WO1995016747A1 - Compositions a base de polyester - Google Patents

Compositions a base de polyester Download PDF

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Publication number
WO1995016747A1
WO1995016747A1 PCT/US1994/014204 US9414204W WO9516747A1 WO 1995016747 A1 WO1995016747 A1 WO 1995016747A1 US 9414204 W US9414204 W US 9414204W WO 9516747 A1 WO9516747 A1 WO 9516747A1
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WO
WIPO (PCT)
Prior art keywords
polyester resin
polyester
weight
resin composition
propylene glycol
Prior art date
Application number
PCT/US1994/014204
Other languages
English (en)
Inventor
William K. Cheung
Paul R. Krumlauf
William Barrick
Jeff W. Tigner
Original Assignee
Owens Corning
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 Owens Corning filed Critical Owens Corning
Publication of WO1995016747A1 publication Critical patent/WO1995016747A1/fr

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Classifications

    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters

Definitions

  • This invention relates generally to polyester resin compositions. More particularly, the invention is directed to chemically thickened polyester resin compositions useful for preparing sheet molding compound (SMC) and bulk molding compound (BMC) formulations; and to the molded articles producible therefrom.
  • SMC sheet molding compound
  • BMC bulk molding compound
  • Unsaturated polyester resin compositions are used in the automotive industry to prepare SMC formulations from which molded parts such as body panels may be manufactured.
  • Such resin compositions typically comprise an unsaturated polyester, a crosslinking monomer, a chemical thickener, and a low profile additive (LPA) , i.e., a thermoplastic polymer that acts to prevent undesirable shrinkage of the molded part as it cures. It is the ability of LPA's to compensate for the shrinkage of thermosetting polymers that leads to their usefulness in SMC formulations. Microphase separation between the LPA and unsaturated polyester occurs during the curing of the resin. As the unsaturated polyester resin and monomer crosslinks, the LPA and crosslinking polyester become increasingly less compatible and a dual phase morphology results.
  • LPA low profile additive
  • unsaturated polyester resins containing an LPA can experience zero shrinkage or even expand upon curing, which is well-known in the art.
  • this microphase separation which occurs upon curing and is beneficial in preventing shrinkage, also improves the smoothness of the resultant molded article.
  • U.S. Patent No. 4,263,198 discloses thickening agents for unsaturated polyester resin compositions, comprising a Group II-A metal oxide or hydroxide, an unsaturated monomer, and an unsaturated polyester which is a reaction product of a dicarboxylic acid and a monohydric alcohol.
  • polyester resin compositions which are less susceptible to humidity variations caused by changing weather conditions and seasonal variations, and therefore which undergo maturation more consistently than conventional polyester resin compositions.
  • the polyester resin composition comprises: an unsaturated polyester, comprising a reaction product of one or more polycarboxylic acids and one or more polyhydric alcohols; monomer; a low molecular weight TMA-modified polyester; and a chemical thickener, comprising a hydroxide or an oxide of a metal from Group 2 of the Periodic Table.
  • the present invention includes a thickening system for polyester resins, comprising: a low molecular weight TMA-modified polyester, comprising a reaction product of trimeUitic anhydride, one or more dicarboxylic acids, and one or more diols; and a chemical thickener, comprising a hydroxide or an oxide of a metal from Group 2 of the Periodic Table.
  • a thickening system for polyester resins comprising: a low molecular weight TMA-modified polyester, comprising a reaction product of trimeUitic anhydride, one or more dicarboxylic acids, and one or more diols; and a chemical thickener, comprising a hydroxide or an oxide of a metal from Group 2 of the Periodic Table.
  • the present invention includes molded articles producible using the thickening systems and polyester resin compositions of the present invention.
  • the polyester resin compositions. and thickening systems of the present invention are particularly useful in SMC formulations for preparing molded articles such as, for example, vehicle body panels.
  • the present invention is directed to polyester resin compositions, polyester resin thickening systems, and to molded articles producible therefrom.
  • the inventive polyester resin compositions comprise, inter alia, an unsaturated polyester, which may be the polycondensation reaction product of one or more polycarboxylic acids and one or more polyhydric alcohols. Either or both of the polycarboxylic acid and polyhydric alcohol must be ethylinically unsaturated. Occasionally, a combination of saturated and unsaturated polycarboxylic acids and/or polyhydric alcohols is used to prepare an unsaturated polyester, according to the present invention. An unsaturated polycarboxylic acid may be used to prepare the unsaturated polyesters of the present invention.
  • unsaturated polycarboxylic acid as it is used herein is meant unsaturated polycarboxylic and dicarboxylic acids and anhydrides, unsaturated polycarboxylic and dicarboxylic acid halides, and unsaturated polycarboxylic and dicarboxylic acid esters.
