WO1997045469A1 - Resine polyester a cristaux liquides - Google Patents

Resine polyester a cristaux liquides Download PDF

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Publication number
WO1997045469A1
WO1997045469A1 PCT/US1996/007779 US9607779W WO9745469A1 WO 1997045469 A1 WO1997045469 A1 WO 1997045469A1 US 9607779 W US9607779 W US 9607779W WO 9745469 A1 WO9745469 A1 WO 9745469A1
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WO
WIPO (PCT)
Prior art keywords
repeat units
liquid crystalline
mole percent
ilia
repeat
Prior art date
Application number
PCT/US1996/007779
Other languages
English (en)
Inventor
Marion Glen Waggoner
Michael Robert Samuels
Original Assignee
E.I. Du Pont De Nemours And Company
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 E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to JP54227197A priority Critical patent/JP3392875B2/ja
Priority to AU59349/96A priority patent/AU5934996A/en
Priority to PCT/US1996/007779 priority patent/WO1997045469A1/fr
Publication of WO1997045469A1 publication Critical patent/WO1997045469A1/fr

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Classifications

    • 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

Definitions

  • liquid crystalline polyesters made from hydroquinone, terephthalic acid, 2,6-naphthalene dicarboxylic acid and 4-hydroxybenzoic acid which have good physical properties, melting points of about 350 ' C or less, and can be manufactured rapidly.
  • Thermotropic liquid crystalline polymers are well known, and are useful as molding resins (for electrical connectors and automotive parts, for example), films, barrier resins, and other uses for thermoplastics. Although these types of polymers are well known, there exists a need for such polymers which have good properties, are easy to prepare, and have relatively low cost.
  • This invention concerns a liquid crystalline polyester consisting essentially of repeat units of the formulas:
  • repeat unit (I) constitutes 50 to 63 mole percent of said repeat units, repeat unit (II) constitutes 18 5 to 25 mole percent of said repeat units, repeat units (Ilia) plus (Illb) constitute 18 5 to 25 mole percent of said repeat units, the molar ratio of (Ilia) (Illb) is 35 65 to 45 55, and the molar ratio of (II) [(Ilia) + (Illb)] is about 1 DETAILS OF THE INVENTION
  • the liquid crystalline polyester described herein is a completely aromatic polyester in which repeat unit (1) is derived from 4-hydroxy benzoic acid (HBA), repeat unit (II) is derived from hydroquinone (HQ), repeat unit (Ma) is derived from terephthalic acid (TPA), and repeat unit (Illb) is derived from 2,6-naphthalene dicarboxylic acid (NDA) Those persons skilled in the art will recognize that the total molar amount of HQ will be substantially equal to the
  • FIGURES Figure 1 is a contour plot of melting points vs the two polymer compositional variables the percent HBA [unit (I)] in the polymer, and amount of TPA (Ilia) in the ratio of (Ilia) (Illb) (as described above)
  • Each contour line represents a constant value for a melting point, which is shown
  • Figure 2 is a contour plot of finishing time (in hours) vs the two polymer compositional variables the percent HBA [unit (I)] in the polymer, and amount of
  • TPA TPA (Ilia) in the ratio of (Ilia) (Illb) (as described above)
  • Each contour line is represents a constant value for the finishing time
  • finishing time is meant the amount of time under full vacuum needed to reach a certain viscosity, as measured by torque on the stirrer (see the Examples)
  • Data from Examples 1-8 was used to calculate the contour plots, even though not all of the polymers made in these Examples are within the claimed composition range
  • the data were statistically analyzed and calculated using a program from SYSTAT, Ine , Evanston, IL, U S A called SYSTAT for Windows,
  • the melting points of the polymer composition range selected herein are about 350 ' C or less This is important to the synthesis of high quality polyesters It has been the experience of the present inventors that when temperatures much above 350'C are required to make a polyester liquid crystalline polymer, degradation of the starting materials and/or polymer products is markedly increased, thereby leading to undesirable effects such as excessive discoloration of the polyester. To avoid crystallization of the polymer, the polymerization is usually run at or above the melting point of the polymer. Therefore melting points of about 350'C or below are desirable. However, in order to have a high use temperature for the polymer, melting points should also be as high as possible, i.e., in this case close to 350" C.
  • the selected polymer compositions have such melting points, as shown by Figure 1.
  • the finishing period should also be reasonably short.
  • polymers with about 50 mole percent or more of HBA-derived repeat units surprisingly have relatively short finishing times. While the absolute value of the finishing times will vary according to the quality of the monomers used, the size and configuration of the equipment used, etc., the relative order for the finishing times shown in Fig. 2 should not change in a set of polymerizations in which all other variables are held constant.
  • the instant liquid crystalline polyesters can be made by methods known to the artisan for making aromatic polyesters.
  • the acetate esters (or other low alkyl ester) of the hydroxyl groups in the basic monomers may be mixed with the diacids and heated, gradually removing byproduct acetic acid, to eventually form the desired polymer.
  • the acetates can be formed in situ by adding slightly more than a stoichiometric amount of acetic anhydride to a mixture of all the monomers, heating the mixture to its boiling point, holding for a short time to acetylate the hydroxyl groups, and then performing the polymerization condensation.
  • the phenyl esters of the carboxylic acid groups in the monomers may be reacted with the hydroxyl groups, while removing byproduct phenol by distillation.
  • the reactants are usually eventually heated above 3 OOX under vacuum to achieve a desirable polymer molecular weight.
  • the polymers disclosed herein may be mixed or compounded with a variety of materials normally mixed with thermoplastics, such as fillers and/or reinforcers such as glass fiber; glass spheres; flaked glass; carbon fiber; carbon blacks; and minerals, such as clay; pigments; colorants; stabilizers; other polymers; tougheners; antioxidants; flame retardants; and plasticizers.
  • a three-liter glass kettle was used as the reaction vessel. Heat was supplied to the vessel via an electrically heated metal bath composed of bismuth and tin. Agitation was provided by a Cole-Parmer Master Servodyne Unit equipped with a 50: 1 gear reducer. Torque (in D.C. millivolts) and RPM were constantly displayed during operation. Vapors boiled from the vessel passed through a one-piece, 2.5 cm O.C. glass column and through a water cooled condenser equipped with a splitter to drain condensed distillate into a 1 liter graduated cylinder. A nitrogen bleed valve was attached to the system to provide a nitrogen blanket prior to the acetylation, polymerization, and distillation steps of the reaction.
  • the set temperature was increased to 370' C to drive off residual acetic acid and maintain a molten resin as it finished under vacuum, which was applied later.
  • the column, condenser, and graduated cylinder were removed, and a nitrogen line which also was attached to pressure/vacuum reading devices, was installed.
  • the Teflon ⁇ bushing around the stir shaft was fully tightened, and vacuum was slowly applied until the system pressure reached 8.4 X 10 4 Pa (abs).
  • Tm melting point
  • the polymer obtained was melt blended in a twin screw extruder with glass fiber to obtain a composition containing 30% by weight of glass fiber.
  • This composition was molded on a single screw injection molding machine with barrel temperatures of about 330-350'C, to obtain standard test pieces.
  • the tensile properties were measured using the ASTM D-638 procedure, the flexural modulus properties were measured by ASTM D-790, and Heat Deflection Temperature (HDT) was measured by ASTM D-648, at 1.82 MPa load. Finishing times and Tm of the unfilled polyester, and physical properties of the glass fiber filled polyesters are found in Table I.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des polyesters à cristaux liquides constitués d'hydroquinone, d'acide térépththalique, d'acide 2,6-napththalènedicarboxylique et d'acide 4-hydroxybenzoïque, et correspondant à une gamme de compositions sélectionnées. Lesdit polymères présentent un point de fusion d'environ 350 °C ou inférieur, de bonnes caractéristiques physiques et peuvent être produits facilement. Ces polymères peuvent être utilisés comme résines à mouler.
PCT/US1996/007779 1996-05-28 1996-05-28 Resine polyester a cristaux liquides WO1997045469A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP54227197A JP3392875B2 (ja) 1996-05-28 1996-05-28 液晶ポリエステル樹脂
AU59349/96A AU5934996A (en) 1996-05-28 1996-05-28 Liquid crystalline polyester resin
PCT/US1996/007779 WO1997045469A1 (fr) 1996-05-28 1996-05-28 Resine polyester a cristaux liquides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/007779 WO1997045469A1 (fr) 1996-05-28 1996-05-28 Resine polyester a cristaux liquides

