WO1988007068A2 - Compositions de moulage contenant des polyesters totalement aromatiques a remplissage de renforcement - Google Patents

Compositions de moulage contenant des polyesters totalement aromatiques a remplissage de renforcement Download PDF

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Publication number
WO1988007068A2
WO1988007068A2 PCT/US1988/000818 US8800818W WO8807068A2 WO 1988007068 A2 WO1988007068 A2 WO 1988007068A2 US 8800818 W US8800818 W US 8800818W WO 8807068 A2 WO8807068 A2 WO 8807068A2
Authority
WO
WIPO (PCT)
Prior art keywords
molding composition
wholly aromatic
component comprises
percent
aromatic polyester
Prior art date
Application number
PCT/US1988/000818
Other languages
English (en)
Other versions
WO1988007068A3 (fr
Inventor
Paul David Frayer
Original Assignee
Dart Industries 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 Dart Industries Inc. filed Critical Dart Industries Inc.
Publication of WO1988007068A2 publication Critical patent/WO1988007068A2/fr
Publication of WO1988007068A3 publication Critical patent/WO1988007068A3/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives

Definitions

  • This invention relates to molding compositions comprising reinforced filled wholly aromatic polyesters. More particularly, this invention relates to molding compositions comprising reinforced filled wholly aromatic polyesters which can be molded into articles having low warpage values and tensile strengths of at least 10,000 pounds per square inch.
  • Wholly aromatic polyesters are known to be self-reinforcing. Attempts to provide additional reinforcement, such as with glass fibers, have not been successful because the reinforcing component has a tendency to decrease the self-reinforcement of the wholly aromatic polyesters. Additionally, the use of a reinforcing component may not provide compositions which have significantly better properties. In some instances, these properties may be worse than the wholly aromatic polyester without the reinforcing component.
  • a decrease in the warpage values of wholly aromatic polyesters can be attained through the use of fillers.
  • the use of fillers can lead to a decrease in the mechanical properties (such as tensile strength) of the molded articles.
  • an object of this invention is to provide useful molding compositions which comprise wholly aromatic polyesters.
  • Another object of this invention is to provide useful molding compositions which comprise reinforced filled wholly aromatic polyesters.
  • Another object of this invention is to provide such compositions which can be molded into useful articles having good mechanical properties, such as tensile strength and impact strength.
  • Another object of this invention is to provide such compositions which can be molded into useful articles having low warpage values.
  • molding compositions which comprise:
  • the tensile strengths recited in this application are determined by the ASTM D-638 method.
  • warpage values recited in this application are determined by the following method:
  • a composition is molded into a connector having dimensions of about 4.65" length, .6" width and .285" thickness.
  • the connector is placed on a flat surface, and the warpage is observed along the length direction of the connector, with the width direction at right angles to the flat surface.
  • the amount of warpage is measured at the center of the connector by determining the distance (in mils) between the center and the flat surface.
  • warpage is measured twice.
  • the first measurement (“as-molded") is taken immediately after the connector is molded.
  • the second measurement is taken after heating the connector in an oven at 500°F. for 10 minutes to simulate soldering conditions.
  • low warpage means a value which is less than about 5 mils as-molded (first measurement) and less than about 15 mils after thermal treatment at 500°F. for 10 minutes (second measurement).
  • the wholly aromatic polyesters useful in this invention have melting temperatures of between about 200°C. and 450°C and comprise repeating units of one or more of the following formulas:
  • X is -O-, -S-, -CO-, or -SO2-, and m and n are independently zero or one, and the total of the integers p + q + r + s + t + u is from approximately 3 to about 800.
  • all of the units of the above formula can be present in a single polyester.
  • a simple embodiment would be homopolymers of units I or IV.
  • the preferred locations of the functional groups are in the para (1,4) and meta (1.3) positions. With respect to the naphthalene moiety, the preferred locations of the functional groups are 1,4; 1,5 and 2,6.
  • the symbols p, q, r, s, t, and u are integers and indicate the number of moieties present in the polyester.
  • the total (p + q + r + s + t + u) can vary from 3 to 800 and, when present, the ratio of q:r, q:u, t:r, t:u, q+t:r, q+t:r+u, and t:r+u, of the moieties can vary from about 10:11 to about 11:10, with the most preferable ratio being 10:10.
  • Exemplary of monomers from which the moieties of formula I may be obtained are: p - hydroxybenzoic acid, phenyl-p- hydroxybenzoate, p-acetoxybenzoic acid and isobutyl-p- acetoxybenzoate.
  • Those monomers from which the moiety of formula II may be obtained include terephthalic acid, isophthalic acid, diphenyl terephthalate, diethyl isophthalate , methylethyl terephthalate and the isobutyl half ester of terephthalic acid.
  • Among the monomers from which the moiety of formula III results are: p,p'-biphenol; p,p'-oxybiphenol; 4'-dihydroxybenzophenone; resorcinol and hydroquinone.
  • Examples of monomers represented by formula IV are: 4- hydroxy-1-naphthoic acid; 5 acetoxy-1-naphthoic acid; and phenyl 5-hydroxy-1-naphthoate.
  • Monomers representing formula V include: 1, 4-naphthalene dicarboxylic acid; 1, 5-naphthalene dicarboxylic acid and 2, 6-naphthalene dicarboxylic acid. The diphenyl esters or dicarbonyl chlorides of these acids can also be used.
