EP0305514A1 - Compositions de polyesters modifiees par impact ayant une meilleure resistance a la chaleur - Google Patents

Compositions de polyesters modifiees par impact ayant une meilleure resistance a la chaleur

Info

Publication number
EP0305514A1
EP0305514A1 EP88904732A EP88904732A EP0305514A1 EP 0305514 A1 EP0305514 A1 EP 0305514A1 EP 88904732 A EP88904732 A EP 88904732A EP 88904732 A EP88904732 A EP 88904732A EP 0305514 A1 EP0305514 A1 EP 0305514A1
Authority
EP
European Patent Office
Prior art keywords
poly
composition
weight
grafted
amount
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
EP88904732A
Other languages
German (de)
English (en)
Inventor
Charles Franklyn Pratt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
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 General Electric Co filed Critical General Electric Co
Publication of EP0305514A1 publication Critical patent/EP0305514A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones

Definitions

  • This invention relates to heat resistant impact modified thermoplastic molding compositions and, more par ⁇ ticularly, to glycidyl methacrylate or glycidyl acrylate grafted EPDM impact modifiers for thermoplastic polyester, copolyester and polyblend molding compositions that also include glassy polymers to improve heat resistance.
  • poly(l,4-butylene terephthalate) or PBT because of its very rapid crytallization from the melt, is uniquely useful as a component in such compositions.
  • Work pieces molded from such polyester resins in comparison with other thermoplastics, offer a high degree of surface hardness and abrasion resist ⁇ ance, high gloss and lower surface friction.
  • poly(1,4-butylene tere ⁇ phthalate) is much simpler to use in injection molding tech ⁇ niques than poly(ethylene terephthalate).
  • thermoplastic linear crystalline polyesters including poly(l,4-butylene tereph ⁇ thalate)
  • EPDM ethylenepropylene nonconjugated diene rubbery terpolymer
  • thermoplastic molding composition consisting of a thermoplastic resin, e.g., polyester, copolyester or block copolyester and a rubbery polymer comprising EPDM epoxidized with, e.g., m- chloroperoxy-benzoic acid and, optionally, a second non- rubbery, glassy thermoplastic polymer, e.g., aromatic poly ⁇ carbonate, to enhance surface characteristics and/or capability.
  • a thermoplastic resin e.g., polyester, copolyester or block copolyester
  • a rubbery polymer comprising EPDM epoxidized with, e.g., m- chloroperoxy-benzoic acid and, optionally, a second non- rubbery, glassy thermoplastic polymer, e.g., aromatic poly ⁇ carbonate, to enhance surface characteristics and/or capability.
  • Epstein U.S. 4,172,859, discloses the use of glassy random copoly ers, e.g., polycarbonate with PET or PBT which contain various polar monomers. He also alludes to the use of materials grafted with various polar monomers, e.g., glycidyl methacrylate (GMA) , to impact modify thermoplastic polyesters including PBT and PET, and polycarbonate. How ⁇ ever, this patent does not deal with and therefore fails to recognize one factor that is critical to the function of EPDM-g-GMA materials as impact modifiers for PBT and poly ⁇ carbonate systems. It does not recognize the benefits of reactive glycidyl ( eth)acrylates as graft monomers over non-reactive polar monomers such as maleic anhydride or n-vinyl pyrrolidone.
  • reactive glycidyl ( eth)acrylates as graft monomers over non-reactive polar monomers such as maleic anhydride or n-vin
  • thermo ⁇ plastic polymers having an amorphous glass transition temper ⁇ ature above about 100°C. can be incorporated in relatively small amounts into thermoplastic polyester compositions comprising glycidyl methacrylate grafted EPDM (EPDM-g-GMA) impact modifiers, and that such compositions will exhibit improved heat resistance as measured conveniently by heat distortion, despite the fact that a major proportion of the composition comprises polyesters having a relatively low glassy transition temperature, e.g., below about 80°C. and especially below about 75°C.
  • the advan ⁇ tageous effect on heat resistance is obtained without dimin ⁇ ishing significantly the impact strength and knit-line characteristics of such compositions.
  • the improved heat resistance of these impact-modified polyester compositions may be due to the reinforcing effect of small regions of glassy polymer in the matrix, offsetting the tend- ency of the polyester, e.g., PET or PBT, to soften at temper ⁇ atures above their relatively low amorphous glass transition temperatures, which for PET is about 73°C. and for PBT is about 59°C.
