WO2000046296A1 - Composition de moulage a base de polyester - Google Patents

Composition de moulage a base de polyester Download PDF

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Publication number
WO2000046296A1
WO2000046296A1 PCT/US1999/030198 US9930198W WO0046296A1 WO 2000046296 A1 WO2000046296 A1 WO 2000046296A1 US 9930198 W US9930198 W US 9930198W WO 0046296 A1 WO0046296 A1 WO 0046296A1
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Prior art keywords
weight
composition
epoxy compound
thermoplastic resin
resin composition
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PCT/US1999/030198
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English (en)
Inventor
Sapna Halim Talibuddin
Vinod R. Sastri
Franciscus Mercx
Estelle Cheret
Robert Russell Gallucci
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General Electric Company
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Publication of WO2000046296A1 publication Critical patent/WO2000046296A1/fr

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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

Definitions

  • the invention relates to a molding composition
  • a molding composition comprising a glass filled polyester resin including an impact modifier and stabilizers.
  • the fibrous glass enhances the mechanical properties and heat distortion of the resin.
  • glass filled crystalline resin blends are often more difficult to mold.
  • the crystalline resin also has poor melt strength and high shrinkage upon cooling. Orientation of glass fibers and differential shrinkage between the glass and resin makes it difficult to obtain good dimensional tolerances.
  • Fiber glass filled parts usually have a higher degree of warp than seen in unfilled resin compositions.
  • glass reinforced blends also have a rough surface.
  • glass fibers can substantially lower the Izod impact strengths of the fiber reinforced compositions, and, also, substantially reduce the biaxial impact (instrumented impact) energies of such compositions.
  • impact modifiers have been added to poly(alkylene terephthalates) including rubbers of polybutadiene, butadiene- styrene copolymers, butadiene-acrylonitrile styrene copolymers, ethylene- propylene rubbers, polyisobutene and polyisoprene, alkyl acrylate acrylate rubbers and acrylate styrene acrylonitrile rubbers.
  • Acrylic based rubbers are preferred for many applications involving exposure to light because of their resistance to yellowing.
  • Blends of thermoplastic polyesters with acrylic rubbers have been described in the art.
  • Japanese 1978 publication, 53-129246 to relates to a polycarbonate and saturated polyester A and B components with the ASA (C) component comprising component (I) of at least one monomer such as styrene grafted on component (II) which is an elastomer based on the cross- linking copolymerization of a mixture of an acrylic ester and a cyclic monomeric compound of triallyl cyanurate and triallyl isocyanurate.
  • U.S. patent 4,096,202 to Franham et. al. describes modifiers based on acrylic rubbers for improving impact strength without significantly increasing melt viscosity for poly (alkylene terephthalates).
  • the impact modifier is a multi-phase composite interpolymer comprising a cross linked acrylic first stage which also contains graf tlinking monomer and a final rigid thermoplastic phase.
  • the crosslinking monomers include poly acrylic and poly methacrylic esters of polyols such as butylene diacrylate and dimethacrylate, trimethylol propane trimethacrylate, and the like; di- and trivinyl benzene, vinyl acrylate and methacrylate, and the like.
  • graftlinking monomers which are polyethylenically unsaturated monomers
  • allyl group-containing monomers of allyl esters of ethyleneically unsaturated acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, allyl acid maleate, allyl acid fumarate, and allyl acid itaconate.
  • the resulting multi-phase composite interpolymer is known in the art as an ASA polymer.
  • thermoplastic molding materials based on polyesters and graft polymers.
  • the thermoplastic molding materials based on a mixture of polybutylene terephthalate and polyethylene terephthalate as essential components, graft polymers having acrylate rubbers as the grafting base, copolymers of vinylaromatic monomers and acrylonitrile or methacrylonitrile and glass fibers.
  • compositions of both Examples also contained the following additives (in each case in % by weight, based on the total weight of A+B): 1.5% by weight of carbon black, 0.1% by weight of talc, 0.8% by weight of pentaerythritol stearate.
  • United States Patent 4J48,956 to Popefellner relates to thermoplastic molding compositions of linear polyesters and styrene/ acrylonitrile modified by alpha-methylstyrene and/ or acrylates.
