WO1998027159A1 - Polyesters renforces tenaces dotes d'une fluidite amelioree - Google Patents

Polyesters renforces tenaces dotes d'une fluidite amelioree Download PDF

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WO1998027159A1
WO1998027159A1 PCT/US1997/023514 US9723514W WO9827159A1 WO 1998027159 A1 WO1998027159 A1 WO 1998027159A1 US 9723514 W US9723514 W US 9723514W WO 9827159 A1 WO9827159 A1 WO 9827159A1
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composition
polymer
weight
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mole
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PCT/US1997/023514
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English (en)
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Bruce Connard Bell
Thomas Eduard Flora
Larry Allen Minnick
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Eastman Chemical Company
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Priority to BR9713952A priority Critical patent/BR9713952A/pt
Priority to EP97951762A priority patent/EP0951510A1/fr
Priority to JP52799098A priority patent/JP2002509565A/ja
Publication of WO1998027159A1 publication Critical patent/WO1998027159A1/fr

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    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a polymer composition
  • a polymer composition comprising a polycarbonate or a polyester, which preferably comprises terephthalic acid and is optionally reinforced with glass fibers.
  • This polymer composition has improved flow, improved toughness and impact resistance, and a high heat deflection temperature.
  • plastics can be substantially toughened by incorporation of a dispersed rubbery phase in the polymer matrix.
  • the rubbery phase acts to absorb the energy of impact or deformation. Adhesion between the rubbery phase and the matrix is important to the transfer of energy.
  • a common example is high impact polystyrene (HIPS) wherein the rubbery polybutadiene (PBD) phase adheres to the brittle polystyrene matrix by virtue of graft copolymers PS-g-PBD that tie the two incompatible phases together.
  • HIPS high impact polystyrene
  • PBD rubbery polybutadiene
  • PS-g-PBD graft copolymers
  • Patent 5,436,296 very good adhesion between the incompatible rubbery particles and the polyester matrix is achieved by including an epoxy (or oxirane) functionalized comonomer in the rubbery polymer that can react directly with the polyester. Reinforcing fillers can have significant negative effects on toughness and impact resistance. Therefore, adhesion between the surfaces of the matrix and the impact modifier is important. As is common practice in the industry, glass fibers are coated with coupling agents and thin films (sizing) that specifically promote adhesion to polyesters and epoxies. The result is good adhesion between all three phases.
  • U.S. Patent 4,172,859 pertains to the toughening of polyesters. Although U.S. Patent 4,172,859 recognizes the necessity of interphase adhesion with the recited criteria of "sites which adhere to the matrix resin," the detrimental effect of this adhesion on the important property of mold flow or melt viscosity is not taught therein. U.S. Patent 4,172,859 recites the phrase "at least one random copolymer.”
  • U.S. Patent 4,753,980 discloses the use of a terpolymer, ethylene-alkyl acrylate-glycidyl methacryols for toughening polyesters. With the inclusion of glycidyl methacrylate (GMA), the terpolymer contains an oxirane (or epoxy) functionality which adheres to or reacts with polyesters, which increases the melt viscosity as more of this toughening agent is added to the polyester.
  • GMA glycidyl methacrylate
  • U.S. Patent 5,436,296 teaches the use of a copolymer of ethylene and glycidyl methacrylate (PE-GMA) as a compatibilizer to modify blends of poly(alkylene terephthalate) (PET) and polyethylene (PE), illustrating that by adding a compatibilizer from between 8 and 15 % based on the weight of the blend, the Izod impact strength and the ductility of the blends increases substantially.
  • PET poly(alkylene terephthalate)
  • PE polyethylene
  • U.S. Patent 5,436,296 recites the role "adhesion between different thermoplastic polymer phases" plays in toughening the blend.
  • Patent 5,436,296 does not show or relate the detrimental effect that this adhesion inducing compatibilizer has on melt flow, except to mention that it is "believed that the addition of the glycidyl group containing copolymer above the preferred range increases the viscosity of the resulting blend such that the viscosity increase causes the inversion of the two polymer matrix" (col. 6).
  • U.S. Patent 4,461,871 addresses the issue of poor melt flow for toughened polyesters, reciting "the flow properties upon injection molding” of toughened polyester compositions "are very poor because of high melt viscosity.”
  • the polyester composition claimed in U.S. Patent 4,461 ,871 comprises three components, (a) an aromatic polyester, (b) a copolymer containing glycidyl groups and (c) a copolymer consisting of ethylene and an ⁇ -olefin which is defined as an unsaturated hydrocarbon "selected from the group consisting of propylene, 1- butene, 1-pentene, 3-methyl-l-pentene, 1-hexene, 1-octene, and the like.” None of the references described above discloses the particular benefits of substantially decreasing melt viscosity of polyesters or copolyesters for better melt flow while maintaining toughness, impact resistance and high heat deflection temperatures.
  • this invention in one aspect, relates to a polymer molding composition, comprising:
  • a first polymer comprising a polyester, a polycarbonate, or a mixture thereof
  • a third polymer comprising at least one second ⁇ -olefin and at least one second alkyl acrylate.
  • the invention further provides a polymer molding composition comprising
  • a dicarboxylic acid component comprising one or more dicarboxylic acids selected from the group consisting of aliphatic dicarboxylic acids having a total of from 3 to 16 carbon atoms, alicyclic dicarboxylic acids having 7 to 12 carbon atoms, aromatic dicarboxylic acids containing a total of from 8 to 16 carbon atoms, and combinations thereof, and
  • glycol component comprising one or more glycols having from 2 to 18 carbon atoms, one or more glycol ethers having from 4 to 12 carbon atoms, and combinations thereof,
