WO1979001034A1 - Liquid crystal copolyesters containing phenylhydroquinone - Google Patents

Liquid crystal copolyesters containing phenylhydroquinone Download PDF

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Publication number
WO1979001034A1
WO1979001034A1 PCT/US1979/000289 US7900289W WO7901034A1 WO 1979001034 A1 WO1979001034 A1 WO 1979001034A1 US 7900289 W US7900289 W US 7900289W WO 7901034 A1 WO7901034 A1 WO 7901034A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
copolyesters
phenylhydroquinone
liquid crystal
radical
Prior art date
Application number
PCT/US1979/000289
Other languages
English (en)
French (fr)
Inventor
W Jackson
G Gebeau
H Kuhfuss
Original Assignee
Eastman Kodak Co
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
Priority claimed from US05/971,987 external-priority patent/US4242496A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of WO1979001034A1 publication Critical patent/WO1979001034A1/en

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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

  • This invention relates to liquid crystal copolyesters prepared from an aromatic dicarboxylic acid, a phenylhydroquinone and a p-acyloxybenzoic acid.
  • liquid crystal polyesters When liquid crystal polyesters are calendared or subjected to other thermoforming operations the polyesters are heated above their softening point. If the softening point of the polyester is high and close to the melting point of the polyester, the calendering or thermoforming operation can cause a substantial reduction in the physical properties of the polyester. For many liquid crystal polyesters the softening point is only 10-30 °C. below the melting point of the polyester and when these polyesters are heated above their softening point a loss of the high strength and high stiffness characteristics of the polyesters occurs.
  • liquid crystal polyesters have softening points substantially lower than their melting points so that the loss of desirable physical properties can be avoided during calendaring or thermoforming.
  • This invention provides copolyesters that have surprisingly low softening points and in some instances the softening points are 100 °C. and more below the melting points.
  • the copolyesters of this invention are prepared from a dicarboxylic acid, which can be terephthalic acid or 2,6-naphthalenedicarboxylic acid or mixtures thereof, phenylhydroquinone or a substituted phenylhydroquinone, and a p-acyloxybenzoic acid.
  • This copolyester can be specifically defined as a copolyester having a fiber-forming molecular weight and having the following radicals :
  • R 1 is or mixtures thereof ,
  • R 2 is hydrogen, chlorine , bromine or a monovalent alkyl radical having one to four carbon atoms , n is 1 , 2 or
  • R 2 is hydrogen and the range of radical (C) is from 30 to 65 mole percent and more preferably the dicarboxylic acid is terephthalic acid.
  • Radical (A) is the radical remaining after removal of the hydroxyl groups from the dicarboxylic acid
  • radical (B) is the radical remaining after removal of the terminal hydrogen atoms from phenylhydroquinone or a substituted phenylhydroquinone
  • radical (C) is the radical remaining after removal of the terminal hydroxyl group and acyl group from a p-acyloxybenzoic acid.
  • the copolyesters of this invention can be prepared by an acidolysis procedure wherein terephthalic acid or 2,6-naphthalenedicarboxylic acid or combinations of terephthalic acid and 2,6-naphthalenedicarboxylic acid, a diacyl ester of phenylhydroquinone and a p-acyloxybenzoic acid are contacted at a temperature of 260°- 300°C. until most of the monocarboxylic acid has evolved. The temperature is then increased to 350-390°C. and the pressure is decreased to form a high molecular weight polymer.
  • the polymer solidifies prior to achieving a fiber-forming molecular weight, its molecular weight may be increased to a fiber-forming value by heating particles of the polymer in. an inert atmosphere or under reduced pressure at a temperature just below the softening point of the polymer.
  • the inherent viscosity of the copolyesters of this invention are at least 0.5, and preferably at least 1.0, measured at 25 C. using 0.1 gram of polymer per 100 ml. of a solvent composed by weight of 25 percent phenol, 35 percent tetrachloroethane, and 40 percent p-chlorophenol.
  • the molecular weights of the copolyesters of the invention are high enough to be in the fiber-forming range.
  • the minimum fiber-forming molecular weight of the polymer is about 5,000.
  • the copolyester of the invention has a molecular weight above 8,000 and can have a molecular weight as high as 20,000. In some instances the molecular weight can range up to 25 , 000 or even higher.
  • a mixture of 8.3 g (0.05 mole) terephthalic acid, 13-5 g (0.05 mole) of the diacetate ester of phenylhydroquinone and 9.0 g (0.05 mole) p-acetoxybenzoic acid was placed in a 100-ml. flask equipped with a stirrer, a short distillation column, and an inlet for nitrogen.
  • the flask was evacuated and purged three times with nitrogen before being lowered into a metal bath maintained at 110°C.
  • the mixture was heated under a nitrogen atmos- phere with stirring to a temperature of 260°C. at which point acetic acid began to distill rapidly from the flask.
  • the above polymer was dried in an oven at 100°C. overnight and injection molded to give 2-1/2 x 3/8 x l/16-inch tensile bars and 5 x 1/2 x 1/8-inch flexure bars for testing.
  • ASTM procedures were used for measuring the tensile strength and elongation (ASTM D1708), flexural modulus (ASTM D790), Izod impact strength (ASTM D256 Method A), and heat deflection temperature (ASTM D648). Bars injection molded at 380°C. were smooth, clear and light amber.
  • Molded flexure bars of this composition were thermoformed at 210°C. using a thermoforming die and a press. The bar was preheated at 210°C. for 30 seconds and easily formed within 20 seconds.
  • Other copolyesters within the scope of the invention containing 2,6-naphthalenedicarboxylic acid instead of all or part of the terephthalic acid can be prepared by a similar procedure but using slightly different reaction temperatures because of differences in melting, points.
  • Crystalline melting points and softening points of copolyesters prepared from 2-phenyl-l,4-phenylene diacetate, terephthalic acid and p-acetoxybenzoic acid are listed below.
  • the softening points (Ts) were determined with a Du Pont 941 Thermomechanical Analyzer, using a 10-g weight on a tipped probe (0.025-in. diameter) and a scan rate of 10 C/min.
  • the melting points (Tm) were determined with a differential scannin calorimeter.
  • Softening points and crystalline melting points of copolyesters prepared from 2-phenyl-l,4-phenylene diacetate, 2,6-naphthalenedicarboxylic acid, and p-acetoxybenzoic acid are as follows:
  • diesters of phenylhydroquinone can be used to prepare the copolyesters of this invention.
  • diesters include the diacetate, dipropionate, dibutyrate and dibenzoate. The diacetate and dipropionate are preferred.
  • the p-acyloxybenzoic acid that provides radical (C) in the copolyester of this invention correspond to the structure
  • R is phenyl or a monovalent alkyl radical of 1 to 8, preferably 1 to 4, carbon atoms.
  • pacyloxybenzoic acids include p-acetoxybenzoic acid, ppropionyloxybenzoic acid, p-butyryloxybenzoic acid, and p-phenoxybenzoic acid.
  • R is a monovalent alkyl radical having one carbon atom, in which case the p-acyloxybenzoic acid is p-acetoxybenzoic acid.
  • the p-acyloxybenzoic acids can be prepared by conventional processes, such as reaction between phydroxybenzoic acid and a carboxylic anhydride, such as acetic anhydride. Other processes for preparation of the p-acyloxybenzoic aromatic carboxylic acids are well known in the art.
  • the copolyesters of this invention can contain other divalent radicals in minor amounts. For example, minor amounts of other isomers of naphtha- lenedicarboxylic acid can be used.
  • the copolyesters of this invention can contain nucleating agents, fillers, pigments, glass fibers, asbestos fibers, antioxidants, stabilizers, plasticizers, lubricants, fire-retardants, and other additives.