  • Examples of the monomers representative of the formulas VI are 1, 4-dihydroxynaphthalene; 2, 6-diacetoxynaphthalene and 1, 5-dihydroxynaphthalene.
  • a preferred class of polyesters has recurring units of formulas VII, VIII, and IX: wherein the total of the integers p + q + r is about 3 to 800, the carbonyl groups of the moiety of formula VII or V III are linked to the oxy groups of the moiety of formula VII or IX; and the oxy groups of the moiety of formula VII or IX are linked to the carbonyl groups of the moiety of formula VII or VIII.
  • polyesters of this invention comprise the precursor formulas VII, VIII and IX wherein the molar ratios are from 0.01:1:1 to 99:1:1 and preferably from 1:1:1 to 5:1:1.
  • reinforcing components useful in this invention are glass fibers, carbon fibers and graphite fibers.
  • a preferred reinforcing component comprises glass fibers.
  • a useful range of the reinforcing component is from about 10 to 20 percent, by volume, based on the molding composition.
  • filler components useful in this invention are talc, aluminum powder, calcium sulfate, wollastonite, inert inorganic pigments, inorganic silicates and carbon black.
  • a preferred filler component comprises talc, calcium sulfate or carbon black.
  • a useful range of the filler component is from about 10 to 30 percent, by volume, based on the molding composition.
  • a preferred range is from about 10 to 20 percent, by volume.
  • the wholly aromatic polyester, reinforcing and filler components may comprise a combination of two or more of these materials.
  • the combination of reinforcing and filler components is from about 20 to 40 percent, by volume, based on the molding composition, and preferably from about 27 to 33 percent, by volume. Amounts not within this range generally do not provide an acceptable tensile and impact strengths and low warpage value for the molded articles.
  • compositions of this invention can be molded, by conventional techniques, into articles which have good mechanical properties, such as dimensional stability, tensile strength and thermal stability.
  • articles which have good mechanical properties, such as dimensional stability, tensile strength and thermal stability.
  • Example of these articles include connectors for use in the electrical/electronics industry.
  • electrically conductive filler materials such as certain aluminum powders and carbon blacks
  • electrically conductive filler materials can be used to great advantage.
  • the wholly aromatic polyesters useful in the present invention can also be chemically modified by various means such as by inclusion in the polyester of monofunctional reactants such as benzoic acid or a higher functional reactant such as trimesic acid or cyanuric chloride.
  • monofunctional reactants such as benzoic acid or a higher functional reactant such as trimesic acid or cyanuric chloride.
  • the benzene rings in these polyesters are preferably unsubstituted but can be substituted with noninterferring substituents, examples of which include halogens (such as chlorine or bromine), lower alkoxy groups (such as methoxy), and lower alkyl groups (such as methyl and ethyl).
  • the invention is further illustrated by the following exampless which are illustrative of certain embodiments designed to teach those of ordinary skill in the art how to practice the invention and to represent the best mode contemplated for carrying out the invention.
  • the wholly aromatic polyesters are prepared by conventional polycondensation methods and formulated with reinforcing and filler materials into molding compositions shown as Examples 1-7 in the following Table.
  • the resulting compositions are molded into electrical connectors, and the tensile strengths and warpage values are shown in the Table.
  • Examples 1 and 2 have good tensile strengths but do not have acceptable warpage values in both measurements.
  • Examples 6 and 7 have acceptable tensile strengths, but the warpage values were not measured as with Examples 1-5. These two examples were molded into large frames, and visual observations showed the warpage to be low and, therefore, acceptable.
  • the wholly aromatic polyester component comprises two wholly aromatic polyesters.
  • the first polyester is made from p-hydroxybenzoic acid; 4,4'- dihydroxybiphenyl; and terephthalic acid in the molar ratio of 2:1:1.
  • the second polyester is made from p-hydroxybenzoic acid; 4,4'- dihydroxybiphenyl; and isophthalic acid in the molar ratio of 3.7:1:1, and is used in an amount of less than 5%, by weight, based on the total molding composition.
  • a composition is made from 12.8 volume percent glass fiber, 19.7 volume percent talc and 67.5 volume percent of a wholly aromatic polyester component comprising two wholly aromatic polyesters.
  • the first polyester is made from p-hydroxybenzoic acid; 4,4'-dihydroxybiphenyl and terephthalic acid in the molar ratios of 2:1:1, respectively
  • the second polyester is made from p-hydroxybenzoic acid; 4,4'-dihydroxybyphenyl, terephthalic acid and isophthalic acid in the molar ratios of 3:1:0.75:0:25, respectively.
  • the second polyester is used in an amount equal to 10.0 percent by weight based on the total molding composition. Molded parts from this composition demonstrated excellent impact strength and low warpage.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On peut mouler avec des compositions de moulage contenant des polyesters totalement aromatiques à remplissage de renforcement des objets utiles ayant une faible déformabilité et une bonne résistance à la rupture par traction.
PCT/US1988/000818 1987-03-20 1988-03-18 Compositions de moulage contenant des polyesters totalement aromatiques a remplissage de renforcement WO1988007068A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2830687A 1987-03-20 1987-03-20
US028,306 1987-03-20