  • inorganic or organic pigments such as glass fibers and glass beads, inorganic or organic pigments, optical brighteners, delustering agents, processing auxiliaries, such as lubricants, mould release agents and agents which promote crystallization, flameproofing agents, nucleating agents and stabilizers, such as phosphorus- organic compounds, for example triphenyl phosphite, can be added during working up of the polyester melt or even prior to the polycondensation reaction or during mixing of the polyesters with modified styrene/ acrylonitrile .
  • thermoplastic molding compositions comprise from 20 to 99% by weight of a polyester, up to 90% by weight of which may be replaced by a polycarbonate or a polyamide, from 0.1 to 7% by weight of a specific sterically hindered aliphatic carbodiimide.
  • the compositions may contain impact modifiers which are generally copolymers, preferably built up from at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and (meth)acrylates having from 1 to 18 carbon atoms in the alcohol component.
  • United States Patent 5,596,049 to Gallucci et. al. describes the stabilization of polyesters using epoxy compounds in combination with a catalyst.
  • the disclosed polyester composition comprises a linear polyester resin, a difunctional epoxy compound and a catalyst.
  • the difunctional epoxy compound has two terminal epoxy functionalities.
  • Examples of preferred difunctional epoxy compounds are 3,4-epoxycyclohexyl-3,4- epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene di-epoxide, and the like.
  • 3,4- epoxycyclohexyl-3,4 epoxycyclohexylcarboxylate is especially preferred.
  • United States Patent 4,894,416 to Gallucci relates to low gloss thermoplastic blends with good physical properties consisting of a blend of ASA and a gloss-reducing amount of a glycidyl (meth)acrylate copolymer.
  • the compositions of the prior art still suffer from limitations with respect to impact, modulus and retention of mechanical properties and melt viscosity under hydrolytic conditions and from poor dimensional stability and warp. Accordingly, there is a need for glass reinforced polyester resin compositions which exhibit consistent and uniform properties together with enhanced properties of improved hydrolysis resistance and reduced warp.
  • compositions of the present invention unexpectedly exhibit reduced warp over compositions employing no epoxide.
  • thermoplastic glass filled resin composition having improved hydrolysis resistance and reduced warp properties
  • a resin blend consisting essentially of an alkylene aryl polyester, a core-shell or graft ASA (alkylacrylate-styrene-acrylonitrile interpolymer) and an effective amount of at least one difunctional epoxy compound.
  • the difunctional epoxy compound includes at least one cyclohexane ring moiety and has two terminal epoxy functional groups. At least one of the two terminal epoxy functional groups is a substituent on the at least one cyclohexane ring moiety.
  • An effective amount of a catalyst compound is utilized.
  • the composition may further contain a carbodiimide stabilizer to improve said performance.
  • FIG. 1 Type I illustrates the USCAR III hydrolysis test procedure.
  • compositions comprising linear polyesters, difunctional epoxides and salts of aliphatic carboxylic acids provide a composition which possesses both improved hydrolytic stability and retention of melt viscosity stability. Further, preferred polyester compositions possess high melt viscosity and reduced warp. The compositions of the present invention unexpectedly exhibit improved results over compositions without epoxides.
  • the preferred difunctional polyepoxy compound is 3,4- epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.
  • the preferred catalysts are salts of an aliphatic or aromatic carboxylic acids.
  • the most preferred catalysts are Group IA (alkaline) metal carboxylates .
  • the epoxy component is at least one difunctional epoxy compound.
  • difunctional epoxy compound is meant a compound having two terminal epoxy functionalities.
  • the compound will contain only carbon, hydrogen and oxygen.
  • the compound will preferably have a molecular weight of below about 1000 to facilitate blending with the polyester resin.
  • Preferred difunctional epoxy compounds will have at least one of the epoxide groups on a cyclohexane ring.
  • Examples of preferred difunctional epoxy compounds are 3,4-epoxycyclohexyl-3,4-epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene di-epoxide, , epoxy cyclohexane adducts of carboxylic acids and the like. Especially preferred is 3,4-epoxycyclohexyl-3,4 epoxycyclohexylcarboxylate.
  • the difunctional epoxide compounds can be made by techniques well known to those skilled in the art.
  • the corresponding alpha, beta- dihydroxy compounds can be dehydrated to produce the epoxide groups, or the correspondingly unsaturated compounds can be epoxidized by treatment with a peracid, such as peracetic acid, in well-known techniques.