  • weight percentages are based on the total weight percentages of the components of said polymer molding composition equaling 100 weight %.
  • the invention further relates to a thermoplastically- formed article formed from the polymer molding composition.
  • the object of the invention is to improve the usefulness of the polymers, and preferably, the thermoplastic polyesters poly(l,4-cyclohexane terephthalate) (PCT) and poly(ethylene terephthalate) (PET) as molding plastics by substantially decreasing the melt viscosity for better melt flow while maintaining the toughness, impact resistance and high heat deflection temperature.
  • PCT poly(l,4-cyclohexane terephthalate)
  • PET poly(ethylene terephthalate)
  • this invention in one aspect, relates to a polymer molding composition, comprising:
  • a first polymer comprising a polyester, a polycarbonate, or a mixture thereof
  • a third polymer comprising at least one second ⁇ -olefin and at least one second alkyl acrylate.
  • This invention relates to a polymer molding composition having at least three components.
  • the first component is a polymer.
  • the polymer is one or more polycarbonates or one or more polyesters or combinations thereof.
  • the polyesters referred to herein include thermoplastic, crystalline or amorphous polyesters produced by conventional polymerization techniques from one or more diols and one or more dicarboxylic acids.
  • the polyesters normally are molding or fiber grade and have an inherent viscosity (I.V.) of about 0.2 to about 2.4 (dL/g), preferably about 0.4 or 0.5 to about 1.2, measured at 25 °C in a 60/40 ratio by weight of phenol/tetrachloroethane at a concentration of
  • the polyesters preferably comprise repeat units derived from a dicarboxylic acid component comprising one or more dicarboxylic acids selected from the group consisting of aliphatic dicarboxylic acids having a total of from 3 to 16 carbon atoms, alicyclic dicarboxylic acids having from 7 to 12 carbon atoms, aromatic dicarboxylic acids containing a total of from 8 to 16 carbon atoms, or a combination thereof, and a glycol component comprising one or more glycols having from 2 to 18 carbon atoms, one or more glycol ethers having from 4 to 12 carbon atoms or a combination thereof.
  • a dicarboxylic acid component comprising one or more dicarboxylic acids selected from the group consisting of aliphatic dicarboxylic acids having a total of from 3 to 16 carbon atoms, alicyclic dicarboxylic acids having from 7 to 12 carbon atoms, aromatic dicarboxylic acids containing a total of from 8 to 16 carbon atoms, or
  • aliphatic-dicarboxylic acid is used to denote straight or branched chain alkanedicarboxylic acids preferably containing from 3 to 16 carbons.
  • Typical aliphatic dicarboxylic acids include, but are not limited to, succinic acid, giutaric acid, adipic acid, sebacic acid, suberic acid, 2,2,4-trimethyladipic, 1,12- dodecanedioic acid and the like.
  • alicyclic dicarboxylic acid is used to denote cycloalkane dicarboxylic acids which preferably contain a total of from 7 to 12 carbon atoms preferably 1,2-, 1,3- and 1,4-cyclohexanedicarboxylic acids.
  • aromatic dicarboxylic acid is used to denote dicarboxylic acid derivatives of benzene, naphthalene, biphenyl, diphenylether, diphenylsulfone and these substituted with C, - C 4 alkyl or halogen (fluorine, chlorine, bromine or iodine).
  • aromatic dicarboxylic acids include, but are not limited to, terephthalic acid, isophthalic acid, phthalic acid, 1 ,4-naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic, 4,4'-biphenyldicarboxylic acid, 2-bromoterephthalic acid, 2,5-dibromoterephthalic acid, tetrachlorophthalic acid and the like.
  • examples of dicarboxylic acids useful in forming the polyester or copolyester of the invention include, but are not limited to terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, 1 ,4-cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylate, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like.
  • isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid and naphthalenedicarboxylate are preferred.
  • naphthalenedicarboxylic acid When cyclohexanedicarboxylic acid is used in the context of the invention, cis-, trans-, or cisl trans mixtures may be used. Any of the naphthalenedicarboxylic acid isomers or mixtures of isomers may be used. In a preferred embodiment, naphthalenedicarboxylic acid isomers include 2,6-, 2,7- 1,4- and 1,5- isomers.
  • Suitable diol components of the described polyesters may be selected from ethylene glycol, 1 ,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 1,4- butanediol, 2,2-dimethyl-l,3-propanediol, 1 ,6-hexanediol, 1,2-cyclohexanediol,
  • Preferred polyesters comprise at least about 50 mole % terephthalic acid residues and/or at least about 50 mole % ethylene glycol and/or 1,4- cyclohexanedimethanol residues.
  • polyesters are those containing from about 75 to 100, more preferably, 90 to 100 mole %, and even more preferably, 95 to 100 mole % terephthalic moieties based on the total mole percentages of the acid components of the polyester equaling 100 mole %.
  • terephthalic moieties include, but are not limited to, terephthalic acid and esters thereof.
  • polyesters also include those containing from about
  • preferred polyesters are those containing from about 90 to 100 mole % terephthalic acid residues and from about 85 to 100 mole %, preferably 90 to 100 % ethylene glycol residues. Also, particularly preferred polyesters are those containing from about 90 to 100 mole % terephthalic acid and 65 to 75 mole % ethylene glycol.
  • terephthalic acid is preferably present in the amount of 60 to 90 mole %.
  • the polyester have repeat units derived from terephthalic acid or dimethyl terephthalate and a glycol selected from the group consisting of ethylene glycol and 1 ,4-cyclohexanedimethanol.
  • isophthalic acid it is preferably present in the amount of 0.1 to 50 mole %, preferably 0.1 to 25 mole %, based the mole percentages of all acids in the acid component of the copolyester equaling 100 mole %.
  • the dicarboxylic acid comprises terephthalic acid or dimethyl terephthalate in the amount of 80 to 99.9 mole % and isophthalic acid in the amount of 0.1 to 20 mole % based on the total mole percentages of the acid component of the polyester equaling 100 mole %.
  • the acid component includes terephthalic acid and naphthalenedicarboxylic acid
  • Copolyesters may be prepared from one or more of the above dicarboxylic acids.
