EP1352028A2 - Verstärkte thermoplastische zusammensetzung und daraus hergestellte artikel - Google Patents

Verstärkte thermoplastische zusammensetzung und daraus hergestellte artikel

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Publication number
EP1352028A2
EP1352028A2 EP01993240A EP01993240A EP1352028A2 EP 1352028 A2 EP1352028 A2 EP 1352028A2 EP 01993240 A EP01993240 A EP 01993240A EP 01993240 A EP01993240 A EP 01993240A EP 1352028 A2 EP1352028 A2 EP 1352028A2
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EP
European Patent Office
Prior art keywords
weight percent
poly
fibers
composition
thermoplastic composition
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.)
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Application number
EP01993240A
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English (en)
French (fr)
Inventor
Adeyinka Adedeji
Thomas J. Hartle
John C. Haylock
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General Electric Co
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General Electric Co
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Publication date
Priority claimed from US09/682,928 external-priority patent/US6545080B2/en
Priority claimed from US09/682,926 external-priority patent/US6660794B2/en
Priority claimed from US09/682,920 external-priority patent/US6815491B2/en
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP1352028A2 publication Critical patent/EP1352028A2/de
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides
    • C08L71/123Polyphenylene oxides not modified by chemical after-treatment

Definitions

  • U.S. Patent No. 4,764,559 to Yamauchi et al. generally describes a composition comprising (a) a polyphenylene ether having a low degree of polymerization, with or without a styrene resin, (b) a polyolefm, and (c) a styrene compound conjugated diene block copolymer or a hydrogenation product thereof.
  • a polyphenylene ether having a low degree of polymerization with or without a styrene resin
  • a polyolefm a polyolefm
  • a styrene compound conjugated diene block copolymer or a hydrogenation product thereof a styrene compound conjugated diene block copolymer or a hydrogenation product thereof.
  • inorganic fillers such as glass fiber, potassium titanate whiskers, talc, and precipitated calcium carbonate
  • U.S. Patent No. 4,863,997 to Shibuya et al. generally describes a composition comprising (a) a polyolefm resin, (b) a polyphenylene ether resin, and (c) a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene that contains 45-80 weight percent of a repeating unit derived from the alkenyl aromatic compound. Addition of fillers, such as glass fiber, wollastonite, potassium titanate whiskers, mica, talc, and calcium carbonate, is described. [0004] U.S. Patent No.
  • U.S. Patent No. 5,081,187 to Maruyama et al. generally describes a composition comprising specific amounts of (a) a polyolefm, (b) a polyphenylene ether, (c) a partially hydrogenated alkenyl aromatic compound-isoprene block copolymer, and (d) an alkenyl aromatic compound-conjugated diene block copolymer.
  • fillers such as glass fiber, wollastonite, potassium titanate, whisker, mica, talc, and calcium carbonate, is described.
  • U.S. Patent No. 5,418,287 to Tanaka et al. generally describes a composition comprising (a) a polyphenylene ether, (b) a crystalline polyolefm resin, and (c) a graft copolymer where the backbone is a copolymer of (i) ethylene or at least one C 3 -C 12 alpha-olefin, and (ii) at least one chain nonconjugated diene.
  • reinforcing agents such as glass fibers, mica, talc, precipitated calcium carbonate, silica, wollastonite, and potassium titanate whisker, is described.
  • compositions comprising: a poly(arylene ether); a poly(alkenyl aromatic) resin in an amount of at least about 10 weight percent of the total of the poly(arylene ether) and the poly(alkenyl aromatic) resin; a polyolefm; a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, wherein the hydrogenated block copolymer has an alkenyl aromatic content of about 40 to about 90 weight percent; an unhydrogenated block copolymer of alkenyl aromatic compound and a conjugated diene; and a reinforcing filler.
  • poly(arylene ether)s containing moieties prepared by grafting vinyl monomers or polymers such as polystyrenes, as well as coupled poly(arylene ether) in which coupling agents such as low molecular weight polycarbonates, quinones, heterocycles and formals undergo reaction in known manner with the hydroxy groups of two poly(arylene ether) chains to produce a higher molecular weight polymer.
  • Poly(arylene ether)s of the present invention further include combinations of any of the above.