  • a peracid such as peracetic acid
  • the difunctional epoxy compound may be employed in any effective amount, but preferably small amounts are use, e.g., at a range of about 0.1 to about 5 percent by weight. However, a particularly preferred range is from about 01 to about 3.5 percent by weight. A more preferred range is from about 0.5 to about 2 percent by weight. Within this particularly preferred range it has been found advantageous to employ in certain compositions from about 1 to about 2.0 percent by weight of the difunctional polyepoxy compound. All percentages are based on the total weight of the blend.
  • catalyst compound Another component of the present invention consists of the catalyst compound.
  • Preferred catalysts are salts free from direct carbon-phosphorous bonds and containing at least one of alkali metal cations and alkaline earth metal cations and halide anions. It is apparent that this class contains a large number of compounds. They include alkali metal halides, alkali metal carboxylates, and alkali metal carbonates.
  • Illustrative compounds within this class are lithium fluoride, lithium iodide, potassium bromide, potassium iodide, sodium acetate, sodium benzoate, sodium caproate, sodium stearate, and potassium oleate.
  • the catalyst component can be present in the composition of the present invention in any effective amount.
  • the catalyst is present in an amount ranging from about 0.001 to about 1 weight percent, more preferably from about 0.03 to about 0.1 weight percent based on the total weight of the resin composition.
  • Carbodiimides can also be used in combination with the epoxides and catalyst of the present invention to improve hydrolysis resistance. Both monomeric and polymeric carbodiimides can be used although polymeric carbodiimides may be preferred due to the potential for lower plate out.Carbodiimides of the following structure may be used:
  • the combination of epoxide with carbodiimide gives surprisingly better color and extends the effectiveness of the more expensive carbodiimide. Overall lower levels of carbodiimide in the blends may reduce the potential generation of unwanted isocyanates by reaction of carbodiimide with water.
  • the epoxy carbodumide combination reduces carbodiimide loading while retaining good hydrolysis resistance with improved color over the epoxide alone. Carbodiimide loadings of 0.01 to 5.0% are preferred.
  • alkylene aryl polyester refers to crystalline thermoplastic polyesters such as polyesters derived from an aliphatic or cycloaliphatic diols, or mixtures thereof, containing from 2 to about 10 carbon atoms and at least one aromatic dicarboxylic acid.
  • Preferred polyesters are derived from an aliphatic diol and an aromatic dicarboxylic acid having repeating units of the following general formula :
  • R is a C-6-C20 aryl radical comprising a decarboxylated residue derived from an aromatic dicarboxylic acid.
  • aromatic dicarboxcylic acids represented by the decarboxylated residue R are isophthalic or terephthalic acid, l,2-di(p- carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4' bisbenzoic acid and mixtures thereof. All of these acids contain at least one aromatic nucleus.
  • Acids containing fused rings can also be present, such as in 1,4- 1,5- or 2,6- naphthalenedicarboxylic acids.
  • the preferred dicarboxcylic acids are terephthalic acid, isophthalic acid, naphthalene dicarboxcylic acid or mixtures thereof.
  • polyesters poly(ethylene terephthalate) (“PET”), and poly(l,4-butylene terephthalate), (“PBT”), poly(ethylene naphthanoate) (“PEN”), poly(butylene naphthanoate), (“PBN”) poly (propylene terephthalate)
  • PET poly(ethylene terephthalate)
  • PBT poly(l,4-butylene terephthalate)
  • PEN poly(ethylene naphthanoate)
  • PBN poly(butylene naphthanoate) poly (propylene terephthalate)
  • polyesters with minor amounts, e.g., from about 0.5 to about 5 percent by weight, of units derived from aliphatic acid and/ or aliphatic polyols to form copolyesters.
  • the aliphatic polyols include glycols, such as poly(ethylene glycol).
  • Such polyesters can be made following the teachings of, for example, U.S. Pat. Nos. 2,465,319 and 3,047,539.
  • the preferred poly(l,4-butylene terephthalate) resin used in this invention is one obtained by polymerizing a glycol component at least 70 mol %, preferably at least 80 mol %, of which consists of tetramethylene glycol and an acid component at least 70 mol %, preferably at least 80 mol %, of which consists of terephthalic acid, or polyester-forming derivatives therefore.