  • dicarboxylic acids includes the corresponding acid anhydrides, esters, and acid chlorides of these acids.
  • the mole percentages of the acids referred to herein equal a total of 100 mole %.
  • the mole percentages of the glycols referred to herein equal a total of 100 mole %. In one embodiment, the glycol component is from 80 to 100 mole % ethylene glycol based on the total percentages of the glycol component equaling 100 mole %.
  • the glycol component of the polyester of the invention contain from about 50 to 100 mole %, preferably, 60 to 100 mole, more preferably 80 to 100 mole %, and even more preferably 90 to 100 mole % of one of the isomers of 1 ,4-cyclohexanedimethanol.
  • the polyesters of this invention may be based on cis-. trans-, or cisl trans mixtures of 1,4-cyclohexanedimethanol.
  • the 1,4- cyclohexanedimethanol useful in the invention have a cisl trans ratio in the range of 60/40 to 10/90, preferably 50/50 to 15/85, and more preferably 40/60 to 25/75. If the level of cis isomer is greater than about 60 mole %, the melting point of the polyester is reduced too much for use in heat resistant applications. If the level of trans isomer is greater than about 90 mole %, the melting point increases too close to the degradation point and molding becomes impractical.
  • the glycol component is aliphatic or alicyclic.
  • the glycol component may comprise up to 40, preferably up to 20 mole %, and more preferably, up to 10 mole %, of one or more additional aliphatic or alicyclic glycols where 1,4-cyclohexanedimethanol is the other glycol as described herein.
  • the copolyester contains 1,4-cyclohexanedimethanol and ethylene glycol
  • polyester resins useful in the blend of this invention are well known and are commercially available. Methods for their preparation are described, for example, in United States Patent Nos. 2,465,319; 2,901,466 and 3,047,539.
  • the polyester is preferably from 40 to 90 % or preferably from 40 to 60% when no glass fiber is present, by weight of the total polymer molding composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.
  • polycarbonates useful within the scope of this invention are normally made by reacting glycols with a carbonate source such as phosgene, dibutyl carbonate and diphenyl carbonate.
  • the polycarbonates of the present invention are preferably based on 4,4'-ispropylidenediphenol (bisphenol-A) reacted with either phosgene, dibutyl carbonate or diphenyl carbonate.
  • bisphenol-A polycarbonate component of these blends is available and would be useful in a wide range of molecular weights.
  • the polycarbonate comprises a polycarbonate of 4,4'-isopropylidenediphenol, 2,2,4,4- tetramethyl-l,3-cyclobutanediol, or a mixture thereof.
  • Suitable examples of commercially available bisphenol A polycarbonates include LEXAN ® , from General Electric, and MAKROLON ® , from Miles, Inc.
  • polycarbonate is the polycarbonate of 2,2,4,4- tetramethyl-l,3-cyclobutanediol.
  • the polycarbonate portion of the present blend can be prepared in the melt, in solution, or by interfacial polymerization techniques well known in the art.
  • polycarbonates are normally made by reacting glycols with a carbonate source such as phosgene, dibutyl carbonate and diphenyl carbonate.
  • the inherent viscosity of the polycarbonate portion of the blends according to the present invention is preferably about 0.3 to about 2.0 dL/g, more preferably from about 0.5 to about 1.2 dL/g, as determined at 25 °C in 60/40 wt/wt phenol tetrachloroethane at a concentration of 0.5 g/100 mL as determined at 25 °C.
  • the polycarbonate is preferably from 50 to 95 % or preferably from 70 to 95% when no glass fibers are present, by weight of the total polymer molding composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.
  • Mixtures of polyester/polycarbonate may also be used within the context of this invention. These mixtures may be made by conventional techniques, including melt processing techniques. For example, pellets of the polyester may be mixed with pellets of the polycarbonate and subsequently melt blended in either a single or twin screw extruder to form a homogenous mixture.
  • the polyester/polycarbonate mixture is preferably from 40 to 95 % by weight of the total polymer molding composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.
  • the second polymer of the polymer molding composition comprises a copolymer based on the monomeric units of at least one ⁇ -olefin, at least one alkyl acrylate, and at least one unsaturated epoxide.
  • the ⁇ -olefins useful in the second polymer of this invention have from 2 to 10 carbon atoms and can be unsubstituted or substituted with one or more alkyl, cycloaliphatic or aryl moieties.
  • useful ⁇ -olefins include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l-pentene, or 1-octene.
  • the ⁇ -olefin is ethylene or propylene, more preferably ethylene. It is preferred that the ⁇ -olefin portion of the second polymer be present in the amount of about 40 to about 90%, even more preferably about 55 to about 75%, by weight based on the total weight of the components of the second polymer.
  • Acrylates useful in the second polymer of this invention include, but are not limited to, alkyl acrylates.
  • alkyl acrylate also includes methacrylates.
  • the alkyl group of the alkyl acrylate preferably contains from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms.
  • the alkyl portion of the alkyl acrylate includes, but is not limited to, methyl, ethyl, propyl. isopropyl, n-butyl, isobutyl and 2-ethylhexyl.
  • the alkyl portion is preferably methyl, n-butyl and 2-ethylhexyl, more preferably methyl. It is preferred that the alkyl acrylate portion of the second polymer be present in the amount of about 10 to about 40%, preferably, about 15 to about 35 weight %, by weight based on the total weight of the terpolymer.
  • Unsaturated epoxides useful in the second polymer preferably have from 4 to 1 1 carbon atoms.
  • unsaturated epoxides having from 4 to 1 1 carbon atoms include, but are not limited to, glycidyl itaconate, allyl glycidyl ether, vinyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate.
  • a preferred class of unsaturated epoxides having from 4 to 1 1 carbon atoms are one or more glycidyl esters of one or more ⁇ , ⁇ -ethylenically unsaturated carboxylic acids.