  • the composition may comprise poly(arylene ether) in an amount of about 10 to about 55 weight percent, based on the total weight of the composition. Within this range, it may be preferred to use the poly(arylene ether) in an amount of at least about 15 weight percent, more preferably at least about 18 weight percent. It may also be preferred to use the poly(arylene ether) in an amount of up to about 55 weight percent, more preferably up to about 50 weight percent.
  • the poly(alkenyl aromatic) resins include homopolymers of an alkenyl aromatic monomer; random copolymers of an alkenyl aromatic monomer, such as styrene, with one or more different monomers such as acrylonitrile, butadiene, alpha-methylstyrene, ethylvinylbenzene, divinylbenzene and maleic anhydride; and rubber-modified poly(alkenyl aromatic) resins comprising blends and or grafts of a rubber modifier and a homopolymer of an alkenyl aromatic monomer (as described above), wherein the rubber modifier may be a polymerization product of at least one C -C ⁇ 0 nonaromatic diene monomer, such as butadiene or isoprene.
  • the stereoregularity of the poly(alkenyl aromatic) resin may be atactic or syndiotactic.
  • Highly preferred poly(alkenyl aromatic) resins include atactic and syndiotactic homopolystyrenes.
  • Suitable atactic homopolystyrenes are commercially available as, for example, EB3300 from Chevron, and PI 800 from BASF.
  • Suitable syndiotactic homopolystyrenes are commercially available, for example, under the tradename QUESTRA® (e.g., QUESTRA® WA550) from Dow Chemical Company.
  • the composition may comprise the poly(alkenyl aromatic) resin in an amount of about 1 to about 50 weight percent, preferably about 3 to about 50 weight percent, based on the total weight of the composition.
  • the composition after molding may be deficient in flexural modulus.
  • the amount of poly(alkenyl aromatic) resin is greater than about 80 weight percent of the total of the poly(arylene ether) and poly(alkenyl aromatic) resin, the composition after molding may be deficient in heat distortion temperature.
  • the relative amounts of poly(alkenyl aromatic) resin and poly(arylene ether) may be chosen so that the poly(arylene ether) and the poly(alkenyl aromatic) resin are present in a single phase having a glass transition temperature of about 130°C to about 180°C.
  • the composition further comprises a polyolefm.
  • the polyolefm may be a homopolymer or copolymer having at least about 80 weight percent of units derived from polymerization of ethylene, propylene, butylene, or a mixture thereof.
  • polyolefm homopolymers include polyethylene, polypropylene, and polybutylene.
  • polyolefm copolymers include random, graft, and block copolymers of ethylene, propylene, and butylene with each other, and further comprising up to 20 weight percent of units derived from C 5 -C 10 alpha olefins (excluding aromatic alpha-olefins).
  • Polyolefms further include blends of the above homopolymers and copolymers.
  • Preferred polyolefms may have a flexural modulus of at least about 100,000 pounds per square inch (psi) at 23°C as measured according to ASTM D790.
  • Suitable polyolefms may comprise, for example, the linear low density polyethylene available from ExxonMobil as LL-6201, the low density polyethylene available from ExxonMobil as LMA-027, the high density polyethylene available from ExxonMobil as HD-6605, the ultra-high molecular weight polyethylene available as Type 1900 from Montell Polyolefms, and the polybutylene (polybutene-1) available as PB01 10 from Montell Polyolefms.
  • the propylene polymer may have a melt flow index of about 0.1 to about 50 g/10 min, preferably about 1 to about 30 g/10 min when measured according to ASTM D 1238 at 2.16 kg and 200°C.
  • the above-described propylene polymers can be produced by various known processes. Commercially available propylene polymers may also be employed.
  • Preferred propylene polymers include homopolypropylenes.
  • Highly preferred propylene polymers include homopolypropylenes having a crystalline content of at least about 20%, preferably at least about 30%.
  • Suitable isotactic polypropylenes are commercially available as, for example, PD403 pellets from Basell (formerly Montell Polyolefms of North America).