  • polyesters used herein have an intrinsic viscosity of from about 0.4 to about 2.0 dl/gas measured in a 60:40 phenol/ tetrachloroethane mixture or similar solvent at 23°-30° C.
  • VALOX Registered TM 315 polyester is particularly suitable for this invention having an intrinsic viscosity of 1.1 to 1.4 dl/g.
  • Blends of polyesters may also be employed in the composition.
  • preferred polyester blends are made from poly(ethylene terephthalate) and poly(l,4-butylene terephthalate).
  • core-shell ASA alkylacrylate-styrene-acrylonitrile interpolymer refers to a thermoplastic resin which comprises a styrene- acrylonitrile matrix in which is dispersed an acrylate elastomer phase as impact modifier.
  • ASA is a multi-phase composite interpolymer comprising about 25 to 95 weight percent of a first elastomeric phase and about 75 to 5 weight percent of a final rigid thermoplastic phase.
  • the first phase or stage is polymerized from about 75 to 99.8 weight percent C2 to C10, preferably a -C ⁇ , most preferably a G. alky (meth) acrylate resulting in an acrylic rubber core having a T g below about 10° C and crosslinked with 0.1 to 5 weight percent crosslinking monomer and further containing 0J to 5 percent by weight graftlinking monomer.
  • the preferred alkyl acrylate is butyl acrylate.
  • the cross-Linking monomer is a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups all of which polymerize at substantially the same rate of reaction.
  • Suitable crosslinking monomers include poly acrylic and poly methacrylic esters of polyols such as butylene diacrylate and dimethacrylate, trimethylol propane trimethacrylate, and the like; di- and trivinyl benzene, vinyl acrylate and methacrylate, and the like.
  • the preferred crosslinking monomer is butylene diacrylate.
  • the graftlinking monomer is a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups, at least one of which polymerizing at substantially different rate of polymerization from at least one other of said reactive groups.
  • the function of the gr---ftlinking monomer is to provide a residual level of unsaturation in the elastomeric phase, particularly in the latter stages of polymerization and, consequently, at or near the surface of the elastomer particles.
  • the rigid thermoplastic phase is subsequently polymerized at the surface of the elastomer, the residual unsaturated addition polymerizable reactive group contributed by the graftlinking monomer participates in the subsequent reaction so that at least a portion of the rigid phase is chemically attached to surface of the elastomer.
  • the final phase or stage monomer system can be comprised of O to Ci ⁇ methacrylate, styrene, acrylonitrile, alkyl acrylates, allyl methacrylate, diallyl methacrylate, and the like, as long as the over T g is at least 20 degrees C.
  • the final stage monomer system is at least 50 weight percent Ci to Q alkyl methacrylate.
  • the final stage polymer be free of units which tend to degrade poly(alkylene terephthalates), for example acid, hydroxyl amino, and amine groups.
  • One or more intermediate phases are optional, for example a middle stage polymerized from about 75 to 100 percent by weight styrene.
  • ASA resins which are commercially available comprise a crosslinked (meth)acrylate elastomer, a crosslinked styrene-acrylonitrile copolymer and a substantially linear styrene-acrylonitrile copolymer.
  • Methylated styrenes such as alpha-methylstyrene or vinyltoluene may be used in place of all or part of the styrene, and it is understood that when styrene is mentioned hereinafter, these methylated styrenes are encompassed.
  • the preferred resins of the ASA type are composed of core-shell impact modifiers in a styrene-acrylonitrile (SAN) matrix.
  • SAN styrene-acrylonitrile
  • the (meth)acrylate elastomer core portion of these resins may be composed of alkyl, or arylalkyl esters of acrylic or methacrylic acids.
  • the alkyl (meth)acrylate alkyl is C2 to Oo with the butyl Q being most preferred, i.e. the core comprises a poly butylacrylate rubber.
  • the core shell portion of the resin may be prepared by a two-step process in which the (meth)acrylate elastomer core (which is often slightly crosslinked with polyfunctional vinyl compounds) is covered with a thermoplastic shell of polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, or similar vinyl polymers or copolymers.
  • compositions may or may not have a comonomer to graft the core shell structure together.
  • ASA resins may be made for instance by the process of U.S. Pat. No. 3,944,631 (Mar. 1976).
