least one aromatic diol and at least one aromatic dicarboxylic acid, as well as wholly aromatic copolyesteramides having recurring units derived from p-hydroxybenzoic acid, at least one aromatic diol, at least one aromatic diacid, and aminophenol. Without the inclusion of recurring units that disrupt the crystalline structure, such polymers tend to have very high melting points, for example, 360°C and above, making them difficult to melt fabricate. Incorporation of recurring units that provide non-parallel or "kinky" linkages is a common means of lowering melting point. These kinky linkages include "meta'Or 1,3- aromatic ring structures.
• Common materials from which meta linkages are derived include m- hydroxybenzoic acid, isophthalic acid, resorcinol, and m- aminophenol.
• U.S. Pat. Nos. 4,563,508; 5,037,939; and 5,066,767 disclose polymers containing recurring units derived from p-hydroxybenzoic acid, terephthalic acid, isophthalic acid, hydroquinone and 4,4'-biphenol;
• U.S. Pat. No. 4,912, 193 discloses polymers having recurring units derived from p- hydroxybenzoic acid, 4, 4 '-biphenol, terephthalic acid and isophthalic acid;
• 4,966,956 discloses polymers having recurring units derived from p-hydroxybenzoic acid, terephthalic acid, isophthalic acid, 4,4'- biphenol and aminophenol;
• U.S. Pat. No. 5,663,276 discloses polymers having recurring units derived from p-hydroxybenzoic acid, terephthalic acid, 4,4'-biphenol, isophthalic acid, hydroquinone and 4,4'- biphenyldicarboxylic acid;
• 5,089,594 discloses polymers having recurring units derived from p-hydroxybenzoic acid, terephthalic acid, isophthalic acid, 4,4'-biphenol, and an aromatic diol, for example, hydroquinone;
• U.S. Pat. No. 4,722,993 discloses polymers having recurring units derived from m- aminophenol, p-hydroxybenzoic acid, terephthalic and/or isophthalic acid, one or more of hydroquinone, 4,4'-biphenol or resorcinol and, if desired, m-hydroxybenzoic acid;
• 5,399,656 discloses polymers having recurring units derived from p-hydroxybenzoic acid, terephthalic acid, resorcinol and an aromatic diol, for example, 4,4'- biphenol;
• U.S. Pat. No. 5,025,082 discloses polymers having recurring units derived from p-hydroxybenzoic acid, terephthalic acid, 4,4'-biphenol, 2,6-naphthalene dicarboxylic acid, and at least one aromatic diol selected from hydroquinone, methylhydroquinone, trimethylhydroquinone, resorcinol and tetramethylbiphenol; and U.S. Pat. No.
• 5,798,432 discloses polymers having recurring units derived from p-hydroxybenzoic acid, 2,6- naphthalene dicarboxylic acid, terephthalic acid, isophthalic acid, hydroquinone, p-aminophenol and 4,4'-biphenol.
• aromatic polymers derived from p-hydroxybenzoic acid, at least one aromatic dicarboxylic acid and at least one aromatic diol and/or aminophenol tend to have highly ordered crystalline structures and, although drawable in the melt, generally lack the ability to be stretched to a significant degree at temperatures below the molten state.
• thermotropic polymers have recurring units derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, at least one aromatic diacid and at least one aromatic diol.
• the incorporation of meta linkages into such polymers is described, for example, in the following: U.S. Pat. No. 4,522,974 disclosing polymers having recurring units derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, hydroquinone and isophthalic and/or terephthalic acid; U.S. Pat. No.
• 4,918, 154 disclosing polymers having recurring units derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, terephthalic and/or isophthalic acid, resorcinol and hydroquinone; and U.S. Pat. No. 4,983,713 disclosing polymers having recurring units derived from p-hydroxybenzoic acid, 6- hydroxy-2-naphthoic acid, terephthalic acid, 4,4'-biphenol, and isophthalic acid.
• the polymers set forth in the examples of these patents tend to have ordered crystalline structures and are not considered to be highly stretchable materials.
• U.S. Patent Nos. 6,132,884; 6,207,790; and 6,222,000 disclose highly stretchable amorphous anisotropic melt-forming polymers having recurring units derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, one or more aromatic monomers that provide the resulting polymer with selected meta-linkages, one or more aromatic diacids, and an aromatic diol and/or hydroxyamine, at least a portion of which is biphenol.
• These patents also disclose stretched articles made from such polymers. According to these patents, in order to produce highly stretchable amorphous anisotropic polymers, it is necessary to provide the polymers with specific recurring units in narrowly defined amounts.