  • thermoplastic compositions comprising:
  • thermoplastic poly ⁇ ester resin having an amorphous glass transition temperature of below about 80°C
  • an effective amount of an impact improving rubbery polymer comprising an EPDM terpolymer grafted with glycidyl methacrylate or glycidyl acrylate or a mixture thereof, alone, or grafted in further combination with a C,-C lfl alkyl methacrylate or acrylate or a mixture thereof; and
  • component (c) a small, effective amount of a heat resistance improving thermoplastic polymer having an amorphous glass transition temperature above about 100°C.
  • Preferred features of the invention are composit- ions as defined above wherein component (a) comprises an amount of from about 30 to about 90 parts by weight, compon ⁇ ent (b) comprises an amount of from about 10 to about 55 parts by weight and component (c) an amount of from about 0.5 to about 15 parts by weight, based on a total composition of 100 parts by weight of (a), (b) and (c) combined.
  • the high-molecular weight linear polyesters used as component (a) in the practice of the present invention are polymeric glycol esters of terephthalic acid and isophthalic acid. They are available commercially or can be prepared by known techniques, such as by the alcoholysis of esters of phthalic acid with a glycol and subsequent polymerization, by heating glycols with free acids or with halide derivatives thereof, and similar processes. These are described in U.S. 2,465,319 and U.S. 3,047,539, and elsewhere.
  • glycol portion of the polyester can contain from 2 to 10 carbon atoms, it is preferred that it contain from 2 to 4 carbon atoms in the form of linear methylene chains.
  • polyesters will be of the family consisting of high molecular weight, polymeric glycol terephthalates or isophthalates having repeating units of the general formula:
  • n is a whole number of from 2 to 4 , and mixtures of such esters, including copolyesters of terephthalic and iso ⁇ phthalic acids of up to about 30 mole percent isophthalic units.
  • polyesters are poly(ethylene terephthalate) and poly(l,4-butylene terephthalate) .
  • high molecular weight polyesters will have an intrinsic viscosity of at least about 0.7 deci ⁇ liters/gram and, preferably, at least 0.8 deciliters/gram as measured in a 60:40 phenol-tetrachloroethane mixture at 30°C. At intrinsic viscosities of at least about 1.0 deciliters/ gram, there is a further enhancement of toughness of the present compositions.
  • Copolyesters useful for the invention are preferably prepared from terephthalic acid and/or isophthalic acid and/or a reactive derivative thereof and one or more glycols, which may be a straight or branched chain aliphatic/cycloaliphatic glycol.
  • the glycol will be ethylene glycol; 2-methyl-l,3-propanediol, 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,9-nonanediol; 1,10-decanediol; neopentyl- glycol; 1,4-cyclohexanediol; 1 r 4-cyclohexanedimethanol; a mixture of any of the foregoing, or the like.
  • suitable aliphatic dicarboxylic acids for the mixed aromatic/aliphatic embodiments ar suberic, sebacic, azelaic, and adipic acids and the like.
  • the copolyesters may be prepared by ester inter ⁇ change in accordance with the standard procedures.
  • the co- polyesters may preferably be derived from at least 50% butylene terephthalate units.
  • the block copolyesters useful in the composition of this invention are prepared by the reaction of terminally re ⁇ active poly(l,4-butylene terephthalate), preferably of low molecular weight, and a terminally reactive copolyester or aliphatic polyester or both in the presence of a catalyst for transesterification, such as zinc acetate, manganese acetate, titanium esters, and the like.
  • the terminal groups can com ⁇ prise hydroxyl, carboxyl, carboalkoxy, and the like, includ- ing reactive derivatives thereof.
  • polymerization is carried out under standard conditions, e.g., 220° to 280°C, in a high vacuum, e.g., 0.1 to 2 mm Hg, to form the block copolymer of minimum randomization in terms of distribution of chain segments.
  • a high vacuum e.g., 0.1 to 2 mm Hg
  • the result of reaction between two terminally reactive groups must be an ester linkage.
  • copolyester designated component of these block copolyesters may be terminally reactive segments of copoly- esters as described above.