Landscapes

  • 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)
PCT/US1979/000289 1978-05-05 1979-05-02 Liquid crystal copolyesters containing phenylhydroquinone WO1979001034A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US90336978A 1978-05-05 1978-05-05
US05/971,987 US4242496A (en) 1978-12-21 1978-12-21 Liquid crystal copolyesters containing phenylhydroquinone
US971987 1978-12-21

Publications (1)

Publication Number Publication Date
WO1979001034A1 true WO1979001034A1 (en) 1979-11-29

Family

ID=27129360

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1979/000289 WO1979001034A1 (en) 1978-05-05 1979-05-02 Liquid crystal copolyesters containing phenylhydroquinone

Country Status (3)

Country Link
EP (1) EP0018973A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS6333490B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1979001034A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0205855A1 (de) * 1985-05-18 1986-12-30 Bayer Ag Thermotrope aromatische Polyester mit hervorragenden mechanischen Eigenschaften und guter Verarbeitbarkeit, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Formkörpern, Filamenten, Fasern und Folien
EP0187734A3 (en) * 1985-01-04 1989-02-08 Monsanto Company Liquid crystalline compositions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529565A (en) * 1983-08-31 1985-07-16 Asahi Kasei Kogyo Kabushiki Kaisha Polyester of substituted or unsubstituted phenoxyhydroquinone
JPH01272630A (ja) * 1988-04-26 1989-10-31 Toray Ind Inc 芳香族ポリエステル