  • the most preferred resins of this group comprise about 15 to about 90% of an uncrosslinked matrix of acrylonitrile-styrene copolymer polymerized and partly grafted on a core- shell impact modifier, typically about 5 to 50% of a crosslinked (meth)acrylate elastomer core with about 15 to about 35% of a crosslinked styrene- acrylonitrile copolymer shell.
  • the crosslinking monomer may be typically a diacrylate of a diol.
  • the shell and core are believed to be linked by having interpenetrating molecular networks, and the term interpolymer is applied to such products having such networks.
  • ASA resins which may be advantageously used in the composition of the invention are the types disclosed in U.S. Pat. Nos. 3,655,824, 3,830,878, 3,991,009, 4,433,102, 4,442,263, 4,096,202 and, 4,409,363, all of which are incorporated herein by reference thereto.
  • These ASA resins have in common the use of the three monomers, namely acrylate ester, styrene (or alpha-methylstyrene), and acrylonitrile, to make a thermoplastic with good impact, heat distortion and weathering characteristics. They differ principally in the method of manufacture and in the detailed structure of the essential rubbery phase and the interphases if any.
  • the ASA resins have relatively similar blending properties in view of their outer continuous phase of acrylonitrile-styrene copolymer.
  • the polyester/ ASA/ glass resin blend preferably consists essentially of the polyester, ASA, fiber glass, cyclohexyl difunctional epoxide and catalyst.
  • the blends comprises about 20 to 80, most preferably 30 to 70 pbw polyester per part of resin blend.
  • the present molding compositions are reinforced or stiffened by the inclusion of a fibrous glass, preferably glass fibers, in amounts ranging from about 3 to 50 pbw of the total composition, preferably from about 7 to about 45 pbw, more preferably from about 10 to about 30 pbw.
  • the glass fiber or filamentous glass employed as reinforcement in the present compositions preferably comprise lime-aluminum borosilicate glass that is relatively soda-free.
  • the filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling.
  • fibrous glass filaments comprised of borosilicate glass that is relatively soda-free. This is known as "E" glass.
  • the filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling.
  • the preferred filaments for plastic reinforcement are made by mechanical pulling.
  • the filament diameters range from about 3 to 30 microns .
  • the filament diameters preferably range from about 10-15 microns. Use of equivalent non-round fiber cross section is also possible.
  • 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, or woven into mats and the like are also not critical to the invention.
  • filamentous glass in the form of chopped strands of from about one- eighth to about 2 inches long.
  • articles molded from the compositions on the other hand, even shorter lengths will be encountered because, during compounding, considerable fragmentation will occur. This is desirable, however, because the best properties are exhibited by thermoplastic injection molded articles in which the filament lengths lie between about 0.000005" and 0.125 ( 1/8 ").
  • the most preferable resin blend optionally includes from 1.0 to about 30, more preferably from 3 to 10 pbw of vinyl aromatic- vinyl cyanide copolymer.
  • the preferred SAN composition comprises 15 to 40, more preferably 30-40, percent by weight AN with the remainder styrene, para- methystyrene, alpha- methyl styrene.
  • the vinyl cyanide compound includes acrylonitrile (AN) and substituted vinyl cyanides such a methacrylonitrile.
  • the copolymer is a styrene-acrylonitrile copolymer (SAN).
  • the preferred SAN is copolymer with the vinyl cyanide being present from about 20 to about 40 pbw based on total weight of the SAN. In the resin portion of the composition, it is desirable to have from about 5 to about 30, and preferable from about 10 to about 20 pbw free SAN based on the total composition.
  • composition of the present invention may include additional components which do not interfere with the previously mentioned desirable properties but enhance other favorable properties.
  • Flame-retardant additives may be present in an amount sufficient to reduce the flammability of the polyester resin, preferably to a UL94 V-0 rating.
  • the amount will vary with the nature of the resin and with the efficiency of the additive. In general, however, the amount of additive will be from 2 to 20 percent by weight based on the weight of resin. A preferred range will be from about 5 to 15 percent.
  • halogenated aromatic flame-retardants include tetrabromobisphenol A polycarbonate oligomer, polybromophenyl ether, brominated polystyrene, brominated BPA polyepoxide, brominated imides, brominated polycarbonate, poly (haloaryl acrylate), poly (haloaryl methacrylate), or mixtures thereof.