  • copolyesters are most pre ⁇ ferably derived from an aliphatic glycol and a mixture of aromatic and aliphatic dibasic acids in which the mole ratio concentration of aromatic to aliphatic acids is from between 1 to 9 to about 9 to 1, with an especially preferred range being from about 3 to 7 to about 7 to 3.
  • terminally reactive aliphatic polyester compon ⁇ ent of these block copolyesters will contain substantially stoichiometric amounts of the- aliphatic diol and the alipha ⁇ tic dicarboxylic acid.
  • aromatic/aliphatic copoly ⁇ esters and aliphatic polyesters are commercially available.
  • One source for such materials is the Ruco Division/Hooker Chemical Company, Hicksville, New York, which designates its compounds as "Rucoflex".
  • the block copolyesters used in the invention prefer ⁇ ably comprise from about 95 to about 50 parts by weight based on the block copolyester of. poly(1,4-butylene terephthalate) segments.
  • the pol (1,4-butylene terephthalate) blocks-, before incorporation into the block copolyesters, will preferably have an intrinsic viscosity of about 0.1 dl./g. and, prefer ⁇ ably, between about 0.1 and about 0.5 dl./g., as measured in a 60:40 mixture of phenol-tetrachloroethane at 30°C.
  • the balance 50 to 5 parts by weight of the copolyester will com- prise blocks of the aforementioned aromatic/aliphatic copolyesters and/or aliphatic polyesters.
  • the poly(l,4-butylene terephthalate) block can be straight chain or branched, e.g., by use of a branching component, e.g., from about 0.05 to about 1 mole percent, based on tere ⁇ phthalate units of a branching component which contains at least 3 ester-forming groups.
  • a branching component e.g., from about 0.05 to about 1 mole percent, based on tere ⁇ phthalate units of a branching component which contains at least 3 ester-forming groups.
  • This can be a polyol, e.g., pentaerythritol, trimethylol-propane, and the like or a poly- basic acid compound, e.g., trimethyl tri estate, and the like.
  • Blends of the foregoing homopolymers, copolymers and/or block copolymers or derivatives thereof are also use ⁇ ful for the invention.
  • the glycidyl ester grafted terpolymer additives used in the rubbery polymeric impact modifier (b) in this invention may be prepared from any of the well known EPDM terpolymer rubbers.
  • EPDM terpolymers useful for preparing the grafted materials used in the invention are commercially available, e.g., Copolymer Corp. (EPSYN* 55) r or may be pre ⁇ pared using a Ziegler-type catalyst.
  • the preparation of typical EPDM terpolymers is described, for example, in Gresham et al., U.S. 2,933,480; Tarney, U.S. 3,000,866; Guglielminp et al., U.S.
  • EPDM terpolymers for the production of the glycidyl ether grafted terpolymers used in this invention comprise ethylene, a C, to C-, g straight or branched chain alpha-olefin, preferably propylene, and a non-conjugated di- olefin.
  • Satisfactory nonconjugated dienes that may be used as the third monomer in the terpolymer include straight chain dienes such as 1,4-hexanediene, cyclic dienes such as cyclo- octadiene and bridged cyclic dienes such as ethylidene norbornene.
  • Preferred EPDM terpolymers are comprised of about 10-95, preferably 45-70 mole percent, by weight ethylene, about 5 to 90, preferably 30-55 mole percent polypropylene and a minor amount of diene monomer, most preferably a poly- unsaturated bridged ring hydrocarbon or halogenated deriva ⁇ tive thereof, most preferably 5-ethylidene-2-norbornene.
  • These EPDM terpolymers have a melt " index of approximately 79 g/10 in., a Mooney viscosity of approximately 78 and a gram molecular weight of about 21,600.
  • the backbone rubber is subsequently graft modified with a graft monomer of epoxy functional acrylate or meth ⁇ acrylate.
  • grafting may occur by various reaction mechanisms at practically any point on the backbone rubber, generally, the grafting takes place at an unreacted point of unsaturation on the polyene. For this reason, it is desir ⁇ able to make use of an ethylene, mono-olefin, polyene back ⁇ bone rubber having at least two unsaturated carbon-to-carbon linkages per 100 carbon atoms and little additional benefit is derived from the use of unsaturated backbone rubber having more than 20 carbon-to-carbon double bonds per 1000 carbon atoms.
  • an unsaturated rubber having from 4-10 carbon-to- ⁇ carbon double bonds per 1000 carbon atoms.