  • one or more glycidyl esters of an ⁇ , ⁇ -elhylenically unsaturated carboxylic acid have the structure I:
  • R is hydrogen; an alkyl group having from about 1 to about 10 carbon atoms; or an alkyl group having from about 1 to about 10 carbon atoms and which comprises a substituted glycidyl ester radical.
  • glycidyl esters having the structure I include, but are not limited to, glycidyl acrylate, glycidyl mcihacrylalc, and glycidyl itaconate.
  • structure 1 is glycidyl methacrylate or glycidyl acrylate. moie piefcr.ihh glycidyl methacryhie.
  • the epoxide be present in the amount of about 1 to 20, preferably 2 to 10 % by weight based on the total weight of the second polymer.
  • the second polymer of the polymer molding composition comprises about 1 to about 20%), preferably about 1 to about 15%, more preferably 2 to about 12%, and even more preferably, about 2 to about 10% by weight of the polymer molding composition based on the total weight percentages of the first, second and third polymers equaling 100 weight %.
  • the second polymer is a random terpolymer.
  • the molecular weight of the second polymer is greater than 20,000. In a preferred embodiment, the molecular weight of the second polymer is a from about 70,000 to about 100,000.
  • the second polymer is E-MA-GMA (ethylene-methyl acrylate-glycidyl methacrylate), wherein,
  • E is the radical formed from ethylene comprising from 40 to 90 weight % of the second polymer E-MA-GMA;
  • MA is the radical formed from methyl acrylate comprising from 10 to 40 weight %, preferably 15 to 35 weight %, and most preferably, 20 to 35 weight % of the second polymer E-MA-GMA;
  • GMA is the radical formed from glycidyl methacrylate and comprising from 1 to 20 weight %, preferably 2 to 10 weight %, and most preferably, 3 to 8 weight % of the second polymer E-MA- GMA.
  • the third polymer is from about 2 to about 20% by weight of the polymer molding composition, wherein the third polymer comprises the monomeric units of at least one ⁇ -olefin and at least one alkyl acrylate.
  • the third polymer is a random copolymer.
  • the ⁇ -olefins useful in the third polymer of this invention have from 2 to 10 carbon atoms and can be unsubstituted or substituted with one or more aliphatic, cycloaliphatic or aryl moieties.
  • useful ⁇ -olefms include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l-pentene, or 1-octene.
  • the ⁇ -olefin for the third polymer is ethylene or propylene, more preferably ethylene.
  • the ⁇ -olefin portion of the third polymer is present in the amount of about 50 to about 90 %, preferably about 65 to about 85 % by weight based on the total weight of the third polymer.
  • the alkyl group of the alkyl acrylate contains from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms.
  • the alkyl portion of the alkyl acrylate portion of the third polymer is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and 2-ethylhexyl.
  • the alkyl portion is preferably methyl, n-butyl and 2-ethylhexyl, more preferably methyl.
  • the alkyl acrylate portion of the third polymer is present in the amount of about 10 to about
  • the molecular weight of the third polymer is greater than 20,000. In another embodiment, the molecular weight of the second polymer is from about 70,000 to about 100,000.
  • the alkyl acrylate and ⁇ -olefin portion of the third polymer are the same or substantially the same as the alkyl acrylate and ⁇ -olefin portion of the second polymer.
  • the polymer molding composition of the present invention contains from about 2 to about 20 weight %, preferably about 2 to about 15 weight %, and most preferably about 3 to about 10 weight % of the third polymer E-RA, wherein,
  • E is the radical formed from ethylene comprising from 50 to 90 weight % of the third polymer E-RA;
  • RA is the radical formed from alkyl acrylate comprising from 10 to
  • the alkyl moiety may be methyl, ethyl, n-butyl, isobutyl, 2-ethylhexyl, or the like.
  • the ethylene copolymers used in the compositions of the present invention can be prepared by direct copolymerization, for example, copolymerization of ethylene, glycidyl methacrylate, and the methyl acrylate in the presence of a free- radical polymerization initiator at elevated temperatures, preferably from 100 to 270°C, and most preferably from 130 to 230°C, and at elevated pressures, preferably at least 70 MPa, and most preferably from 140 to 350 Mpa.
  • direct copolymerization for example, copolymerization of ethylene, glycidyl methacrylate, and the methyl acrylate in the presence of a free- radical polymerization initiator at elevated temperatures, preferably from 100 to 270°C, and most preferably from 130 to 230°C, and at elevated pressures, preferably at least 70 MPa, and most preferably from 140 to 350 Mpa.
  • the polymer molding composition comprises a first polymer that is from 40 to 90 % by weight of the total composition, a second polymer that is from 9 to 40 % by weight of the total composition, and a third polymer that is from 1 to 20 % by weight of the total composition, based on the total weight percentages of the first, second, and third polymers equaling 100 %.
  • the polymer molding composition comprises a first polymer, wherein the first polymer comprises a polyester and/or a polycarbonate; the second polymer comprises an ⁇ -olefin of from 40 to 90 % by weight of the second polymer, an alkyl acrylate of from 9 to 40 % by weight of the second polymer, and an unsaturated epoxide of from 1 to 20 % by weight of the second polymer; and a third polymer comprising an ⁇ -olefin of from 50 to 90 % by weight of the third polymer and an alkyl acrylate of from 10 to 50 % by weight of the third polymer, wherein the sum of the first, second, and third polymers equals 100%.
  • the polymer molding composition comprises:
  • a first polymer comprising a polyester containing repeat units derived from terephthalic acid and 1 ,4-cyclohexanedimethanol and having an inherent viscosity from about 0.5 to 2.0 g/dL;
  • a third polymer of ethylene and an alkyl acrylate where the alkyl moiety is preferably methyl, ethyl, n-butyl, isobutyl, 2-ethylhexyl, or the like, wherein the third polymer is preferably about 1 to 20% by weight, wherein
  • the invention further relates to a polymer molding composition
  • a polymer molding composition comprising
  • glycol component comprising one or more glycols having from 2 to 18 carbon atoms, one or more glycol ethers having from 4 to 12 carbon atoms, and combinations thereof,