  • Suitable unsaturated polycarboxylic acids include, but are not necessarily limited to, maleic acid, maleic anhydride, fumaric acid, methyl maleic acid, itaconic acid, methyl itaconic acid, ⁇ ,/3-methyleneglutaric acid, etc., as well as mixtures thereof.
  • a preferred unsaturated polycarboxylic acid comprises maleic acid.
  • unsaturated polycarboxylic acids may be reacted with polyhydric alcohols to prepare the unsaturated polyester resins of the present invention.
  • suitable polyhydric alcohols include, but are not necessarily limited to, ethylene glycol, propylene glycol including 1,2-propylene glycol and 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6- hexanediol, 1,8-octanediol, neopentyl glycol, 2-methyl-l,3- propanediol, glycerol, trimethylol propane, 1,2,6- hexanetriol, 1,2,4-butanetriol, trimethylol ethane, erythritol, pentaerythritol, quinitol, mannitol, sorbitol, methylglycoside, diethylene glycol, triethylene glycol
  • the unsaturated polyesters of the present invention additionally may be prepared utilizing saturated polycarboxylic acids and/or unsaturated polyhydric alcohols alone or in combination with the unsaturated polycarboxylic acids and/or polyhydric alcohols listed above.
  • Suitable saturated polycarboxylic acids include, but are not necessarily limited to, terephthalic acid, phthalic acid, phthalic acid anhydride, terephthaloyl chloride, isophthalic acid, tetrahydrophthalic acid anhydride, trimeUitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, succinic acid, adipic acid, sebacic acid, suberic acid, azelaic acid, succinic anhydride, azelaoyl chloride, etc.
  • Suitable unsaturated polyhydric alcohols include, but are not necessarily limited to, 2,5—dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl- 4-octyne-3,6—diol, 2-butene-l,4-diol, and the like, as well as mixtures thereof.
  • the acid value to which the unsaturated polyester is condensed is not sharply critical, and may range over wide limits from about 20 to about 100. An acid number of less than about 70 is preferred. The number average molecular weight of the unsaturated polyester may vary over a considerable range from about 500 to about 5,000.
  • Methods for reacting polycarboxylic acids together with polyhydric alcohols to produce unsaturated polyesters are well-known in the art.
  • a preferred unsaturated polyester resin comprises a reaction product of maleic anhydride and propylene glycol, reacted together in a ratio of about 1.1:1 by weight, to produce an unsaturated polyester having an acid value from about 27 to about 33.
  • a ratio of about as it is used herein is meant that the ratio may vary either higher or lower by about 20%.
  • Monomers for use in the polyester resin compositions according to the present invention include, but are not necessarily limited to, styrene, divinyl benzene, vinyl toluene, chlorostyrene, ⁇ -methylstyrene, dimethylstyrene, diallyl phthalate, triallyl cyanurate, acrylic acid esters, acrylonitrile, vinyl acetate, methyl aerylate, methyl methacrylate, ethylstyrene, isopropylstyrene, divinyl ether, diallyl ether, vinyl allyl ether, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, allyl acrylate, allyl methacrylate, vinyl benzoate, allyl benzoate, triallylamine, vinyl chloride, and the like, as well as mixtures thereof.
  • Preferred monomers comprise styrene and/or divinyl benzene.
  • the polyester resin compositions of the present invention additionally comprise a thickening system, for effecting maturation of the polyester resin composition.
  • the inventive thickening system comprises a low molecular weight trimellitic anhydride (TMA)-modified polyester and a chemical thickener.
  • TMA trimellitic anhydride
  • Use of the inventive thickening system makes the inventive polyester resin compositions much less susceptible to humidity variations caused by changing weather conditions and seasonal variations. Thus, substantial, consistent maturation of polyester resin compositions is achieved.
  • the low molecular weight TMA-modified polyester for use according to the present invention is prepared by reacting together trimellitic anhydride, one or more aliphatic or aromatic dicarboxylic acids, and one or more diols.
  • Suitable aliphatic dicarboxylic acids include, but are not necessarily limited to, adipic acid, sebacic acid, octadecanoic acid, suberic acid, azelaic acid, succinic acid, undecanoic acid, glutaric acid, pimelic acid, oxalic acid, maleic acid, maleic anhydride, fumaric acid, methyl maleic acid, itaconic acid, methyl itaconic acid, a, ⁇ - methyleneglutaric acid, and the like, as well as mixtures thereof.
  • Suitable aromatic dicarboxylic acids include, but are not necessarily limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyletherdicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, and the like, as well as mixtures thereof.
  • a preferred dicarboxylic acid comprises adipic acid.
  • Diols useful for preparing the low molecular weight TMA-modified polyester according to the present invention may be aliphatic or aromatic.
  • Suitable aliphatic diols include, but are not necessarily limited to, ethylene glycol, propylene glycol, including 1,2—propylene glycol and 1,3-propylene glycol, 1,4—butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8- octanediol, 1,4—cyclohexanedimethanol, 2,5-dimethyl-3- hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2-butene- 1,4-diol, etc., as well as mixtures thereof.
  • Aromatic diols include, but are not necessarily limited to, hydroquinone, resorcinol, 2,2-bis-(4-hydroxyphenyl)propane, bis-(4-hydroxypheny1) methane, 4,4-thiodiphenol, bis-(4- hydroxyphenyl)sulfone, 4,4-oxydiphenyl, 4,4- dihydroxybiphenol, dihydroxynaphthalene, and the like, as well as mixtures thereof.
