EP0309575A1 - Agents modifiants epdm greffes par methacrylate de glycidyle dans des compositions fibreuses de polyester renforce - Google Patents

Agents modifiants epdm greffes par methacrylate de glycidyle dans des compositions fibreuses de polyester renforce

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Publication number
EP0309575A1
EP0309575A1 EP88904731A EP88904731A EP0309575A1 EP 0309575 A1 EP0309575 A1 EP 0309575A1 EP 88904731 A EP88904731 A EP 88904731A EP 88904731 A EP88904731 A EP 88904731A EP 0309575 A1 EP0309575 A1 EP 0309575A1
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EP
European Patent Office
Prior art keywords
composition
weight
poly
amount
component
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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.)
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EP88904731A
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German (de)
English (en)
Inventor
Angelika Howard Mchale
Charles Franklyn Pratt
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General Electric Co
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General Electric Co
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Publication of EP0309575A1 publication Critical patent/EP0309575A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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

  • This invention relates to impact modified reinforced thermoplastic molding compositions and, more particularly, to glycidyl methacrylate or glycidyl acrylate grafted EPDM impact modifiers for fiber reinforced thermoplastic polyester, copolyester and polyblend molding compositions.
  • polyesters are particularly advantageous as film and fiber formers.
  • poly(ethylene terephthalate) or PET has become an important constituent of injection moldable compositions.
  • poly(1,4-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 resistance, high gloss and lower surface friction.
  • poly(1,4-butylene terephthalate) is much simpler to use in injection molding techniques than poly(ethylene terephthalate).
  • the dimensional stability of poly(1,4-butylene terephthalate) in jection moldings is very good even at temperatures near or well above the glass temperature of poly(1,4-butylene terephthalate).
  • polyesters which are impact resistant at relatively high and relatively low ambient temperatures.
  • other mechanical properties such as modulus of elasticity, tensile strength at yield and at break should be impaired either not at all or only to an acceptable degree.
  • thermoplastic linear crystalline polyesters including poly(1,4-butylene terephthalate)
  • EPDM ethylenepropylene nonconjugated diene rubbery terpolymer
  • EPDM is capable of impact-modifying PBT polyester compositions, e.g., Coran et al., U.S. 4,141,863 and Tanaka et al., U.S. 4,290,927, such compositions often suffer from "incompatibility" resulting in streaks or delamination of molded or extruded parts.
  • thermoplastic molding composition consisting of a thermoplastic resin, e.g., polyester, copolyester or block copolyester and an EPDM epoxidized with, e.g., m-chloroperoxy-benzoic acid.
  • reinforcing agents e.g., fibrous glass
  • U.S. 3,769,260 discloses that a functionalized rubber improves impact strength of polyesters, and suggests a range of 0.02 to 20 microns in diameter for the dispersed rubber phase particles.
  • Glass fibers are claimed as a filler in the '260 Patent but the unnotched Izod impact strengths are not particularly high.
  • Epstein, U.S. 4,172,859 discloses the use of random copolymers containing various polar monomers and glass fibers, up to 50 weight percent, are claimed as fibrous reinforcement. 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.
  • GMA glycidyl methacrylate
  • GMA glycidyl methacrylate
  • fibrous reinforcing agents such as glass fibers
  • thermoplastic polyester compositions comprising glycidyl methacrylate grafted EPDM (EPDM-g-GMA) impact modifiers, and that such compositions and glass fibers, will exhibit increased impact strength without significantly diminishing the "stiffness" of the material as measured conveniently by tensile strength, and tensile and flexural modulus.
  • EPDM-g-GMA glycidyl methacrylate grafted EPDM
  • glass fibers and, optionally, a nucleating agent, impact strength and resistance to heat are both enhanced.
  • improved impact modified reinforced thermoplastic compositions comprising:
  • thermoplastic polyester resin (a) a high molecular weight thermoplastic polyester resin
  • a fibrous reinforcing agent comprising using as said rubbery polymer an EPDM terpolymer grafted with 2% or more by weight based on said terpolymer of glycidyl methacrylate or glycydyl acrylate or a mixture thereof, alone, or grafted in further combination with a C 1 -C 18 alkyl methacrylate or acrylate or a mixture thereof.
  • component (a) comprises poly(1,4-butylene terephthalate) in an amount of from about 30 to about 80 parts by weight; component (b) comprises from about 1.5 to about 35 parts by weight; and component (c) comprises glass fibers in an amount of from about 5 to about 45 parts by weight, based on a total composition of 100 parts by weight of (a), (b) and (c) combined.
  • compositions as defined above wherein component (a) comprises poly(ethylene terephthalate); component (b) comprises a preblend of EPDM grafted with glycidyl methyl methacrylate and poly(ethylene terephthalate) in a ratio of from 1:1 to about 10:1 of the former to the latter; component (c) comprises glass fibers; and further comprising (d) an effective amount of a nucleating agent.
  • 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.
  • Preferred 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 isophthalic acids of up to about 30 mole percent isophthalic units.
  • polyesters are poly( ethylene terephthalate) and poly(1,4-butylene terephthalate).
  • high molecular weight polyesters will have an intrinsic viscosity of at least about 0.7 deciliters/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-1,3-propanediol, 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,9-nonanediol; 1,10-decanediol; neopentylglycol; 1,4-cyclohexanediol; 1,4-cyclohexanedimethanol; a mixture of any of the foregoing, or the like.
  • suitable aliphatic dicarboxylic acids for the mixed aromatic/aliphatic embodiments are suberic, sebacic, azelaic, and adipic acids and the like.