  • the point of ethylenic unsaturation on the epoxy functional graft monomer must be sufficiently reactive to react directly with the unsaturation of the polyene; or to react with a graft chain originating at, or for combination with, the polyene unsaturation.
  • Such levels of reactivity require the alpha-beta situation of the ethylenic unsatura ⁇ tion as found in, for example, an epoxy functional esters of acrylic acid or alkyl acrylic acid.
  • a free radical initia ⁇ tor such as a dialkyl peroxide may be used to promote the graft reaction.
  • Such initiator is generally used in an amount within the range of 1-5 parts per 100 parts by weight of the unsaturated rubber, and preferably in an amount within the range of 1-2 percent by weight.
  • Preferred as the graft monomer herein is glycidyl methacrylate (GMA) .
  • the graft chain formed by the grafting process on the backbone rubber need not be a homopolymer or even be of entirely epoxy functional graft monomers.
  • com ⁇ binations of the two above-mentioned epoxy functional graft monomers may be used as well as combinations of either or both with other C, -C, g alkyl acrylates or methacrylates, wherein C,-C, a may be straight chain or branched, e.g., methyl, ethyl, isopropyl, 2-ethyl-hexyl, decyl, ri-octodecyl, and the like.
  • Particularly useful such comonomer grafts are grafts of glycidyl acrylate and/or glycidyl methacrylate and methyl methacrylate.
  • the gel content of the elastomeric material be controlled either during polymerization or in subsequent processing to achieve a value of greater than about 10% by weight and less than 80%. With a gel content too low impact strength is high, but knit line strength is low. With a gel content too high, both impact strength and knit line strength not as high as desirable.
  • Gel content in an especially convenient analysis is measured by the weight percent of remaining elastomeric material after extraction in hexane or toluene. Gel content is an indication of the degree of cross-linking in the elastomeric material.
  • the cross ⁇ link reaction may be a direct rubber backbone to rubber back ⁇ bone joining, an epoxy functionality to epoxy functionality or rubber backbone joining, or a graft chain free radical addition to a second graft chain or to a rubber backbone.
  • cross-linking may be achieved by the addition of a cross-linking agent to effectively achieve any of the above reactions.
  • a cross-linking agent may be added to effectively achieve any of the above reactions.
  • any of several steps to control gel content may be taken.
  • Thermal aging will increase gel content.
  • In- creasing the amount of epoxy functional graft monomer will increase gel content.
  • Increasing the amount of polyene mono- ene monomer in the rubber backbone will increase gel content.
  • the addition of a cross-linking agent will increase gel con ⁇ tent.
  • graft monomers with greater tendency to cross-link will increase gel content, for example, a homo- polymer graft of glycidyl acrylate will cross-link more readily than a homopolymer graft of glycidyl methacrylate or a copolymer graft of glycidyl acrylate and methyl meth ⁇ acrylate.
  • gel content of the elastomeric material used in this invention should range up to no higher than about 80%.
  • cross-linking should be uni ⁇ formly dispersed throughout the elastomeric material. It is preferred in the present invention that the elastomeric material have an epoxy functionality of at least 2.5 epoxy functionalities per 1000 carbon atoms, and prefer ⁇ ably between about 5.0 and 13 epoxy functionalities per 1000 carbon atoms. Epoxy functionality means those epoxy sites which remain in the impact modifier resin after the loss of such functionalities as may react in the cross-linking reac ⁇ tion.
  • a graft level of above about 1.0%, preferably above about 1.5%, and most preferably, above about 2% by weight is necessary to provide the minimum level of epoxy as shown above.
  • the maximum is not particularly criti ⁇ cal, e.g., up to 10-15% by weight can be used, although no particular advantage is achieved above about 10% by weight.
  • the grafting reaction may be carried out in solvent solution with the unsaturated rubber backbone present in a concentration which may range from 10-30 percent by weight, with constant stirring, at an elevated temperature within the range of 125-200°C. for a time ranging from 1/2 to 2 hours.
  • the reaction condition can be varied depending somewhat upon the type and amount of catalyst and temperature conditions, - as is well known to those skilled in the art.