• the polymers described by all three of these patents are required to contain both meta- linkages and at least about 5 mole percent of recurring units derived from biphenol.
• LCPs that are stretchable at lower temperatures have a diverse range of end-use applications.
• Amorphous LCPs having a Tg (i.e., onset of the glass transition temperature as measured by differential scanning calorimetry or "DSC") of 150°C or less that are highly stretchable at temperatures above Tg, but below the temperature at which the LCP is in the molten state, are of particular interest in the production of articles that are stretched, drawn or otherwise processed at lower temperatures.
• Liquid crystalline polymers that are stretchable at temperatures below the processing temperatures of conventional film-forming polymers may be particularly desirable for use in the production of multilayer articles having one or more layers of such conventional film-forming polymers, for example, films, laminates, blow-molded containers, and the like.
• the barrier, mechanical and/ or optical properties of liquid crystalline polymers may provide advantages that are typically not obtained from conventional thermoplastics.
• EP0 928 683 A2 published July 14, 1999, discloses a variety of multilayer laminates, including laminates formed from wholly aromatic, liquid crystalline polymers of the type disclosed in U.S. Patent No. 5,656,714.
• highly stretchable anisotropic melt-forming polymers can be derived from p-hydroxybenzoic acid, 6- hydroxy-2-naphthoic acid, terephthalic acid, isophthalic acid, and hydroquinone.
• recurring unit III is:
• the aromatic ring structure of recurring unit V may be substituted in a manner similar to that described for recurring unit I.
• Representative of the precursors from which recurring unit V may be derived are hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, and 2-phenylhydroquinone.
• Recurring unit V is present in the polymers of the subject invention in an amount of from about 10 to about 27.5 mole percent, preferably from about 15 to about 25 mole percent
• recurring unit V may be substituted with linkages derived from 4 -aminophenol, and/ or a portion of recurring unit I may be substituted with linkages derived from 4-aminobenzoic acid.
• linkages derived from 4 -aminophenol When such other units are present, the total amount thereof typically should not exceed about 5 mole percent of the resulting polymer. It will be apparent to those skilled in the art that the total amount of dioxy and oxy-amino units present in the subject polymers will be substantially equal to the total amount of dicarboxy units.
• the various recurring units will be present in the resultant polymers in a random configuration.
• the polymers are wholly aromatic materials.
• the polymers formed by the process of this invention commonly exhibit a weight average molecular weight of from about 10,000 to about 80,000.
• the molecular weight of preference will depend, in part, on the intended end-use application. For example, in fiber and film applications, weight average molecular weights of from about 20,000 to about 40,000 are commonly of interest.
• the polymers typically exhibit an inherent viscosity (IN ), measured at 25°C as a 0.1% by weight solution of polymer in a mixture of equal volumes of pentafluorophenol and hexafluoroisopropanol, of at least about l.Odl/g, with polymers having inherent viscosities of from about 3.0dl/g to about 7.0dl/g being of particular interest in many applications.
• I inherent viscosity
• Characteristic of the subject polymers is the formation of an anisotropic melt phase.
• an anisotropic melt phase is the formation of an anisotropic melt phase.
• Such thermotropic properties are manifest at a temperature which is amenable for melt processing to form shaped articles.
• Anisotropy in the melt may be confirmed by conventional polarized light microscopy techniques.
• the polymers of this invention have a degree of stretchability of at least about 100% and preferably have a degree of stretchability of at least about 200%, measured in accordance with the Tape Stretching Procedure set forth below; polymers having a degree of stretchability of at least about 500%, pursuant to such procedure are of particular interest.
• the liquid crystalline polymers of this invention also have much greater gas barrier resistance than many non-liquid crystalline thermoplastics conventionally used in packaging applications, for example, polyolefins and polyalkylene terephthalates.
• the barrier properties of the subject polymers coupled with their ability to be stretched to a high degree at temperatures typically used to stretch such non-liquid crystalline thermoplastics, i.e., from about 140°C to about 200°C, make the subject polymers particularly well-suited for use in multilayer laminates and containers for food and other packaging applications that require oxygen permeability resistance.
• the polymers of this invention are typically prepared by a polymerization reaction that proceeds through the acetylated form of the hydroxycarboxylic acid and diol reactants.
• reactants having pre -acetylated hydroxyl groups heat the reaction mix to polycondensation temperature and maintain reaction until a desired polymer viscosity is reached.
• acetylate in situ in which case the aromatic hydroxycarboxylic acid and aromatic diol are reacted with acetic anhydride, acetic acid by-product is removed, the esterified reactants together with the aromatic diacid are heated to polycondensation temperature, and reaction is maintained until a desired polymer viscosity is reached.