  • the composition may comprise polyolefm in an amount of about 10 to about 60 weight percent, based on the total weight of the composition. Within this range, a polyolefm amount of at least about 15 weight percent may be preferred. Also within this range, a polyolefm amount of up to about 50 weight percent may be preferred, and an amount of up to about 40 weight percent may be more preferred.
  • the composition comprises a hydrogenated alkenyl aromatic compound conjugated diene block copolymer having an alkenyl aromatic content of about 40 to about 90 weight percent (hereinafter referred to as the "hydrogenated block copolymer").
  • the hydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, in which the aliphatic unsaturated group content in the block (B) is reduced by hydrogenation.
  • the arrangement of blocks (A) and (B) includes a linear structure, a grafted structure, and a radial teleblock structure having a branched chain.
  • linear structures embracing diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block), and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures as well as linear structures containing 6 or more blocks in total of A and B. More preferred are diblock, triblock, and tetrablock structures, with the A-B-A triblock structure being [0033]
  • the alkenyl aromatic compound providing the block (A) is represented by formula
  • R and R each independently represent a hydrogen atom, a Cj-C 8 alkyl group, a C -C 8 alkenyl group, or the like;
  • R 4 and R 8 each independently represent a hydrogen atom, a C ⁇ -C 8 alkyl group, a chlorine atom, a bromine atom, or the like;
  • R -R each independently represent a hydrogen atom, a Cj-C 8 alkyl group, a C -C 8 alkenyl group, or the like, or R 4 and R 5 are taken together with the central aromatic ring to form a naphthyl group, or R and R are taken together with the central aromatic ring to form a naphthyl group.
  • alkenyl aromatic compounds include styrene, p-methylstyrene, alpha-methylstyrene, vinylxylenes, vinyltoluenes, vinylnaphthalenes, divinylbenzenes, bromostyrenes, chlorostyrenes, and the like, and combinations comprising at least one of the foregoing alkenyl aromatic compounds.
  • styrene, alpha-methylstyrene, p-methylstyrene, vinyltoluenes, and vinylxylenes are preferred, with styrene being more preferred.
  • conjugated diene examples include 1,3-butadiene, 2 -methyl- 1,3-butadiene, 2,3-dimethyl- 1,3-butadiene, 1,3-pentadiene, and the like. Preferred among them are 1,3-butadiene and 2-methyl- 1,3-butadiene, with 1,3-butadiene being more preferred.
  • the hydrogenated block copolymer may contain a small proportion of a lower olefinic hydrocarbon such as, for example, ethylene, propylene, 1-butene, dicyclopentadiene, a non-conjugated diene, or the like.
  • a lower olefinic hydrocarbon such as, for example, ethylene, propylene, 1-butene, dicyclopentadiene, a non-conjugated diene, or the like.
  • the content of the repeating unit derived from the alkenyl aromatic compound in the hydrogenated block copolymer may be about 40 to about 90 weight percent, based on the total weight of the hydrogenated block copolymer, with the lower limit of the alkenyl aromatic compound content preferably being about 50 weight percent, more preferably about 55 weight percent, and with the upper limit of the alkenyl aromatic compound content preferably being up to about 85 weight percent, more preferably up to about 75 weight percent, yet more preferably up to about 70 weight percent.
  • the hydrogenated block copolymer is preferably hydrogenated to such a degree that fewer than 50%, more preferably fewer than 20%, yet more preferably fewer than 10%, of the unsaturated bonds in the aliphatic chain moiety derived from the conjugated diene remain unreduced.
  • the aromatic unsaturated bonds derived from the alkenyl aromatic compound may be hydrogenated to a degree of up to about 25%.
  • the hydrogenated block copolymer preferably has a number average molecular weight of about 5,000 to about 500,000 AMU, as determined by gel permeation chromatography (GPC) using polystyrene standards. Within this range, the number average molecular weight is preferably at least about 10,000 AMU, more preferably at least about 30,000 AMU, yet more preferably at least about 45,000 AMU. Also within this range, the number average molecular weight is preferably up to about 300,000 AMU, more preferably up to about 200,000 AMU, yet more preferably up to about 150,000 AMU.
  • GPC gel permeation chromatography
  • the molecular weight distribution of the hydrogenated block copolymer as measured by GPC is not particularly limited.
  • the copolymer may have any ratio of weight average molecular weight to number average molecular weight.