Publications (1)

Publication Number Publication Date
WO1997045469A1 true WO1997045469A1 (fr) 1997-12-04

Family

ID=22255170

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/007779 WO1997045469A1 (fr) 1996-05-28 1996-05-28 Resine polyester a cristaux liquides

Country Status (3)

Country Link
JP (1) JP3392875B2 (fr)
AU (1) AU5934996A (fr)
WO (1) WO1997045469A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6890988B2 (en) 2002-02-27 2005-05-10 Sumitomo Chemical Company, Limited Aromatic polyester

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169933A (en) * 1977-08-08 1979-10-02 Eastman Kodak Company Liquid crystal copolyesters containing terephthalic acid and 2,6-naphthalenedicarboxylic acid
US4337191A (en) * 1979-11-05 1982-06-29 Fiber Industries, Inc. Polyester of para-hydroxy benzoic acid, 2,6-naphthalene dicarboxylic acid, terephthalic acid and methylhydroquinone exhibiting improved hydrolytic stability and which is capable of forming an anisotropic melt
EP0357207A2 (fr) * 1988-08-01 1990-03-07 Eastman Kodak Company Polyesters cristallins liquides transformables à l'état fondu

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169933A (en) * 1977-08-08 1979-10-02 Eastman Kodak Company Liquid crystal copolyesters containing terephthalic acid and 2,6-naphthalenedicarboxylic acid
US4337191A (en) * 1979-11-05 1982-06-29 Fiber Industries, Inc. Polyester of para-hydroxy benzoic acid, 2,6-naphthalene dicarboxylic acid, terephthalic acid and methylhydroquinone exhibiting improved hydrolytic stability and which is capable of forming an anisotropic melt
EP0357207A2 (fr) * 1988-08-01 1990-03-07 Eastman Kodak Company Polyesters cristallins liquides transformables à l'état fondu

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
W.J. JACKSON, JR: "Liquid Crystal Polymers", MACROMOLECULES, vol. 16, no. 7, 1983, pages 1027 - 1038, XP002022434 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6890988B2 (en) 2002-02-27 2005-05-10 Sumitomo Chemical Company, Limited Aromatic polyester

Also Published As

Publication number Publication date
JP3392875B2 (ja) 2003-03-31
JP2000511220A (ja) 2000-08-29
AU5934996A (en) 1998-01-05

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