• the aromatic diacid reactant may, but need not, be present during the acetylation reaction. If the acetylation and polycondensation reactions are conducted in a single reactor, it is common to charge the reactor with the reactant materials in a single step. Using separate acetylation and polymerization reactors, it may be desirable to introduce the diacid component to the polymerization reactor as opposed to the acetylation reactor.
• the acetylation and polycondensation reactions are typically conducted in the presence of suitable catalysts.
• Such catalysts are well known in the art and include, for example, alkali and alkaline earth metal salts of carboxylic acids, such as, for example, potassium acetate, sodium acetate, magnesium acetate, and the like.
• Such catalysts are typically used in amounts of from about 50 to about 500 parts per million based on the total weight of the recurring unit precursors.
• Acetylation is generally initiated at temperatures of about 90°C.
• reflux is desirably employed to maintain vapor phase temperature below the point at which acetic acid by-product and anhydride begin to distill.
• Temperatures during the initial stage of acetylation typically range from between 90° to 150°C, preferably about 100° to about 130°C.
• the reaction mixture is then heated to final melt temperature of about 150° to about 220°C, preferably about 150° to about 200°C, with temperatures of 180° to 200°C being of particular interest.
• the vapor phase temperature should exceed the boiling point of acetic acid but remain low enough to retain residual acetic anhydride.
• Multilayer laminates may further contain one or more adhesive layers formed from adhesive materials such as, for example, polyester polyurethanes, polyether polyurethanes, polyester elastomers, polyether elastomers, polyamides, polyether polyamides, polyether polyimides, functionalized polyolefins, and the like.
• adhesive materials such as, for example, polyester polyurethanes, polyether polyurethanes, polyester elastomers, polyether elastomers, polyamides, polyether polyamides, polyether polyimides, functionalized polyolefins, and the like.
• Exemplary of such adhesives are ethylene-maleic anhydride copolymers, ethylene-methyl acrylate copolymers, ethylene-methyl acrylate copolymer grafted with maleic anhydride, ethylene-methyl acrylate maleic acid terpolymer, ethylene- gylcidyl methacrylate copolymer, ethylene- methylacrylate-glycidyl methacrylate terpolymer, ethylene-methyl methacrylate-acrylic acid terpolymer, ethylene-vinyl acetate copolymer, alkoxysilane modified ethylene-ethylacrylate copolymer, ethylene-acrylic acid copolymer, and blends of polypropylene grafted with maleic anhydride with a dimer based polyamide.
• compositions containing the subject polymers may contain one or more additional optional components such as for example, colorants, lubricants, processing aids, stabilizers, fillers, reinforcing agents, and the like. Fillers and reinforcing agents are not, however, typically present in compositions used in fiber, film and blow molding applications.
• HNA 6-hydroxy-2-naphthoic acid
• IA means isophthalic acid
• TA means terephthalic acid
• HQ means hydroquinone. All polymerizations were conducted in the presence of 60 ppm potassium acetate, using sufficient acetic anhydride to completely acetylate the hydroxyl groups present.
• Polymers are melt spun into tapes using a MicromeltTM apparatus.
• the apparatus is equipped with a 0.127mm by 6.35mm die.
• Melt temperatures typically vary between about 290-310°C depending upon the melt characteristics of the sample.
• Throughput rates are set at 0.45cc/min; take-up roller speeds are 2 rpm; and pack pressures typically range from about 80 kg/cm 2 to about 100kg/cm 2 , depending upon the T g (or T m ) of the polymer.
• the resulting tapes will have an approximate thickness of 0.05mm and a width of about 6mm. Five test specimens, each 12.7cm in length are cut from each tape.
• the thickness of the specimens is measured to the nearest 0.0025mm and the width to the nearest 0.25mm.
• the specimens are placed in a preheated Instron oven, allowed 6 minutes to come to temperature and then tested on an Instron type universal tester (equipped with a thermal chamber), set to a test temperature of 150°C.
• the gauge length is set at 25mm and the crosshead speed is set at 50.8mm/min.
• the % break strain is calculated at the break point for each specimen and is reported as an average of the five specimens tested.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyesters Or Polycarbonates (AREA)
• Artificial Filaments (AREA)

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• 2001
  • 2001-08-21 US US09/933,645 patent/US6514611B1/en not_active Expired - Lifetime
• 2002
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  • 2002-08-07 JP JP2003523521A patent/JP4102300B2/ja not_active Expired - Fee Related
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