  • high amounts of graft monomer are to be attached to the backbone rubber, it has been found to be advantageous to carry out the graft reaction in the melt state of the backbone rubber, i.e., extruder grafting. This process is simply performed by feed ⁇ ing the backbone rubber, an excess of graft monomer, and an appropriate catalyst to a melt extruder and mixing and react ⁇ ing the feed components at an elevated temperature.
  • thermoplastic polymers useful as component (c) in the practice of this invention comprise a range of materials that are well known to those skilled in this art.
  • these heat resistance improv ⁇ ing polymers also known as "glassy” polymers, have amorphous glass transition temperatures preferably above about 100°C, more preferably above about 110°C.
  • Suitable as component (c) are such polymers including but not limited to polyphenylene oxides alone, or in combination with styrene resins, amorphous polyamides, polyamide-imides, polyaryl ethers, polycarbonates, polyetherimides, polyimides, styrene copolymers such as styrene-acrylonitrile (SAN), polysulfones, and thermoplastic polyurethanes.
  • polymers including but not limited to polyphenylene oxides alone, or in combination with styrene resins, amorphous polyamides, polyamide-imides, polyaryl ethers, polycarbonates, polyetherimides, polyimides, styrene copolymers such as styrene-acrylonitrile (SAN), polysulfones, and thermoplastic polyurethanes.
  • SAN copolymers Especially preferred are SAN copolymers, polysulfones, pol (polyphenylene ethers) and polycarbonates available respectively under the tradenames TY IL*880 (Dow Chemical), UDEL* 2100 (Union Carbide), PPO* and LEXAN*131 (General Electric Company) .
  • the glass transition tempera- tures (Tg) for these preferred glassy polymers are all above 100°C, e.g., Poly-SAN, 110°C; polysulfone, 190°C; poly- (phenylene ether), 110-135°C; and poly(bisphenol A carbon ⁇ ate), 150°C.
  • unsuitable as component (c) herein are crystal- line polymers such as crystalline nylons and crystalline poly(phenylene sulfides) .
  • unsuitable polymers include acrylics, polyacrylonitrile (PAN), polystyrenes, styrene- methyl-methacrylate copolymers, and polyvinyl chloride poly ⁇ mers and copolymers. The latter all have amorphous glass transition temperatures of below about 100°C. and will not be suitable.
  • the quantity of the glassy polymer com ⁇ ponent (c) will not be substantial in comparison to the rest of components (a) and (b). Typically, only a heat resistance improving amount of the glassy polymer is required.
  • the polyester component (a) will comprise an amount of from about 30 to about 90 parts by weight
  • the rubbery polymer of component (b) will comprise an amount of from about 10 to about 55 parts by weight
  • component (c) will comprise an amount of from about 0.5 to about 15 preferably 1 to 10 parts by weight, based on a total composition of 100 parts by weight of (a), (b) and (c) combined.
  • the rubbery polymer of component (b) may comprise a "preblend" of EPDM grafted with glycidyl methacrylate and the -polyester resin, e.g., PBT in a ratio of from about 1:1 to about 10:1 of the impact modifier to the polyester.
  • this impact modifying "pre ⁇ blend" can comprise EPDM-g-GMA and PBT in a ratio of 3:1 respectively.
  • the above described elastomeric material is physical ⁇ ly dispersed in a thermoplastic polymer melt to form discrete particles of rubbery polymer in a continuous phase of a thermo ⁇ plastic matrix resin or blend.
  • At least an impact strength improving amount of elastomeric material is dispersed in the matrix resin.
  • the elastomeric material constitute at least 1.5 percent by weight, preferably 3-5 to 80 percent, most preferably 10 to 55 percent, by weight based on total thermoplastic content, including elastomeric material, of the molding composition. It will be apparent that, while the indicated composition range is optimum for making toughened rigid plastic articles, acceptable molding materials can still be made from mixtures with rubber con ⁇ tents much higher than this range.
  • Thermoplastic elastomer type molding compounds are produced when the elastomer con- tent exceeds 55 weight percent, and even mixtures above the phase inversion composition, i.e., those in which the thermo ⁇ plastic resin phase is sem ⁇ r noncontinuously interdispersed in a rubbery polymer matrix can be used to make flexible molded articles with excellent properties. 80 weight percent elastomer is a typical upper limit.