  • the copolyesters may be prepared by ester interchange in accordance with the standard procedures.
  • the copolyesters 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 reactive poly(1,4-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 comprise hydroxyl, carboxyl, carboalkoxy, and the like, including 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.
  • the copolyester designated component of these block copolyesters may be terminally reactive segments of copolyesters as described above. These copolyesters are most preferably 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.
  • the terminally reactive aliphatic polyester component of these block copolyesters will contain substantially stoichiometric amounts of the aliphatic diol and the aliphatic dicarboxylic acid.
  • both the aforementioned aromatic/aliphatic copolyesters 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 preferably comprise from about 95 to about 50 parts by weight based on the block copolyester of poly(1,4-butylene terephthalate) segments.
  • the poly(1,4-butylene terephthalate) blocks, before incorporation into the block copolyesters, will preferably have an intrinsic viscosity of about 0.1 dl./g.
  • the balance 50 to 5 parts by weight of the copolyester will comprise blocks of the aforementioned aromatic/aliphatic copolyesters and/or aliphatic polyesters.
  • the poly(1,4-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 terephthalate 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 terephthalate 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 polybasic acid compound, e.g., trimethyl trimestate, 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), or may be prepared 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;
  • EPDM terpolymers for the production of the glycidyl ether grafted terpolymers used in this invention comprise ethylene, a C 3 to C 16 straight or branched chain alpha-olefin, preferably propylene, and a non-conjugated diolefin.
  • 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 cyclooctadiene 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 polyunsaturated bridged ring hydrocarbon or halogenated derivative thereof, most preferably 5-ethylidene-2-norbornene.
  • These EPDM terpolymers have a melt index of approximately 79 g/10 min., 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 methacrylate.
  • 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 desirable to make use of an ethylene, mono-olefin, polyene backbone 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. In the preferred practice of this invention, use is made of 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 unsaturation as found in, for example, an epoxy functional esters of acrylic acid or alkyl acrylic acid.
  • a free radical initiator 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.
  • combinations of the two above-mentioned epoxy functional graft monomers may be used as well as combinations of either or both with other C 1 -C 18 alkyl acrylates or methacrylates, wherein C 1 -C 18 may be straight chain or branched, e.g., methyl, ethyl, isopropyl, 2-ethyl-hexyl, decyl, n-octodecyl, and the like.
  • comonomer grafts are grafts of glycidyl acrylate and/or glycidyl methacrylate and methyl methacrylate. It is preferred in the present invention that 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, the impact modifier is difficult to disperse.
  • Gel content in an especially convenient analysis, according to ASTM D-3616, 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 backbone 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.
  • any of several steps to control gel content may be taken.
  • Thermal aging will increase gel content.
  • Increasing the amount of epoxy functional graft monomer will increase gel content.
  • Increasing the amount of polyene monoene monomer in the rubber backbone will increase gel content.
  • the addition of a cross-linking agent will increase gel content.
  • the use of graft monomers with greater tendency to cross-link will increase gel content, for example, a homopolymer 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 methacrylate.
  • gel content of the elastomeric material used in this invention should range up to no higher than about 80%.
  • cross-linking can be carried on well past this level, as has been mentioned, high levels of cross-linking diminish the dispersibility of the elastomeric material and lead to non-uniform mixing. Also, such high levels of localized cross-linking will create brittle areas within the elastomeric material which will decrease rubbery character. It is apparent that cross-linking should be uniformly dispersed throughout the elastomeric material.
  • the elastomeric material have an epoxy functionality of at least 2.5 epoxy functionalities per 1000 carbon atoms, and preferably 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 reaction.
  • GMA or GA as the epoxy functional graft monomer
  • a graft level of above about 1%, preferably above about 1.5% and most preferably above about 2-by weight is used to provide the minimum level of epoxy as shown above.
  • the maximum is not particularly critical, e.g., up to 10-15% by weight can be used, but no special advantage is seen if these amounts are exceeded.
  • 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 feeding the backbone rubber, an excess of graft monomer, and an appropriate catalyst to a melt extruder and mixing and reacting the feed components at an elevated temperature.
  • the fibrous reinforcing agents useful as component (c) in the practice of this invention comprise a range of materials including but not limited to glass, graphite, wollastonite, carbons, metals, e.g., aluminum, iron, nickel, stainless steel and the like, titanates, e.g., titanate whiskers, quartz, mixtures of the foregoing and the like.
  • the polyester component (a) will comprise from about 30 to about 80, preferably from about 40 to about 70, parts by weight
  • the rubbery polymer (b) will comprise from about 1.5 to 35, preferably 5 to 25 percent by weight
  • the reinforcing agent (c) will comprise from about 1 to about 80 parts by weight of the total composition.
  • the preferred reinforcing fillers are of glass and it is preferred to use fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass.
  • E lime-aluminum borosilicate glass