  • a preferred diol comprises a mixture of ethylene glycol and propylene glycol.
  • the trimellitic anhydride may be in the form of an acid.
  • trimellitic anhydride as it is used herein is meant to include trimellitic acid as well as trimellitic anhydride.
  • the low molecular weight TMA-modified polyester for use according to the present invention may be prepared from the foregoing compounds by any conventional method such as, for example, the reaction of the TMA, the carboxylic acid or acid chloride, and the alcohol in the presence of a base; dehydration of the TMA, acid, and alcohol through physical or chemical means; reaction of the TMA, an ester derivative (such as a methyl ester) of the carboxylic acid, and the alcohol; or the reaction of the TMA, the carboxylic acid, and a derivative (such as an acetate) of the alcohol.
  • any conventional method such as, for example, the reaction of the TMA, the carboxylic acid or acid chloride, and the alcohol in the presence of a base; dehydration of the TMA, acid, and alcohol through physical or chemical means; reaction of the TMA, an ester derivative (such as a methyl ester) of the carboxylic acid, and the alcohol; or the reaction of the TMA, the carboxylic acid, and a derivative (such as
  • a preferred low molecular weight TMA-modified polyester comprises a reaction product of TMA, propylene glycol, ethylene glycol, and adipic acid, reacted together in a ratio of about 1:1:1:2 by weight, to an acid value from about 20 to about 90.
  • the acid value is from about 30 to about 70.
  • the thickener system additionally comprises a chemical thickener, comprising a hydroxide or oxide of a metal from Group 2 of the Periodic Table, e.g., magnesium and calcium hydroxides and oxides, as well as mixtures thereof.
  • a preferred chemical thickener comprises magnesium hydroxide.
  • the chemical thickener is suspended in a carrier which is not reactive therewith such as, for example, a solution of polymethylmethacrylate in an organic solvent.
  • a carrier which is not reactive therewith
  • the thickening systems may be prepared by blending together the low molecular weight TMA-modified polyester and chemical thickener utilizing conventional mixing apparatus.
  • the concentration of chemical thickener may range from about 50 to about 95 by weight, based upon the total weight of the thickener system.
  • the chemical thickener comprises from about 65 to about 85, by weight.
  • the various components of the polyester resin compositions of the present invention may be present in the following concentrations, expressed as percentages by weight of the total weight of the unsaturated polyester, monomer, low molecular weight TMA-modified polyster, and chemical thickener: unsaturated polyester from about 35% to about 80%, preferably from about 55% to about 70%; monomer from about 10% to about 50%, preferably from about 15% to about 35; TMA-modified polyester from about 0.5% to about 5%, preferably from about 1% to about 3%; and chemical thickener from about 3% to about 25%, preferably from about 5% to about 20%.
  • the polyester resin compositions of the present invention may optionally include other ingredients which are conventionally used to prepare, for example, an SMC formulation.
  • the polyester resin composition may include an LPA which is a thermoplastic material that, when mixed with an unsaturated polyester and a crosslinker, will result in a multiphase system upon curing of the unsaturated polyester. This phenomenon results in a reduction or the elimination of shrinkage of the ultimately molded article during the curing process.
  • LPA is a thermoplastic material that, when mixed with an unsaturated polyester and a crosslinker, will result in a multiphase system upon curing of the unsaturated polyester. This phenomenon results in a reduction or the elimination of shrinkage of the ultimately molded article during the curing process.
  • Suitable LPA's include, but are not necessarily limited to, saturated polyesters, homopolymers and copolymers of acrylic acid esters and methacrylic acid esters, cellulose acetate butyrate, homopolymers and copolymers of vinyl acetate, polyether polyols, polycaprolactam-based polymers, styrene/butadiene copolymers, modified cellulosic polymers, alkyl oxide polymers, and the like, as well as mixtures thereof.
  • a preferred LPA comprises a saturated polyester.
  • a particularly preferred LPA comprises a saturated polyester which is a reaction product of propylene glycol, ethylene glycol, and adipic acid, reacted together in a ratio of about 1:1.6:2.56 by weight, to an acid value from about 2 to about 15.
  • the acid value is from about 9.5 to about 12.
  • Yet another preferred saturated polyester LPA is prepared from these same precursors polymerized to a molecular weight from about 1,000 to about 3,000.
  • Polypropylene glycol having a number average molecular weight from about 400 to about 1,000 may be utilized in the inventive polyester resin compositions in an amount sufficient to enhance the surface smoothness of an SMC molded article produced therefrom. While not wishing to be bound by any particular theory regarding the mechanism by which the polypropylene glycol improves the surface smoothness of molded articles, it is believed that the polypropylene glycol remains compatible with the unsaturated polyester while it cures and therefore does not phase separate from the crosslinking unsaturated polyester (as does an LPA, which phase separates to reduce the shrinkage of the molded part) .