  • Compounding of the rubber, thermoplastic resin and reinforcing agent is carried out by standard techniques, for ' example, by simple melt blending or dry mixing and melt extruding at an appropriate elevated temperature for any given thermoplastic matrix. The resultant admixture is then molded into a thermoplastic piece of specific dimensions or further extruded into a film or sheet product.
  • the particle size of the rubber grafted with glycidyl esters will be selected to provide that at least 60 weight percent of such particles, and preferably more than 70 weight percent of them are greater than 1 micron in diameter.
  • Such composi ⁇ tions combine optimum notched Izod impact strength, with knit-line strength, and these are vastly superior to those obtained with compositions wherein, for example, only about 50 weight percent of the particles exceed 1 micron in dia ⁇ meter.
  • Particle size can be measured in any of the ways known in this art, but an especially convenient way is to use a computerized particle size analyzer to measure photomicro ⁇ graphs of scanning electron microscopy (SEM) images. Compounding can be carried out in conventional • equipment.
  • a single screw extruder is fed with a dry blend of the polyester, glassy polymer and the additive ingredients, e.g., antioxidant and/ or stabilizer, the screw employed having a long transition and metering section to insure melting.
  • a twin screw extrusion machine e.g., a 28 mm or 30 mm or even 90 mm Werner Pfleiderer machine can be fed with resin and additives at the feed port.
  • a generally suitable machine temperature will be about 450°F. to 570°F.
  • the compounded composition can be extruded and cut up into molding components such as conventional granules, pellets, etc., by standard techniques.
  • compositions of this invention can be molded in any equipment conventionally used for thermoplastic composi ⁇ tions.
  • any equipment conventionally used for thermoplastic composi ⁇ tions For example, with poly(l,4-butylene terephthalate) good results will be obtained in an injection molding machine, e.g., of the Newbury type or a Cincinnati 75 ton type with conventional cylinder temperature, e.g., 450°F. and conven- . tional mold temperatures, e.g., 150°F.
  • composi ⁇ tions may contain other additives known in the art, includ ⁇ ing, but without limitation, mold release agents, flow pro ⁇ moters, antioxidants , coloring agents, coupling agents, and stabilizers including transesterification stabilizers.
  • the elastomeric containing molding compositions of this invention may be used as molding pellets and may contain pigments, dyes, stabilizers, plasticizers, and the like. One may readily determine which are necessary and suitable for a particular application.
  • Impact modified PBT compositions in accordance with the present invention were blended and suitable workpieces were molded for testing.
  • the impact modifier was used as a 75/25 w/w concentrate in PBT.
  • Blends were tumble-mixed and extruded on a WP-30 twin screw extruder. The materials were subsequently dried and molded on a 75 ton Cincinnati injec ⁇ tion molding machine. Compositions and results are set forth in Table 1.
  • composition parts by weight
  • EPDM-g-GMA b 17.25 EPDM-g-GMA C 18 18 18
  • Hindered Phenol Antioxidant . 0.3 0.3 0.3 Hindered Phenol Antioxidant/ . — — — (0.3/
  • polyester resins can be used, such as poly( ethylene terephthalate) or copolyesters derived from one or more aliphatic and/or aromatic dicarboxy- lic acids and one or more straight or branched chain alipha ⁇ tic or cycloaliphatic glycols including random or block copolyesters.
  • blow molding including injection blow molding can be used.
  • glycidyl methacrylate a mixture of glycidyl methacrylate and methyl methacrylate, a mixture of glycidyl acrylate and methyl methacrylate or a mixture of glycidyl methacrylate and octadecyl methacrylate can be used.
  • poly- (styrene-acrylonitrile) polysulfone or polycarbonate as glassy polymers
  • other thermoplastic polymers such as poly- (2,6-dimethyl-l,4-phenylene ether) resin can be added in effective amounts to improve heat resistance.
  • additives known to those skilled in the art may be added in conventional amounts to the impact modified composi ⁇ tions herein including but without limitation, antioxidants, nucleating agents, mold release agents, flow promoters, coloring agents, flame retardants, coupling agents and stabilizers.