  • Some of these hydrogenated block copolymers have a hydrogenated conjugated diene polymer chain to which crystallinity is ascribed. Crystallinity of the hydrogenated block copolymer can be determined by the use of a differential scanning calorimeter (DSC), for example, DSC-LI Model manufactured by Perkin-Elmer Co. Heat of fusion can be measured by a heating rate of, for example, 10°C/min in an inert gas atmosphere such as nitrogen. For example, a sample may be heated to a temperature above an estimated melting point, cooled by decreasing the temperature at a rate of 10°C/min, allowed to stand for about 1 minute, and then heated again at a rate of 10°C/min.
  • DSC differential scanning calorimeter
  • the hydrogenated block copolymer may have any degree of crystallinity.
  • those hydrogenated block copolymers having a melting point of about -40°C to about 160°C or having no definite melting point (i.e., having non-crystallinity), as measured according to the above-described technique are preferred.
  • the hydrogenated block copolymer may have any glass transition temperature (T g ) ascribed to the hydrogenated conjugated diene polymer chain. From the standpoint of low-temperature impact strength of the resulting resin composition, it preferably has a T g of up to about -60°C, more preferably up to about -120°C.
  • T g glass transition temperature
  • the glass transition temperature of the copolymer can be measured by the aforesaid DSC method or from the visco-elastic behavior toward temperature change as observed with a mechanical spectrometer.
  • Particularly preferred hydrogenated block copolymers are the styrene-(ethylene-butylene) diblock and styrene-(ethy]ene-butylene)-styrene triblock copolymers obtained by hydrogenation of styrene-butadiene and styrene-butadiene-styrene triblock copolymers, respectively.
  • the hydrogenated block copolymer may be synthesized by block polymerization followed by hydrogenation as described, for example, in U.S. Patent No. 4,863,997 to Shibuya et al.
  • Suitable hydrogenated block copolymers include the styrene-(ethylene-butylene) diblock and styrene-(ethy]ene-butylene)-styrene triblock copolymers commercially available as, for example, TUFTEC® HI 043 sold by Asahi Chemical.
  • the composition may comprise the hydrogenated block copolymer in an amount of about 1 to about 20 weight percent, preferably about 1 to about 15 weight percent, more preferably about 1 to about 10 weight percent, based on the total weight of the composition.
  • the reinforcing fillers may be in the form of glass roving cloth, glass cloth, chopped glass, hollow glass fibers, glass mat, glass surfacing mat, and non-woven glass fabric, ceramic fiber fabrics, and metallic fiber fabrics.
  • synthetic organic reinforcing fillers may also be used including organic polymers capable of forming fibers.
  • Illustrative examples of such reinforcing organic fibers are poly(ether ketone), polyimide benzoxazole, poly(phenylene sulfide), polyesters, aromatic polyamides, aromatic polyimides or polyetherimides, acrylic resins, and poly(vinyl alcohol). Fluoropolymers such as polytetrafluoroethylene, may be used.
  • Such reinforcing fillers could be in the form of monofilament or ultifilament fibers and could be used either alone or in combination with another type of fiber, through, for example, coweaving or core- sheath, side-by-side, orange-type or matrix and fibril constructions or by other methods known to one skilled in the art of fiber manufacture. They may be in the form of, for example, woven fibrous reinforcements, non-woven fibrous reinforcements, or papers.
  • Preferred reinforcing fillers include glass fibers.
  • Preferred glass fibers may have diameters of about 2 to about 25 micrometers, more preferably about 10 to about 20 micrometers, yet more preferably about 13 to about 18 micrometers.
  • the length of the glass fibers may be about 0.1 to about 20 millimeters, more preferably about 1 to about 10 millimeters, yet more preferably about 2 to about 8 millimeters.
  • Longer glass fibers may also be used, as, for example, in so-called in-line compounding for long fiber filled parts in a one-step process without a pelletization step.
  • Equipment for such in-line compounding is commercially available as, for example, the Husky 3000 kiloNewton (330 ton) molding machine from Husky, Ontario, Canada.
  • Use of long fiber composites for injection molding is also described in U.S. Patent Nos. 4,559,262 to Cogswell et al. and 6,258,453 Bl to Montsinger.