  • weight percentages are based on the total weight percentages of the components of said polymer molding composition equaling 100 weight %.
  • Glass fibers that are used in the present invention conventionally have an average standard diameter of greater than 5 ⁇ .
  • the length of the glass filaments and whether or not they are bundled into fibers and the fibers bundled, in turn, into yarns, ropes or rovings, and the like, are not critical to this invention.
  • filamentous glass in the form of chopped strands of from about 1.5 mm to about 10 mm long, and preferably less than about 6 mm long. In the pellets and molded articles of the compositions on the hand, even shorter lengths will be encountered, because during compounding, considerable fragmentation occurs.
  • glass filaments are dispersed uniformly and the molded articles exhibit uniform and balanced mechanical properties, especially surface smoothness.
  • the amount of the glass fibers can vary broadly from 10 to 50 % by weight, and most preferably 10 to 40 % by weight, based on the total composition.
  • These glass fibers are conventionally sized with coupling agents, such as aminosilanes and epoxysilanes and titanates, and adhesion promoters, such as epoxies, urethanes, cellulosics, starch, cyanurates, and the like.
  • the polyester when the glass fiber is present in the polymer molding composition, the polyester is preferably from 75 to 85 % by weight of the total composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.
  • the polycarbonate when the glass fiber is present in the polymer molding composition, the polycarbonate is preferably from 50 to 80 % by weight of the total composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.
  • the polymer molding composition comprises: (a) a first polymer comprising a polyester containing repeat units derived from terephthalic acid and 1 ,4-cyclohexanedimethanol and having an inherent viscosity from about 0.5 to 2.0 g/dL;
  • glass fibers preferably about 10 to 40% by weight of the total composition
  • additives such as stabilizers; inhibitors of degradation (i.e. oxidative, hydrolytic, thermal and ultraviolet light); flame retardants; fibrous and particulate fillers; reinforcing agents; lubricants; mold release agents; nucleating agents; and colorants (i.e. dyes and pigments) might also be desirable in such formulations.
  • Such additives are generally present at 0.1 to about 20 weight % based on the total weight of said polymer composition.
  • Useful flame retardants include, but are not limited, to brominated polystyrene; decabromodiphenyl oxide; and l,2-bis(tetrabromophthaIimide)ethane combined in combination with sodium antimonate or antimony oxide.
  • examples of other reinforcing agents that might be useful in addition to glass fibers include, but are not limited to, carbon fibers, mica, clay, talc, wollastonite, calcium carbonate or a combination thereof.
  • the polymer compositions of the invention may be reinforced with a mixture of glass and other reinforcing agents as described above, such as mica or talc, and/or with other additives.
  • the polymer compositions of the invention containing reinforcing agents may be molded at mold temperatures from about 30 to 120°C and, therefore, easily molded without the need for expensive mold heating equipment.
  • the preferred molding temperature of the glass filled polymer compositions of the invention is in the range of from 50 to 110°C.
  • compositions with improved flow described in this invention can be prepared by melt blending, in a closed system, the matrix resin PCT and the two copolymers into a uniform mixture in a multi-screw extruder such as a Werner- Pfleiderer extruder having generally kneading blocks, mixing elements and at least one reverse pitch to generate high shear.
  • a multi-screw extruder such as a Werner- Pfleiderer extruder having generally kneading blocks, mixing elements and at least one reverse pitch to generate high shear.
  • Other conventional plasticating devices such as a Brabender, Banbury mill, or the like, may be used for blending the composition.
  • the blends may be made by dry mixing together components followed by melt fabrication of the dry mixture by extrusion.
  • a wide range of useful articles can be made from the toughened polymer compositions of this invention by conventional molding methods employed in the fabrication of thermoplastic articles, for example, molded parts such as electrical and electronic connectors; and extruded shapes such as tubing, films, sheets, fibers and laminates.
  • E-MA-GMA ethylene-methyl acrylate-glycidyl methacrylate
  • the prepared compositions had fixed 20% glass fiber 492AA from Owens-Coming; 5.75% Uniplex 809 plasticizer (a polyalkylene ether which is a hydroxyl functional polyethylene glycol endcapped with ethyl hexanoate or reacted so that the ends of the polyethylene glycol is an ethyl hexanoate ester); a bis(2-ethylhexanoate) of poly(ethylene glycol) from Unitex; and 0.25 % carbon black, Black Pearls 800.
  • Uniplex 809 plasticizer a polyalkylene ether which is a hydroxyl functional polyethylene glycol endcapped with ethyl hexanoate or reacted so that the ends of the polyethylene glycol is an ethyl hexanoate ester
  • a bis(2-ethylhexanoate) of poly(ethylene glycol) from Unitex and 0.25 % carbon black, Black Pearls 800.
  • compositions were compounded at 300°C in a Werner-Pfleiderer ZSK-30 corotating, intermeshing twin screw extruder with 5 kneading elements, a Berstorff mixing element and 3 turbines, using calibrated loss in weight feeders.
  • the hot strand exiting the die was quenched in water, pelletized, then dried overnight at 100°C in desiccating ovens and molded in a Boy 50-S injection molding machine with the barrel temperature set at 300 °C and the test bar mold at lOO°C.
  • the molded bars were tested at about 25 °C and 50% relative humidity using the following test procedures:
  • E-MA-GMA and E-MA together give an unexpected benefit not derived with either of these components alone.
  • Table 6 shows an optimal compositions with regard to melt viscosity and HDT that include both E-MA-GMA and E-MA.
  • compositions that are optimal with regard to melt viscosity and HDT include both E-MA-GMA and E-MA.
  • PCT containing both E-MA-GMA and E-MA provides the best results with respect to toughness and Izod impact strength.

