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.

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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)

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• 1988
  • 1988-03-18 JP JP63504351A patent/JPH01502833A/ja active Pending
  • 1988-03-18 EP EP88904738A patent/EP0312585A1/de not_active Withdrawn
  • 1988-03-18 PT PT87028A patent/PT87028B/pt not_active IP Right Cessation
  • 1988-03-18 WO PCT/US1988/000818 patent/WO1988007068A2/en not_active Ceased
  • 1988-03-18 IL IL85788A patent/IL85788A0/xx unknown
  • 1988-03-18 AU AU17803/88A patent/AU1780388A/en not_active Abandoned
  • 1988-03-19 CN CN88101868A patent/CN1030244A/zh active Pending

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