Publications (2)

Publication Number Publication Date
WO1988007068A2 true WO1988007068A2 (fr) 1988-09-22
WO1988007068A3 WO1988007068A3 (fr) 1988-12-29

Family

ID=21842705

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/000818 WO1988007068A2 (fr) 1987-03-20 1988-03-18 Compositions de moulage contenant des polyesters totalement aromatiques a remplissage de renforcement

Country Status (7)

Country Link
EP (1) EP0312585A1 (fr)
JP (1) JPH01502833A (fr)
CN (1) CN1030244A (fr)
AU (1) AU1780388A (fr)
IL (1) IL85788A0 (fr)
PT (1) PT87028B (fr)
WO (1) WO1988007068A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482639A2 (fr) * 1990-10-24 1992-04-29 E.I. Du Pont De Nemours And Company Polyesters liquides cristallins thermotropes à partir de 2-méthylhydroquinone
EP0630955A1 (fr) * 1993-06-25 1994-12-28 Sumitomo Chemical Company, Limited Composition de résine polyester liquide cristalline et réflecteurs pour lampes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267289A (en) * 1980-07-03 1981-05-12 Celanese Corporation Blend of wholly aromatic polyesters
JPS5710641A (en) * 1980-06-24 1982-01-20 Sumitomo Chem Co Ltd Wholly aromatic copolyester resin composition
US4318841A (en) * 1980-10-06 1982-03-09 Celanese Corporation Polyester of 6-hydroxy-2-naphthoic acid, para-hydroxy benzoic acid, terephthalic acid, and resorcinol capable of readily undergoing melt processing to form shaped articles having increased impact strength
US4375530A (en) * 1982-07-06 1983-03-01 Celanese Corporation Polyester of 2,6-naphthalene dicarboxylic acid, 2,6-dihydroxy naphthalene, terephthalic acid, and hydroquinone capable of forming an anisotropic melt
EP0261869A2 (fr) * 1986-09-26 1988-03-30 Sumitomo Chemical Company, Limited Composition de résines synthétiques contenant des polyarylates et des polyesters
EP0264290B1 (fr) * 1986-10-17 1994-01-26 Polyplastics Co. Ltd. Composition pour moulage par injection