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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

L'invention a trait à une composition de moulage de polymères, renfermant (a) un premier polymère, notamment un polyester, un polycarbonate, ou un mélange de ceux-ci; (b) un deuxième polymère comportant au moins une première α-oléfine, au moins un premier acrylate d'alkyle, et au moins une résine époxyde insaturée; et (c) un troisième polymère comportant au moins une deuxième α-oléfine et au moins un deuxième acrylate d'alkyle. Cette invention a en outre trait à un article formé de façon thermoplastique préparé à partir des compositions de moulage de polymères décrites.
PCT/US1997/023514 1996-12-19 1997-12-17 Polyesters renforces tenaces dotes d'une fluidite amelioree WO1998027159A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR9713952A BR9713952A (pt) 1996-12-19 1997-12-17 Composição de moldagem de polìmero, e, artigo de formação termoplástica.
EP97951762A EP0951510A1 (fr) 1996-12-19 1997-12-17 Polyesters renforces tenaces dotes d'une fluidite amelioree
JP52799098A JP2002509565A (ja) 1996-12-19 1997-12-17 流動性が改良された靱性強化ポリエステル

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US3245296P 1996-12-19 1996-12-19
US98884797A 1997-12-11 1997-12-11
US08/988,847 1997-12-11
US60/032,452 1997-12-11