  • Glass fibers comprising a sizing to increase their compatibility with the polyolefm or the poly(arylene ether) are particularly preferred.
  • Suitable sizings are described, for example, in U.S. Patent No. 5,998,029 to Adzima et al.
  • Suitable glass fibers are commercially available as, for example, product numbers 147A-14P (14 micrometer diameter) and 147A-17P (17 micrometer diameter) from Owens Corning.
  • Preferred reinforcing fillers further include talc.
  • talc There are no particular limitations on the physical characteristics of the talc.
  • Preferred talcs may have an average particle size of about 0.5 to about 25 micrometers. Within this range, it may be preferred to use a talc having an average particle size up to about 10 micrometers, more preferably up to about 5 micrometers.
  • a talc that is F.D.A. compliant (i.e., compliant with U.S. Food and Drug Administration regulations).
  • Suitable talcs include, for example, the F.D.A. compliant talc having an average particle size of about 3.2 micrometers sold as CIMPACT® 610(C) from Luzenac.
  • the compatibility of the reinforcing filler and the polyolefm may be improved not just with sizings on the surface of the reinforcing fillers, but also by adding to the composition a graft copolymer comprising a polyolefm backbone and polar grafts formed from one or more cyclic anhydrides.
  • a graft copolymer comprising a polyolefm backbone and polar grafts formed from one or more cyclic anhydrides.
  • Such materials include graft copolymers of polyolefms and C 4 -Cj cyclic anhydrides, such as, for example, those available from ExxonMobil under the tradename EXXELOR® and from DuPont under the tradename FUSABOND®.
  • polyolefin-graft-cyclic anhydride copolymers examples include the po]ypropylene-graft-po]y(maleic anhydride) materials supplied by ExxonMobil as EXXELOR® PO1020 and by DuPont as FUSABOND® M613-05. Suitable amounts of such materials may be readily determined and are generally about 0.1 to about 10 weight percent, based on the total weight of the composition. Within this range, a polyolefin-graft-cyclic anhydride copolymer amount of at least about 0.5 weight percent may be preferred. Also within this range, a polyolefin-graft-cyclic anhydride copolymer amount of up to about 5 weight percent may be preferred.
  • Preferred reinforcing fillers further include organoclays.
  • an organoclay is a layered silicate clay, derived from layered minerals, in which organic structures have been chemically incorporated.
  • Illustrative examples of organic structures are trimethyldodecylammonium ion and
  • N,N'-didodecylimidazolium ion Since the surfaces of clay layers, which have a lattice-like arrangement, are electrically charged, they are capable of binding organic ions.
  • layered minerals employed in this invention other than that they are capable of undergoing an ion exchange with the organic ions.
  • Preferred organoclays include layered minerals that have undergone cation exchange with organocations and or onium compounds.
  • Illustrative of such layered minerals are the kaolinite group, the montmorillonite group, and the illite group which can include hydromicas, phengite, brammallite, glaucomite, celadonite and the like.
  • Preferred layered minerals include those often referred to as 2:1 layered silicate minerals like muscovite, vermiculite, saponite, hectorite and montmorillonite, wherein montmorillonite is often preferred.
  • the layered minerals described above may be synthetically produced. However, most often they are naturally occurring and commercially available. Organoclays and their preparation are described, for example, in U.S. Patents Nos. 4,569,923, 4,664,842, 5,110,501, and 5,160,454 to Knudson, Jr.
  • the composition comprises the reinforcing filler in an amount of about 1 to about 50 weight percent, preferably about 5 to about 50 weight percent, based on the total weight of the composition.
  • the reinforcing filler is an organoclay, it may be preferred to use it in an amount of at least about 5 weight percent, more preferably at least about 10 weight percent. Also when the reinforcing filler is an organoclay, it may be preferred to use it in an amount of up to about 45 weight percent, more preferably up to about 50 weight percent.
  • the composition may, optionally, further comprise a polypropylene-polystyrene graft copolymer.
  • the polypropylene-polystyrene graft copolymer is herein defined as a graft copolymer having a propylene polymer backbone and one or more styrene polymer grafts.