  • Examples of other suitable flame retardants are brominated polystyrenes such as polydibromostyrene and polytribromostyrene, decabromobiphenyl ethane, tetrabromobiphenyl, brominated alpha , omega - alkylene-bi-s-phthalimides, e.g. N,N'-e ylene-bis-tetrabromophthalimide, oligomeric brominated carbonates, especially carbonates derived from tetrabromobisphenol A, which, if desired, are end-capped with phenoxy radicals, or with brominated phenoxy radicals, or brominated epoxy resins.
  • Other aromatic carbonate flame retardants are set forth in U.S. Patent 4,636,544 to Hepp.
  • the flame retardants are typically used with a synergist, particularly inorganic antimony compounds.
  • a synergist particularly inorganic antimony compounds.
  • Such compounds are widely available or can be made in known ways.
  • Typical, inorganic synergist compounds include Sb2 ⁇ s; SbS ; and the like.
  • antimony trioxide Sb2 ⁇ 3
  • Synergists such as antimony oxides, are typically used at about 0.5 to 15, and more preferably from 1 to 6 percent by weight based on the weight percent of resin in the final composition.
  • the final composition may contain polytetrafluoroethylene
  • PTFE PTFE type resins or copolymers used to reduce dripping in flame retardant thermoplastics.
  • the blend may also contain colorants, mold releases, lubricants, antioxidants, UV stabilizers and other similar additives to enhance performance.
  • the blends of this invention can be processed by various techniques including injection molding, blow molding, extrusion into sheet, film or profiles, compression molding, etc. They can also be formed into a variety of articles for use in, for example; electrical connectors, electrical devices, computers, building and construction, outdoor equipment, trucks and automobiles. Illustrative of the various molded articles are connectors, outdoor electrical enclosures and cabinets, structural parts in outdoor lighting applications, telecom enclosure housings, industrial power plugs. Important applications are automotive exterior parts such as door handles and luggage racks.
  • Tables 1-3 The components of the formulations presented in Tables 1-3 were tumble blended and then extruded on a 2 ; 5" 30:1 L/D HPM single-screw extruder equipped with a vacuum vented, double-wave screw. A processing profile of 490-510 from feed-zone to die-head was employed. The compositions were dried at 250°F for 4 hours and then injection molded into test specimens on an 85 ton Van Dorn molding machine with a barrel set temperature of 500-510 , 150 mold temperature, 12 s injection time, 14-18 s hold time and 100 psi back pressure.
  • Tensile bars of Type I and Type V, Izod bars and 4.0" diameter disks, all of 0.125" thickness were employed for tensile, unnotched Izod impact and instrumented impact tests, respectively, while 4.0" diameter, edge gated disks of 0.062" thickness were used for as- molded warp tests.
  • Type I tensile bars and instrumented impact discs were aged according to the USCAR III hydrolysis test procedure, as illustrated in Fig. 1.
  • Test parts were exposed to 60 temperature/ humidity cycles. After each exposure, samples were held under ambient conditions prior to testing. Tensile and instrumented impact tests were conducted as per ASTM D638 and ASTM D3763 procedures, respectively. Sample compositions and test results are presented in Table 1.
  • Epoxide ERL 4221 0 1.50 0 1.50
  • ERL4221 is 3,4 -epoxycyclohexylmethyl-3,4-epoxy cyclohexane carboxylate from Union Carbide Co.
  • Irganox 1076 is a hindered phenol ester antioxidant from the Ciba Geigy Co.
  • Example 1 clearly shows that the epoxide modified samples (Examples 1 and 2) exhibit significantly lower as-molded warp and superior tensile and impact properties on hydro-aging over the corresponding unmodified PBT/ ASA blends (Comparative examples A and B). Improved properties are especially evident after 40 & 60 cycles of aging.
  • Examples 3-8 Pressurized Steam Aging Sample pellets, Izod bars and type V tensile bars were aged by suspending these above water in a pressure steam sterilizer, Model No. 25X, Wisconsin Aluminum Foundry Company, at 100% relative humidity, 110°C temperature and 0.5 kg/ cm 2 pressure. After each exposure, samples were held under ambient conditions prior to testing.
  • Epoxide ERL 4221 0 0.20 1.20 2.40
  • Polyester 4 56.30 56.35 56.30 56.30 56.30
  • Epoxy ERL 4221 1.20 0 0.36 0.60 0.84
  • Carbodiimide STABAXOL I 0 1.20 0.84 0.60 0.36
  • Staboxol I is 2,2',6,6'-tetraisopropyl diphenyl carbodiimide from Wyrough & Loser Co.