Publications (1)

Publication Number Publication Date
WO1998027159A1 true WO1998027159A1 (fr) 1998-06-25

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PCT/US1997/023514 WO1998027159A1 (fr) 1996-12-19 1997-12-17 Polyesters renforces tenaces dotes d'une fluidite amelioree

Country Status (5)

Country Link
EP (1) EP0951510A1 (fr)
JP (1) JP2002509565A (fr)
CN (1) CN1247551A (fr)
BR (1) BR9713952A (fr)
WO (1) WO1998027159A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
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WO2001021702A1 (fr) * 1999-09-23 2001-03-29 Eastman Chemical Company Formulations ameliorees de pct contenant des imides halogenes, un ou plusieurs composes phenoxy et des fibres de renforcement
WO2001021704A1 (fr) * 1999-09-23 2001-03-29 Eastman Chemical Company Procede permettant d'ameliorer la stabilite au vieillissement au four de formulations de pct par l'addition de composes phenoxy
WO2001025325A2 (fr) * 1999-09-23 2001-04-12 Eastman Chemical Company Formulations de pct ameliorees, contenant des imides halogenes, de l'antimoniate de sodium et des fibres de renforcement
WO2001027200A2 (fr) * 1999-09-23 2001-04-19 Eastman Chemical Company Compositions ameliorees a base de poly(cyclohexylenedimethylene terephtalte) contenant des imides halogenes, des modificateurs de la resistance aux chocs a fonction de caoutchouc et des fibres de renforcement
JP2002265765A (ja) * 2001-03-08 2002-09-18 Toagosei Co Ltd ポリエステル組成物
US7378470B2 (en) 2004-06-08 2008-05-27 Lanxess Deutschland Gmbh Molding compositions based on a thermoplastic polyester with improved flowability
EP2100918A1 (fr) * 2006-12-25 2009-09-16 Mitsubishi Rayon Co. Ltd. Agent améliorant la fluidité, composition de résine de polycarbonate aromatique et article moulé à partir de cette composition
US8021628B2 (en) 2005-01-20 2011-09-20 3M Innovatice Properties Company Structured polymer films
US8071673B2 (en) 2005-04-06 2011-12-06 Lanxess Deutschland Gmbh Moulding compositions based on a thermoplastic polycarbonate
US8642699B2 (en) 2008-03-11 2014-02-04 Mitsubishi Rayon Co., Ltd. Fluidity improver for aromatic polycarbonate resin, process for producing the fluidity improver for aromatic polycarbonate resin, aromatic polycarbonate resin composition, and molded product
US8729205B2 (en) 2003-09-30 2014-05-20 Mitsubishi Rayon Co., Ltd. Flowability improver for engineering plastics, thermoplastic resin compositions containing the same and molded articles of the compositions
US8734909B2 (en) 2010-03-10 2014-05-27 Eastman Chemical Company Methods and apparatus for coating substrates
CN103946247A (zh) * 2011-11-07 2014-07-23 沙特基础创新塑料Ip私人有限责任公司 在硬盘驱动器和半导体应用中使用的清洁聚碳酸酯材料
US8865261B2 (en) 2012-12-06 2014-10-21 Eastman Chemical Company Extrusion coating of elongated substrates
US9289795B2 (en) 2008-07-01 2016-03-22 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
CN106032430A (zh) * 2014-09-02 2016-10-19 富士施乐株式会社 树脂组合物和树脂成型体
US9604251B2 (en) 2008-07-16 2017-03-28 Eastman Chemical Company Thermoplastic formulations for enhanced paintability, toughness and melt processability
US9616457B2 (en) 2012-04-30 2017-04-11 Innovative Coatings, Inc. Pressurization coating systems, methods, and apparatuses
US9744707B2 (en) 2013-10-18 2017-08-29 Eastman Chemical Company Extrusion-coated structural members having extruded profile members
US9920526B2 (en) 2013-10-18 2018-03-20 Eastman Chemical Company Coated structural members having improved resistance to cracking
JP2020532630A (ja) * 2017-09-06 2020-11-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 熱可塑性ポリエステル成形組成物

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DE102005050957A1 (de) * 2005-10-25 2007-04-26 Lanxess Deutschland Gmbh Formmassen auf Basis eines thermoplastischen Polyesters mit verbesserter Fließfähigkeit
KR101266294B1 (ko) * 2008-12-19 2013-05-22 제일모직주식회사 폴리에스테르/폴리카보네이트 얼로이 수지 조성물
WO2014076971A1 (fr) 2012-11-19 2014-05-22 三井化学株式会社 Composition de résine de polyester, son procédé de fabrication et module caméra comportant ladite composition de résine de polyester
KR101849830B1 (ko) * 2015-06-30 2018-04-18 롯데첨단소재(주) 내충격성 및 광신뢰성이 우수한 폴리에스테르 수지 조성물 및 이를 이용한 성형품

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EP0747070A2 (fr) * 1995-06-06 1996-12-11 Advanced Cardiovascular Systems, Inc. Ballonnet pour cathéter à usage médical

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EP0747070A2 (fr) * 1995-06-06 1996-12-11 Advanced Cardiovascular Systems, Inc. Ballonnet pour cathéter à usage médical