  • a preferred polypropylene glycol has a number average molecular weight range from about 650 to about 750. Such a polypropylene glycol is available from BASF Corporation having the product designation P710. Methods for preparing polypropylene glycols are well-known in the art.
  • Catalysts may be incorporated into the polyester resin compositions of the present invention in small amounts.
  • Such catalysts are well-known and include, by way of example but not limitation, organic peroxides and per-acids such as tertiary butyl perbenzoate, tertiary butyl peroctate, benzoyl peroxide, etc.
  • organic peroxides and per-acids such as tertiary butyl perbenzoate, tertiary butyl peroctate, benzoyl peroxide, etc.
  • the catalyst accelerates the polymerization reaction between the unsaturated polyester and mixture of monomers.
  • a preferred catalyst comprises tertiary butyl perbenzoate.
  • a mold release agent may be included in the polyester resin compositions, and is particularly useful when an SMC sheet is prepared.
  • Typical mold release agents include, but are not necessarily limited to, calcium stearate, zinc stearate, magnesium stearate, organic phosphate esters, and the like.
  • a preferred mold release agent comprises calcium stearate.
  • Suitable pigments which may be incorporated into the polyester resin compositions of the present invention include inorganic and organic pigments such as, for example, carbon black, iron oxide, titanium dioxide, and the like, as well as mixtures thereof. Fibers and fillers may likewise be added to the polyester resin compositions of the present invention, and are particularly useful for preparing SMC formulations.
  • Reinforcing fibers including glass or mineral fibers, glass fiber fabrics, chopped glass strands, chopped or continuous strand glass fiber mats, asbestos fibers, cotton fibers, synthetic organic fibers, metal fibers, and the like, as well as combinations thereof, may be added to the polyester resin compositions to impart strength and integrity to molded articles produced therefrom.
  • Preferred reinforcing fibers comprise glass fibers.
  • nonreinforcing fillers may be added to reduce the overall cost of the polyester resin composition without significantly sacrificing the desirable physical properties thereof.
  • Such fillers may include calcium carbonate, clay, talc, silica, calcium silicate, and the like, as well as mixtures thereof.
  • a preferred filler comprises calcium carbonate.
  • the polyester resin composition is utilized in an SMC formulation, comprising A-side and B-side components.
  • the A-side component comprises the unsaturated polyester, low molecular weight TMA-modified polyester, monomer, and optionally, an LPA, polypropylene glycol, a catalyst, mold release agent, fillers, and reinforcing fibers.
  • the B-side component comprises the chemical thickener.
  • the A- and B-side components are individually mixed in conventional blending equipment at conventional temperatures, and thereafter blended together and formed into SMC sheets which undergo maturation for a period of time prior to being molded and cured by conventional techniques.
  • the actual maturation and molding procedures will, of course, depend upon the SMC formulation, the nature of the article to be molded, the molding conditions, etc.
  • SMC sheets undergo maturation for up to several days, after which they are molded at temperatures from about 120°C to about 175"C for periods of time up to about 5 minutes.
  • molded articles may be prepared comprising the cured polyester resin compositions of the present invention.
  • ingredients, concentrations, and process conditions described hereinabove for the preparation of polyester resin compositions, polyester resin thickening systems, and the molded articles made therefrom, are not sharply critical to the successful practice of the present invention, except as noted otherwise.
  • the ingredients, concentrations, and reaction conditions recited are generally disclosed in terms of their broadest application to the practice of the invention. Occasionally, the ingredients, concentrations, or reaction conditions as described may not be applicable to each embodiment included within the disclosed scope. Where this occurs, it will readily be recognizable by those ordinarily skilled in the art.
  • either the invention may be practiced by conventional modifications, e.g., by using alternative, conventional ingredients or concentrations, by routine modifications of reaction conditions, etc., or different ingredients, concentrations, or reaction conditions which are otherwise conventional will be applicable to the practice of the present invention.
  • polyester resin compositions are prepared by conventional methods:
  • Example composition (MW « 700) Tertiary Butyl Perbenzoate 1.5 1.5 1.5 Calcium Stearate 4 4 4 Calcium Carbonate 220 225 225 SMC sheets are prepared from the foregoing compositions, matured for several days, and analyzed as set forth in Table II. It is observed that the Example composition undergoes maturation at a rate significantly greater than that of a similar composition containing no TMA-modified polyester (Comparison 1) . The maturation of the Example composition is similar to that of the composition containing the more aggressive conventional calcium oxide chemical thickener (Comparison 2) .
  • polyester resin compositions may be used in bulk molding compounds or other molding formulations conventionally -known in the art.