  • the propylene polymer material that forms the backbone or substrate of the polypropylene-polystyrene graft copolymer is (a) a homopolymer of propylene; (b) a random copolymer of propylene and an olefin selected from the group consisting of ethylene and C 4 -C 10 olefins, provided that, when the olefin is ethylene, the polymerized ethylene content is up to about 10 weight percent, preferably up to about 4 weight percent, and when the olefin is a C 4 -C J O olefin, the polymerized content of the C 4 -C ⁇ o olefin is up to about 20 weight percent, preferably up to about 16 weight percent; (c) a random terpolymer of propylene and at least two olefins selected from the group consisting of ethylene and C 4 -C ⁇ o alpha-olefins, provided that the polymerized C 4
  • the C 4 -C ⁇ 0 olefins include the linear and branched C -C ⁇ 0 alpha-olefins such as, for example, 1-butene, 1-pentene, 3-methyl-l-butene, 4-methyl-l-pentene, 1-hexene, 3,4-dimethyl-l-butene, 1-heptene, 1-octene, 3-methyl-hexene, and the like.
  • Propylene homopolymers and impact-modified propylene homopolymers are preferred propylene polymer materials.
  • propylene homopolymers and random copolymers impact modified with an ethylene-propylene-diene monomer rubber having a diene content of about 2 to about 8 weight percent also can be used as the propylene polymer material.
  • Suitable dienes include dicyclopentadiene, 1,6-hexadiene, ethylidene norbornene, and the like.
  • styrene polymer used in reference to the grafted polymer present on the backbone of propylene polymer material in the polypropylene-polystyrene graft copolymer, denotes (a) homopolymers of styrene or of an alkyl styrene having at least one C ⁇ -C linear or branched alkyl ring substituent, especially a p-alkyl styrene; (b) copolymers of the (a) monomers with one another in all proportions; and (c) copolymers of at least one (a) monomer with alpha-methyl derivatives thereof, e.g., alpha-methylstyrene, wherein the alpha-methyl derivative constitutes about 1 to about 40% of the weight of the copolymer.
  • polypropylene-polystyrene graft copolymers are described, for example, in U.S. Patent No. 4,990,558 to DeNicola, Jr. et al.
  • Suitable polypropylene-polystyrene graft copolymers are also commercially available as, for example, PI 045H1 and P1085Hl from Basell.
  • the polypropylene-polystyrene graft copolymer may be used in an amount of about 0.5 to about 20 weight percent, based on the total weight of the composition. Within this range, it may be preferred to use at least about 1.0 weight percent of the polypropylene-polystyrene graft copolymer. Also within this range, it may also be preferred to use up to about 15 weight percent, more preferably up to about 10 weight percent, yet more preferably up to about 8 weight percent, of the polypropylene-polystyrene graft copolymer.
  • the composition may, optionally, further comprise an ethyl ene/alpha-olefin elastomeric copolymer.
  • the alpha-olefin component of the copolymer may be at least one C -C ⁇ 0 alpha-olefin.
  • Preferred alpha-olefins include propylene, 1-butene, and 1-octene.
  • the elastomeric copolymer may be a random copolymer having about 25 to about 75 weight percent ethylene and about 75 to about 25 weight percent alpha-olefin. Within these ranges, it may be preferred to use at least about 40 weight percent ethylene; and it may be preferred to use up to about 60 weight percent ethylene.
  • the ethylene/alpha-olefm elastomeric copolymer may typically have a melt flow index of about 0.1 to about 20 g/10 min at 2.16 kg and 200°C, and a density of about 0.8 to about 0.9 g/ml.
  • Particularly preferred ethylene/alpha-olefin elastomeric copolymer rubbers include ethylene-propylene rubbers, ethyl ene-butylene rubbers, ethylene- octene rubbers, and mixtures thereof.
  • the ethylene/alpha-olefm elastomeric copolymer may be prepared according to known methods or obtained commercially as, for example, the neat ethylene-propylene rubber sold as NISTALON® 878 by ExxonMobil Chemical and the ethylene-butylene rubber sold as EXACT® 4033 by ExxonMobil Chemical.