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021702A1 (fr) * 1999-09-23 2001-03-29 Eastman Chemical Company Formulations ameliorees de pct contenant des imides halogenes, un ou plusieurs composes phenoxy et des fibres de renforcement
WO2001021704A1 (fr) * 1999-09-23 2001-03-29 Eastman Chemical Company Procede permettant d'ameliorer la stabilite au vieillissement au four de formulations de pct par l'addition de composes phenoxy
WO2001025325A2 (fr) * 1999-09-23 2001-04-12 Eastman Chemical Company Formulations de pct ameliorees, contenant des imides halogenes, de l'antimoniate de sodium et des fibres de renforcement
WO2001027200A2 (fr) * 1999-09-23 2001-04-19 Eastman Chemical Company Compositions ameliorees a base de poly(cyclohexylenedimethylene terephtalte) contenant des imides halogenes, des modificateurs de la resistance aux chocs a fonction de caoutchouc et des fibres de renforcement
WO2001025325A3 (fr) * 1999-09-23 2001-11-22 Eastman Chem Co Formulations de pct ameliorees, contenant des imides halogenes, de l'antimoniate de sodium et des fibres de renforcement
WO2001027200A3 (fr) * 1999-09-23 2002-01-10 Eastman Chem Co Compositions ameliorees a base de poly(cyclohexylenedimethylene terephtalte) contenant des imides halogenes, des modificateurs de la resistance aux chocs a fonction de caoutchouc et des fibres de renforcement
JP2002265765A (ja) * 2001-03-08 2002-09-18 Toagosei Co Ltd ポリエステル組成物
US8729205B2 (en) 2003-09-30 2014-05-20 Mitsubishi Rayon Co., Ltd. Flowability improver for engineering plastics, thermoplastic resin compositions containing the same and molded articles of the compositions
US7378470B2 (en) 2004-06-08 2008-05-27 Lanxess Deutschland Gmbh Molding compositions based on a thermoplastic polyester with improved flowability
EP1992662A3 (fr) * 2004-06-08 2008-12-03 Lanxess Deutschland GmbH Matières moulables à base de polyester thermoplastique présentant une fluidité améliorée
US8021628B2 (en) 2005-01-20 2011-09-20 3M Innovatice Properties Company Structured polymer films
US8071673B2 (en) 2005-04-06 2011-12-06 Lanxess Deutschland Gmbh Moulding compositions based on a thermoplastic polycarbonate
EP2100918A1 (fr) * 2006-12-25 2009-09-16 Mitsubishi Rayon Co. Ltd. Agent améliorant la fluidité, composition de résine de polycarbonate aromatique et article moulé à partir de cette composition
EP2100918A4 (fr) * 2006-12-25 2009-12-23 Mitsubishi Rayon Co Agent améliorant la fluidité, composition de résine de polycarbonate aromatique et article moulé à partir de cette composition
US8202943B2 (en) 2006-12-25 2012-06-19 Mitsubishi Rayon Co., Ltd. Fluidity-improving agent, aromatic polycarbonate resin composition, and shaped article thereof
US8642699B2 (en) 2008-03-11 2014-02-04 Mitsubishi Rayon Co., Ltd. Fluidity improver for aromatic polycarbonate resin, process for producing the fluidity improver for aromatic polycarbonate resin, aromatic polycarbonate resin composition, and molded product
US10576491B2 (en) 2008-07-01 2020-03-03 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
US9289795B2 (en) 2008-07-01 2016-03-22 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
US9604251B2 (en) 2008-07-16 2017-03-28 Eastman Chemical Company Thermoplastic formulations for enhanced paintability, toughness and melt processability
US8734909B2 (en) 2010-03-10 2014-05-27 Eastman Chemical Company Methods and apparatus for coating substrates
CN103946247A (zh) * 2011-11-07 2014-07-23 沙特基础创新塑料Ip私人有限责任公司 在硬盘驱动器和半导体应用中使用的清洁聚碳酸酯材料
US9616457B2 (en) 2012-04-30 2017-04-11 Innovative Coatings, Inc. Pressurization coating systems, methods, and apparatuses
US9919503B2 (en) 2012-12-06 2018-03-20 Eastman Chemical Company Extrusion coating of elongated substrates
US8865261B2 (en) 2012-12-06 2014-10-21 Eastman Chemical Company Extrusion coating of elongated substrates
US9744707B2 (en) 2013-10-18 2017-08-29 Eastman Chemical Company Extrusion-coated structural members having extruded profile members
US9920526B2 (en) 2013-10-18 2018-03-20 Eastman Chemical Company Coated structural members having improved resistance to cracking
CN106032430A (zh) * 2014-09-02 2016-10-19 富士施乐株式会社 树脂组合物和树脂成型体
CN106032430B (zh) * 2014-09-02 2018-05-18 富士施乐株式会社 树脂组合物和树脂成型体
JP2020532630A (ja) * 2017-09-06 2020-11-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 熱可塑性ポリエステル成形組成物

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EP0951510A1 (fr) 1999-10-27
BR9713952A (pt) 2000-03-21
CN1247551A (zh) 2000-03-15
JP2002509565A (ja) 2002-03-26

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