  • Table 3 depicts the effect of various mixtures of epoxide and carbodiimide on melt viscosity and mechanical properties of as-prepared and hydro-aged PBT/ ASA compositions. Note that Example 4 is carried forward from Table 2 for purposes of comparison. For the Examples of Table 4 the total level of stabilizer , i.e. sum of epoxide and carbodiimide loadings, is the same at 1.2 parts per hundred.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention se rapporte à une composition de résine thermoplastique contenant de la fibre de verre, qui présente une résistance à l'hydrolyse améliorée et une aptitude réduite au gauchissement. Cette composition comprend un mélange de résines composé principalement d'un polyester aryle-alkylène, d'un ASA de type à noyau et enveloppe (interpolymère d'alkylacrylate-styrène-acrylonitrile) et d'une quantité efficace d'au moins un composé époxy bifonctionnel comportant au moins une fraction cyclique de cyclohexane et ayant au moins deux groupes fonctionnels époxy terminaux, l'un au moins des deux groupes fonctionnels époxy terminaux étant un substituant sur ladite fraction cyclique de cyclohexane. Ladite composition comporte également une quantité efficace d'un composé catalyseur et de 0 à 5 % d'un carbodiimide.
PCT/US1999/030198 1999-02-03 1999-12-17 Composition de moulage a base de polyester WO2000046296A1 (fr)

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US24333099A 1999-02-03 1999-02-03
US09/243,330 1999-02-03

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WO2000046296A1 true WO2000046296A1 (fr) 2000-08-10

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2325256A1 (fr) * 2008-09-10 2011-05-25 NTN Corporation Corps moulé par injection, palier coulissant en résine, roue dentée en résine, couronne de support en résine, joint d'étanchéité en résine et palier de roulement
KR101367251B1 (ko) 2011-06-23 2014-02-25 제일모직 주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
EP3632938B1 (fr) * 2018-10-05 2023-05-03 Trinseo Europe GmbH Monomère aromatique à vinylidène substitué et polymères d'esters (méth)acrylates cycliques

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EP0310977A2 (fr) * 1987-10-07 1989-04-12 BASF Aktiengesellschaft Compositions à mouler thermoplastiques, renforcées par des fibres de verre, à base de polyester et de polymères greffés
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EP0712899A1 (fr) * 1994-11-19 1996-05-22 General Electric Company Résines de polyesters renforçees par des fibres de verre et stables à l'hydrolyse
US5596049A (en) * 1991-07-18 1997-01-21 General Electric Company Stabilization of polyesters using epoxy compounds in combination with a catalyst
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EP0310977A2 (fr) * 1987-10-07 1989-04-12 BASF Aktiengesellschaft Compositions à mouler thermoplastiques, renforcées par des fibres de verre, à base de polyester et de polymères greffés
EP0386546A2 (fr) * 1989-03-06 1990-09-12 General Electric Company Compositions à mouler thermoplastiques
US5596049A (en) * 1991-07-18 1997-01-21 General Electric Company Stabilization of polyesters using epoxy compounds in combination with a catalyst
JPH05287181A (ja) * 1992-04-09 1993-11-02 Mitsubishi Rayon Co Ltd ウエルド強度及び耐熱安定性に優れた高流動性熱可塑性樹脂組成物
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JPH0987491A (ja) * 1995-09-22 1997-03-31 Nippon G Ii Plast Kk 耐候性改良樹脂組成物および照明器具用成形品

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2325256A1 (fr) * 2008-09-10 2011-05-25 NTN Corporation Corps moulé par injection, palier coulissant en résine, roue dentée en résine, couronne de support en résine, joint d'étanchéité en résine et palier de roulement
EP2325256A4 (fr) * 2008-09-10 2012-12-19 Ntn Toyo Bearing Co Ltd Corps moulé par injection, palier coulissant en résine, roue dentée en résine, couronne de support en résine, joint d'étanchéité en résine et palier de roulement
KR101367251B1 (ko) 2011-06-23 2014-02-25 제일모직 주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
EP3632938B1 (fr) * 2018-10-05 2023-05-03 Trinseo Europe GmbH Monomère aromatique à vinylidène substitué et polymères d'esters (méth)acrylates cycliques

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