  • Ethylene/alpha-olefm elastomeric copolymers may also be obtained commercially as blends in polyolefms such as, for example, the ethylene-propylene rubber pre-dispersed in polypropylene sold as product numbers Profax 7624 and Profax 8623 from Basell, and the ethylene-butylene rubber pre-dispersed in polypropylene sold as Catalloy K021P from Basell.
  • the amount of ethylene/alpha-olefin elastomeric copolymer may be expressed as a fraction of the total of polyolefm and ethylene/alpha-olefin elastomeric copolymer.
  • its amount may be expressed as about 1 to about 30 weight percent, preferably about 3 to about 30 weight percent, based on the combined weight of polyolefm and ethylene/alpha-olefin elastomeric copolymer.
  • the composition further comprises an unhydrogenated block copolymer of alkenyl aromatic compound and a conjugated diene (referred to hereinafter as an "unhydrogenated block copolymer").
  • the unhydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, in which the aliphatic unsaturated group content in the block (B) has not been reduced by hydrogenation.
  • the alkenyl aromatic compound (A) and the conjugated diene (B) are defined in detail above in the description of the hydrogenated block copolymer.
  • the arrangement of blocks (A) and (B) includes a linear structure and a so-called radial teleblock structure having a branched chain.
  • Preferred of these structures are linear structures embracing diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block), and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures as well as linear structures containing 6 or more blocks in total of A and B. More preferred are diblock, triblock, and tetrablock structures, with the A-B-A triblock structure being particularly preferred.
  • the unhydrogenated block copolymer may comprise about 10 to about 90 weight percent of the (A) blocks. Within this range, it may be preferred to use at least about 20 weight percent (A) blocks. Also within this range, it may be preferred to use up to about 50 percent (A) blocks.
  • Particularly preferred unhydrogenated block copolymers include styrene-butadiene diblock copolymers and styrene-butadiene-styrene triblock copolymers.
  • Suitable unhydrogenated block copolymers may be prepared by known methods or obtained commercially as, for example, KRATON® D series polymers, including KRATON® Dl 101 and Dl 102, from Kraton Polymers (formerly a division of Shell Chemical). Suitable unhydrogenated block copolymers further include the styrene-butadiene radial teleblock copolymers available as, for example, K-RESTN® KR01, KR03, KR05, and KR10 sold by Chevron Phillips Chemical Company.
  • the unhydrogenated block copolymers may be used at about 0.5 to about 20 weight percent, based on the total weight of the composition. Within this range, it may be preferred to use at least about 1 weight percent, more preferably at least about 2 weight percent, of the unhydrogenated block copolymers. Also within this range, it may be preferred to use up to about 15 weight percent, preferably up to about 10 weight percent, of the unhydrogenated block copolymers.
  • the composition may, optionally, further comprise a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, wherein the hydrogenated block copolymer has an alkenyl aromatic content of about 10 to less than 40 weight percent.
  • the alkenyl aromatic compound and the conjugated diene compound are the same as those defined above for the hydrogenated block copolymer having an alkenyl aromatic content of about 40 to about 90 weight percent.
  • Such materials are commercially available as, for example, KRATON® G1650 and G1652 from Kraton Polymers.
  • the hydrogenated block copolymer having an alkenyl aromatic content of about 10 to less than 40 weight percent may be used at about 1 weight percent to about 20 weight percent, based on the total weight of the composition.
  • the composition may comprise one or more additives known in the art.
  • additives may include, for example, stabilizers, mold release agents, processing aids, flame retardants, drip retardants, nucleating agents, UV blockers, dyes, pigments, particulate fillers (i.e., fillers having an aspect ratio less than about 3), antioxidants, anti-static agents, blowing agents, and the like.
  • additives are well known in the art and appropriate amounts may be readily determined.
  • the composition comprises: about 10 to about 55 weight percent of a poly(arylene ether); about 3 to about 50 weight percent of a poly(alkenyl aromatic) resin; wherein the amount of poly(alkenyl aromatic) resin is at least about 10 weight percent of the total of the poly(arylene ether) and the poly(alkenyl aromatic) resin; about 10 to about 60 weight percent of a polyolefin; about 1 to about 20 weight percent of a hydrogenated block copolymer of alkenyl aromatic compound and a conjugated diene having an alkenyl aromatic content of about 40 to about 90 weight percent; about 1 to about 20 weight percent of an unhydrogenated block copolymer of alkenyl aromatic compound and a conjugated diene; and about 1 to about 50 weight percent of a reinforcing filler; wherein all weight percents are based on the total weight of the composition.