  • C low soda glass
  • the filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling.
  • the preferred filaments for plastics reinforcement are made by mechanical pulling, the filament diameters range from about 0.00012 to 0.00075 inch, but this is not critical to the present invention.
  • the length of the glass filaments and whether or not they are bundled into fibers and the fibers bundled in turn to yarns, ropes or rovings, or woven into mats, and the like, are also not critical to the invention.
  • the filamentous glass in the form of chopped strands of from about 1/8 inch to about 1 inch long, preferably less than 1/4 inch 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 inch and 0.125 (1/8) inch.
  • the sized filamentous glass reinforcement comprises from about 1 to about 80% by weight based on the combined weight of glass and polyesters and preferably from about 5 to about 50% by weight. Especially preferably the glass will comprise from about 5 to about 40% by weight based on the combined weight of glass and resins.
  • up to about 60% of glass can be present without causing flow problems.
  • the above described elastomeric material is physically dispersed in a thermoplastic polymer melt to form discrete particles of rubbery polymer in a continuous phase of a thermoplastic matrix resin or blend. At least an impact strength improving amount of elastomeric material is dispersed in the matrix resin. Generally, this requires that 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 contents much higher than this range.
  • Thermoplastic elastomer type molding compounds are produced when the elastomer content exceeds 55 weight percent, and even mixtures above the phase inversion composition, i.e., those in which the thermoplastic resin phase is semi- or 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 compositions 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 diameter.
  • 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 photomicrographs of scanning electron microscopy (SEM) images.
  • SEM scanning electron microscopy
  • Compounding can be carried out in conventional equipment. For example, after pre-drying the thermoplastic polyester resin, e.g., at 125°C. for 4 hours, a single screw extruder is fed with a dry blend of the polyester, reinforcing agent and the additive ingredients, the screw employed having a long transition and meterin section to insure melting.
  • a twin screw extrusion machine e.g., a 28 mm Werner Pfleiderer machine can be fed with resin and additives at the feed port. In either case, a generally suitable machine temperature will be about 450°F. to 520°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 compositions.
  • any equipment conventionally used for thermoplastic compositions For example, with poly(1,4-butylene terephthalate) good results will be obtained in an injection molding machine, e.g., of the Newbury type with conventional cylinder temperature, e.g., 480-500°F. and conventional mold temperatures, e.g., 150°F.
  • poly(ethylene terephthalate) because of the lack of uniformity of crystallization from interior to exterior of thick pieces, somewhat less conventional but still well known techniques can be used.
  • a nucleating agent such as a LiOH, sodium stearate, graphite or a metal oxide, e.g., ZnO or MgO can be included as component (d) and standard mold temperaures of from about 150°F. to 230°F. will be used.
  • compositions may contain other additives known in the art, including, but without limitation, nucleating agents, mold release agents, flow promoters, coloring agents, coupling agents, and 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.
  • EXAMPLE 1 An impact modified glass reinforced PBT composition was prepared and suitable workpieces were molded for testing. EPDM grafted with 4.5% glycidyl methacrylate (EPDM-g-GMA) and a 21% gel content was used as an impact modifier.
  • the modifier can be prepared by use of a procedure in copending application 337-1997 (8CT-4294), e.g., Example 9(a).
  • Mooney Viscosity 50; (Copolymer Chemical and Rubber Corporation); 0.1 parts by weight of hindered phenolic antioxidant, IRGANOX ® 1076, Ciba-Geigy Corporation; 7.4 parts by weight of glycidyl methacrylate; and 0.56 parts by weight of 2,5-di-methyl-2,5-di(t-butyl-peroxy) hexane initiator can be passed through a Werner-Pfleiderer WP57 twin screw extruder. Zone temperatures of 200°C. and screw speeds of 150 rpm can be used. The water cooled strands of elastomeric material which emerge can be chopped into pellets.
  • composition parts by weight
  • the EPDM-g-GMA modified PBT composition exhibits excellent mechanical properties, e.g., flexural modulus, tensile strength and tensile modulus and impact strength.
  • the molded article prepared in Example 1 was examined under a scanning electron microscope (SEM). In the
  • EPDM-g-GMA impact modified glass reinforced composition the fibers showed no separation from the matrix and the exposed fibers had very rough surfaces, indicating a high degree of adhesion of the matrix to the glass.
  • EPDM-g-GMA was added.
  • Compositions and test results are set forth in Table 2. TABLE 2: Thermoplastic Compositions PET/EPDM-g-GMA/Glass
  • composition parts by weight
  • PET/EPDM-g-GMA Conc. b 8.0 16.0 8.0 16.0
  • EXAMPLES 6-15 In the following Examples 6-15, the EPDM-g-GMA and glass contents were varied. PBT compositions were blended according to the procedure of Example 1 except that a Buss Kneader was used for extrusion. Articles suitable for testing were molded. Compositions and test results are set forth in Table 3.
  • compositions of high impact strength and good resistance to heat can be prepared in accordance with the present invention.
  • composition parts by weight
  • polyester resins such as copolyesters derived from one or more aliphatic and/or aromatic dicarboxylic acids and one or more straight or branched chain aliphatic 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 or glycidyl acrylate alone can be used.
  • additives known to those skilled in the art may be added in conventional amounts to the impact modified compositions herein including but without limitation, nucleating agents, mold release agents, flow promoters, coloring agents, flame retardants, coupling agents and stabilizers. All such obvious variations are within the full intended scope of the appended claims.