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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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une composition à base de résine polyester comprend un polyester insaturé, un monomère, et un système épaississant composé d'un polyester modifié par anhydride trimellitique et de faible poids moléculaire, ainsi que d'un épaississant chimique.
PCT/US1994/014204 1993-12-15 1994-12-12 Compositions a base de polyester WO1995016747A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16686093A 1993-12-15 1993-12-15
US08/166,860 1993-12-15

Publications (1)

Publication Number Publication Date
WO1995016747A1 true WO1995016747A1 (fr) 1995-06-22

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PCT/US1994/014204 WO1995016747A1 (fr) 1993-12-15 1994-12-12 Compositions a base de polyester

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994853A (en) * 1974-04-09 1976-11-30 Hooker Chemicals & Plastics Corporation Tack free polymerizable polyester compositions
WO1992001727A1 (fr) * 1990-07-23 1992-02-06 Owens-Corning Fiberglas Corporation Additifs thermoplastiques peu contractibles et utilisation de ces additifs dans des compositions de resines de polyester insature

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994853A (en) * 1974-04-09 1976-11-30 Hooker Chemicals & Plastics Corporation Tack free polymerizable polyester compositions
WO1992001727A1 (fr) * 1990-07-23 1992-02-06 Owens-Corning Fiberglas Corporation Additifs thermoplastiques peu contractibles et utilisation de ces additifs dans des compositions de resines de polyester insature

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