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5474852A (en) * 1977-11-29 1979-06-15 Teijin Ltd Polyester resin composition
US4563508A (en) * 1984-05-18 1986-01-07 Dart Industries, Inc. Injection moldable aromatic polyesters compositions and method of preparation
JPS6131470A (ja) * 1984-07-24 1986-02-13 Daicel Chem Ind Ltd 改質副生カ−ボンブラツク及びその高導電性樹脂組成物
JPS6168801A (ja) * 1984-09-11 1986-04-09 日本油脂株式会社 導電性フイラ−
JPS6169866A (ja) * 1984-09-12 1986-04-10 Polyplastics Co 複合材料組成物
JPH0739534B2 (ja) * 1986-12-10 1995-05-01 ポリプラスチックス株式会社 表面特性の良好な液晶性ポリエステル樹脂組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5710641A (en) * 1980-06-24 1982-01-20 Sumitomo Chem Co Ltd Wholly aromatic copolyester resin composition
US4267289A (en) * 1980-07-03 1981-05-12 Celanese Corporation Blend of wholly aromatic polyesters
US4318841A (en) * 1980-10-06 1982-03-09 Celanese Corporation Polyester of 6-hydroxy-2-naphthoic acid, para-hydroxy benzoic acid, terephthalic acid, and resorcinol capable of readily undergoing melt processing to form shaped articles having increased impact strength
US4375530A (en) * 1982-07-06 1983-03-01 Celanese Corporation Polyester of 2,6-naphthalene dicarboxylic acid, 2,6-dihydroxy naphthalene, terephthalic acid, and hydroquinone capable of forming an anisotropic melt
EP0261869A2 (fr) * 1986-09-26 1988-03-30 Sumitomo Chemical Company, Limited Composition de résines synthétiques contenant des polyarylates et des polyesters
EP0264290B1 (fr) * 1986-10-17 1994-01-26 Polyplastics Co. Ltd. Composition pour moulage par injection

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, Vol. 6, No. 073, C-101, & JP,A,57 010 641 (20.01.1982) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482639A2 (fr) * 1990-10-24 1992-04-29 E.I. Du Pont De Nemours And Company Polyesters liquides cristallins thermotropes à partir de 2-méthylhydroquinone
EP0482639A3 (en) * 1990-10-24 1992-11-19 E.I. Du Pont De Nemours And Company Thermotropic liquid crystalline polyesters from 2-methylhydroquinone
EP0630955A1 (fr) * 1993-06-25 1994-12-28 Sumitomo Chemical Company, Limited Composition de résine polyester liquide cristalline et réflecteurs pour lampes
US5529716A (en) * 1993-06-25 1996-06-25 Sumitomo Chemical Company, Limited Liquid crystal polyester resin composition and lamp reflector

Also Published As

Publication number Publication date
PT87028A (pt) 1988-04-01
WO1988007068A3 (fr) 1988-12-29
EP0312585A1 (fr) 1989-04-26
JPH01502833A (ja) 1989-09-28
AU1780388A (en) 1988-10-10
PT87028B (pt) 1992-06-30
CN1030244A (zh) 1989-01-11
IL85788A0 (en) 1988-09-30

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