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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

Des compositions de moulage de polyesters, copolyesters et de mélanges vinyliques thermoplastiques modifiés par impact par l'EPDM (monomère de diène d'éthylène propylène) greffé par méthacrylate de glycidyle présentent une grande résistance à l'impact et une bonne résistance à la chaleur lorsque des renforcements fibreux, tels que des fibres de verre, sont ajoutés au mélange.
EP88904731A 1987-03-19 1988-03-09 Agents modifiants epdm greffes par methacrylate de glycidyle dans des compositions fibreuses de polyester renforce Withdrawn EP0309575A1 (fr)

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US2770787A 1987-03-19 1987-03-19
US27707 1987-03-19

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EP0309575A1 true EP0309575A1 (fr) 1989-04-05

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EP88904731A Withdrawn EP0309575A1 (fr) 1987-03-19 1988-03-09 Agents modifiants epdm greffes par methacrylate de glycidyle dans des compositions fibreuses de polyester renforce

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EP (1) EP0309575A1 (fr)
JP (1) JPH01500599A (fr)
AU (1) AU605596B2 (fr)
BR (1) BR8806241A (fr)
WO (1) WO1988007064A1 (fr)

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CN113831693A (zh) * 2020-06-24 2021-12-24 合肥杰事杰新材料股份有限公司 一种pbt复合材料及其制备方法

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CN110760166A (zh) * 2018-07-26 2020-02-07 比亚迪股份有限公司 纤维增强聚合物合金组合物、纤维增强聚合物合金及其制备方法和应用

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AU605596B2 (en) 1991-01-17

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