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3160602A (en) * 1960-06-01 1964-12-08 Gen Electric Process of producing aromatic polyesters
US3637595A (en) * 1969-05-28 1972-01-25 Steve G Cottis P-oxybenzoyl copolyesters
US3778410A (en) * 1972-09-28 1973-12-11 Eastman Kodak Co Process for preparing a final copolyester by reacting a starting polyester with an acyloxy aromatic carboxylic acid
US4064108A (en) * 1974-10-04 1977-12-20 Teijin Limited Novel polyesters prepared from mixture of hydroquinone and bisphenols
US4066620A (en) * 1975-04-29 1978-01-03 E. I. Du Pont De Nemours And Company Copolyester capable of forming anisotropic melt and shaped articles thereof
US4067852A (en) * 1976-05-13 1978-01-10 Celanese Corporation Melt processable thermotropic wholly aromatic polyester containing polybenzoyl units
US4075262A (en) * 1975-08-12 1978-02-21 E. I. Du Pont De Nemours And Company Copolyesters capable of forming an anisotropic melt
US4083829A (en) * 1976-05-13 1978-04-11 Celanese Corporation Melt processable thermotropic wholly aromatic polyester
BE860959A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1976-11-19 1978-05-18 Du Pont
US4118372A (en) * 1974-05-10 1978-10-03 E. I. Du Pont De Nemours And Company Aromatic copolyester capable of forming an optically anisotropic melt
US4140846A (en) * 1978-05-04 1979-02-20 Eastman Kodak Company Liquid crystal copolyesters containing 4-carboxybenzenepropionic acid
US4146702A (en) * 1977-08-08 1979-03-27 Eastman Kodak Company Liquid crystal copolyesters prepared from an aromatic dicarboxylic acid, a substituted hydroquinone and a m-acyloxybenzoic acid
US4153779A (en) * 1978-06-26 1979-05-08 Eastman Kodak Company Liquid crystal copolyester containing a substituted phenylhydroquinone
US4156070A (en) * 1977-08-08 1979-05-22 Eastman Kodak Company Liquid crystal copolyesters prepared from an aromatic dicarboxylic acid, a substituted hydroquinone and resorcinol

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3160602A (en) * 1960-06-01 1964-12-08 Gen Electric Process of producing aromatic polyesters
US3637595A (en) * 1969-05-28 1972-01-25 Steve G Cottis P-oxybenzoyl copolyesters
US3778410A (en) * 1972-09-28 1973-12-11 Eastman Kodak Co Process for preparing a final copolyester by reacting a starting polyester with an acyloxy aromatic carboxylic acid
US4118372A (en) * 1974-05-10 1978-10-03 E. I. Du Pont De Nemours And Company Aromatic copolyester capable of forming an optically anisotropic melt
US4064108A (en) * 1974-10-04 1977-12-20 Teijin Limited Novel polyesters prepared from mixture of hydroquinone and bisphenols
US4066620A (en) * 1975-04-29 1978-01-03 E. I. Du Pont De Nemours And Company Copolyester capable of forming anisotropic melt and shaped articles thereof
US4075262A (en) * 1975-08-12 1978-02-21 E. I. Du Pont De Nemours And Company Copolyesters capable of forming an anisotropic melt
US4067852A (en) * 1976-05-13 1978-01-10 Celanese Corporation Melt processable thermotropic wholly aromatic polyester containing polybenzoyl units
US4083829A (en) * 1976-05-13 1978-04-11 Celanese Corporation Melt processable thermotropic wholly aromatic polyester
BE860959A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1976-11-19 1978-05-18 Du Pont
US4146702A (en) * 1977-08-08 1979-03-27 Eastman Kodak Company Liquid crystal copolyesters prepared from an aromatic dicarboxylic acid, a substituted hydroquinone and a m-acyloxybenzoic acid
US4156070A (en) * 1977-08-08 1979-05-22 Eastman Kodak Company Liquid crystal copolyesters prepared from an aromatic dicarboxylic acid, a substituted hydroquinone and resorcinol
US4140846A (en) * 1978-05-04 1979-02-20 Eastman Kodak Company Liquid crystal copolyesters containing 4-carboxybenzenepropionic acid
US4153779A (en) * 1978-06-26 1979-05-08 Eastman Kodak Company Liquid crystal copolyester containing a substituted phenylhydroquinone

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0187734A3 (en) * 1985-01-04 1989-02-08 Monsanto Company Liquid crystalline compositions
EP0205855A1 (de) * 1985-05-18 1986-12-30 Bayer Ag Thermotrope aromatische Polyester mit hervorragenden mechanischen Eigenschaften und guter Verarbeitbarkeit, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Formkörpern, Filamenten, Fasern und Folien

Also Published As

Publication number Publication date
JPS55500215A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1980-04-10
EP0018973A1 (en) 1980-11-26
JPS6333490B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1988-07-05

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