Landscapes

  • 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

Des compositions de moulage de polyesters thermoplastiques modifiés par impact par des caoutchoucs d'EPDM (monomère de diène éthylènepropylène) greffés par du méthacrylate de glycidyle présentent une meilleure resistance à la chaleur avec l'addition de polymères vitreux, c'est-à-dire des polymères thermoplastiques ayant des températures de transition de verre amorphe supérieures à environ 100°C, par exemple, le poly(styrène-acrylonitrile), le poly(sulfone) aromatique, le poly(phénylène éther) et/ou le poly(carbonate) aromatique, sans diminuer de manière significative la résistance à l'impact ni les caractéristiques des lignes de jonction.
EP88904732A 1987-03-19 1988-03-09 Compositions de polyesters modifiees par impact ayant une meilleure resistance a la chaleur Ceased EP0305514A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US2796887A 1987-03-19 1987-03-19
CA000580100A CA1333731C (fr) 1987-03-19 1988-10-13 Compositions de polyester resistant aux chocs et a resistance amelioree a la chaleur
US27968 1993-03-08

Publications (1)

Publication Number Publication Date
EP0305514A1 true EP0305514A1 (fr) 1989-03-08

Family

ID=25672173

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88904732A Ceased EP0305514A1 (fr) 1987-03-19 1988-03-09 Compositions de polyesters modifiees par impact ayant une meilleure resistance a la chaleur

Country Status (5)

Country Link
EP (1) EP0305514A1 (fr)
JP (1) JPH01500600A (fr)
AU (1) AU613376B2 (fr)
CA (1) CA1333731C (fr)
WO (1) WO1988007065A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112020003949A2 (pt) * 2017-09-06 2020-09-08 Basf Se composições de modelagem, processo de preparação, uso das composições e modelagens

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172859A (en) * 1975-05-23 1979-10-30 E. I. Du Pont De Nemours And Company Tough thermoplastic polyester compositions
JPS5787926A (en) * 1980-11-25 1982-06-01 Dainippon Printing Co Ltd White bottle made of synthetic resin
JPS5937161A (ja) * 1982-08-24 1984-02-29 東洋紡績株式会社 耐熱性容器
EP0149192A3 (fr) * 1983-12-29 1985-08-14 General Electric Company E.P.D.M. époxydé comme modificateur de la résistance aux chocs pour polyester thermoplastique
WO1986004076A1 (fr) * 1985-01-11 1986-07-17 Copolymer Rubber And Chemical Corporation Polyester presentant une resistance aux chocs amelioree

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8807065A1 *

Also Published As

Publication number Publication date
CA1333731C (fr) 1994-12-27
AU1792588A (en) 1988-10-10
JPH01500600A (ja) 1989-03-01
WO1988007065A1 (fr) 1988-09-22
AU613376B2 (en) 1991-08-01

Similar Documents

Publication Publication Date Title
US4080354A (en) Thermoplastic polyester resin compositions
AU659724B2 (en) Engineering resin-propylene polymer graft composition
JPH02380B2 (fr)
EP0110222A1 (fr) Masses à mouler à base de polyester thermoplastique et de polyéthylène linéaire à basse densité
US5026776A (en) Olefinic impact modifiers for, and blends with, thermoplastic polyesters resins
EP0105388A1 (fr) Masses à mouler modifiées à base de polyesters thermoplastiques et articles formés à partir de ces masses
EP0135677A1 (fr) Composition de résine de polyester
JP2674040B2 (ja) 熱可塑性樹脂組成物
CA1327663C (fr) Compositions thermoplastiques de polyamide-polyarylate
CA1326090C (fr) Modificateurs olefiniques de la resistance a l'impact, et melanges de ceux-ci avec des resines de polyester thermoplastiques
EP0402279A1 (fr) Compositions de polymères résistantes au choc
EP0149192A2 (fr) E.P.D.M. époxydé comme modificateur de la résistance aux chocs pour polyester thermoplastique
JPH01123854A (ja) 熱可塑性樹脂組成物
JPH075814B2 (ja) 繊維強化熱可塑性樹脂組成物
US5314948A (en) Olefinic impact modifiers for, and blends with, thermoplastic polyester resins
CA1333731C (fr) Compositions de polyester resistant aux chocs et a resistance amelioree a la chaleur
AU605596B2 (en) Glycidyl methacrylate grafted epdm modifiers in fiber reinforced polyester compositions
CA2011335A1 (fr) Compose de resine de polyester thermoplastique a resistance accrue aux chocs
CA2171330C (fr) Composition de resine polyester thermoplastique
US5391639A (en) Blends of polyphenylene ether and modified polyesters
US5179169A (en) Olefinic impact modifiers for, and blends with, thermoplastic polyester resins
EP0357459A2 (fr) Composition de moulage d'un copolymère styrène-anhydride maléique et de téréphtalate de polybutylène
KR0143082B1 (ko) 열가소성 폴리에스테르 수지용 올레핀성 내충격성 개량제 및 이와 열가소성 폴리에스테르 수지와의 블렌드
JPS5920695B2 (ja) ポリエステル弾性体組成物
JPH09216979A (ja) シボ面を有する成形品

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19890220

17Q First examination report despatched

Effective date: 19901009

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19910721