  • the composition exhibits improved property balances.
  • the composition exhibits an improved balance between stiffness and impact strength.
  • the composition may exhibit a flexural modulus at 23°C, measured according to ASTM D790, of at least about 300, preferably at least about 350, kilopounds per square inch (kpsi).
  • the composition may exhibit an Izod Notched Impact Strength measured at 23°C according to ASTM D256 of at least about 1 footpound per inch (ft-lb/in), preferably at least about 1.5 ft-lb/in, more preferably at least about 2 ft-lb/in.
  • ASTM parts were molded on a 120 tonne molding machine (manufacturer: Van Dorn) at 100-120°F mold temp and a 450-550°F barrel temperature.

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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)
EP01993240A 2000-12-28 2001-12-11 Verstärkte thermoplastische zusammensetzung und daraus hergestellte artikel Withdrawn EP1352028A2 (de)

Applications Claiming Priority (13)

Application Number Priority Date Filing Date Title
US25883500P 2000-12-28 2000-12-28
US25884000P 2000-12-28 2000-12-28
US25889600P 2000-12-28 2000-12-28
US258896P 2000-12-28
US258840P 2000-12-28
US258835P 2000-12-28
US682928 2001-11-01
US09/682,928 US6545080B2 (en) 2000-12-28 2001-11-01 Glass-filled poly(arylene ether)-polyolefin composition and articles derived therefrom
US682920 2001-11-01
US682926 2001-11-01
US09/682,926 US6660794B2 (en) 2000-12-28 2001-11-01 Glass-filled poly(arylene ether)-polyolefin composition and articles derived therefrom
US09/682,920 US6815491B2 (en) 2000-12-28 2001-11-01 Reinforced thermoplastic composition and articles derived therefrom
PCT/US2001/047701 WO2002057363A2 (en) 2000-12-28 2001-12-11 Reinforced thermoplastic composition and articles derived therefrom

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EP1352028A2 true EP1352028A2 (de) 2003-10-15

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JP (1) JP2004517998A (de)
CN (1) CN1484676A (de)
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US8057873B2 (en) * 2008-04-28 2011-11-15 Sabic Innovative Plastics Ip B.V. Injection molded article and method for the manufacture thereof
EP2288658A4 (de) * 2008-06-17 2012-01-04 Polyone Corp Thermoplastische elastomere mit hervorragenden abriebfestigkeitseigenschaften
US8653167B2 (en) * 2011-05-26 2014-02-18 Sabic Innovative Plastics Ip Molding composition for photovoltaic junction boxes and connectors
CN102408697A (zh) * 2011-09-20 2012-04-11 福建奥峰科技有限公司 一种增强聚苯醚(ppo)组合物及其制备方法和用途
US8975329B2 (en) * 2011-12-02 2015-03-10 Sabic Global Technologies B.V. Poly(phenylene ether) articles and compositions
CN102850654A (zh) * 2012-09-24 2013-01-02 吴江市信许塑料鞋用配套有限公司 一种橡塑鞋底材料的制备方法
JP6175339B2 (ja) * 2013-10-01 2017-08-02 旭化成株式会社 樹脂組成物及びその成形体
CN107207850B (zh) * 2015-03-27 2019-08-16 旭化成株式会社 树脂组合物、成型体、配管机械部件
US10189990B2 (en) 2015-04-27 2019-01-29 Sabic Global Technologies B.V. Poly(phenylene ether) composition and article
JP6763698B2 (ja) * 2016-05-31 2020-09-30 旭化成株式会社 樹脂組成物及び成形体
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EP4050065A4 (de) * 2019-10-21 2022-11-23 Asahi Kasei Kabushiki Kaisha Harzzusammensetzungen und verfahren zu deren herstellung, formteile, maschinenteile und gehäuse

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CN1484676A (zh) 2004-03-24
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WO2002057363A2 (en) 2002-07-25
JP2004517998A (ja) 2004-06-17

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