WO2001070884A1 - Composition a base de melange de polymeres de carbonate - Google Patents

Composition a base de melange de polymeres de carbonate Download PDF

Info

Publication number
WO2001070884A1
WO2001070884A1 PCT/US2001/001653 US0101653W WO0170884A1 WO 2001070884 A1 WO2001070884 A1 WO 2001070884A1 US 0101653 W US0101653 W US 0101653W WO 0170884 A1 WO0170884 A1 WO 0170884A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
carbonate polymer
copolymer
polymer blend
blend composition
Prior art date
Application number
PCT/US2001/001653
Other languages
English (en)
Inventor
Paul H. W. J. Dumont
Dagmar J. J. M. Van Heur
Original Assignee
The Dow Chemical Company
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 The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to AU2001227946A priority Critical patent/AU2001227946A1/en
Publication of WO2001070884A1 publication Critical patent/WO2001070884A1/fr

Links

Classifications

    • 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
    • C08L51/04—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 rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • CARBONATE POLYMER BLEND COMPOSITION This invention relates to a carbonate polymer blend composition compnsing a rubber- modified monovinylidene aromatic copolymer.
  • This invention relates particularly to a carbonate polymer blend composition having, when molded, reduced anisotropic impact behavior
  • Carbonate polymers denved from reactions of dihydroxyorgamc compounds, particularly the dihyd ⁇ c phenols, and carbonic acid de ⁇ vatives such as phosgene have found extensive commercial application because of their excellent physical properties
  • These thermoplastic polymers appear suitable for the manufacture of molded parts wherein impact strength, ngidity, toughness, heat resistance, excellent electncal properties, glass-like transparency and good clanty are required.
  • polymers are expensive in pnce and require a high amount of energy expenditure in extrusion and molding processes
  • said polymers may contain additives that reduce costs and lower the temperatures required for molding processes.
  • the blends resulting from the processing of carbonate polymer and additive generally exhibit improved melt flow properties at the sac ⁇ fice of other desirable features such as heat resistance, and impact strength
  • blends of carbonate polymer and additive often do not exhibit a desirable degree of anisotropic impact behavior.
  • Anisotropic property behavior of polymer compositions in molded articles refers to a difference in property values measured along axes in different directions Reduction of anisotropic property behavior for polymer compositions leads to more uniform property performance in molded articles. More uniform property performance in molded articles facilitates the part designer's ability to design safe, reliable and cost effective molded articles
  • the present invention is such a desirable carbonate polymer blend composition
  • the composition possesses a desirable balance of good processability, good thermal and physical properties, and especially, improved anisotropic impact behavior
  • the composition is a heterogeneous blend comprising an aromatic carbonate polymer blended with an effective amount of a rubber-modified copolymer comprising a monovinylidene aromatic monomer, an ethylenically unsaturated nitnle monomer, and an ester of acrylic acid, especially n-butyl acrylate
  • the rubber-modified copolymer is a composition prepared using bulk, mass-solution or mass-suspension polymenzation techniques
  • the present invention is a process for prepa ⁇ ng a carbonate polymer blend composition which exhibits a desirable balance of good processability, good thermal and physical properties, and especially, improved anisotropic impact behavior wherein a carbonate polymer is blended with an effective amount of a rubber-modified copolymer comprising a monovinylidene aromatic monomer
  • the present invention involves a method of molding or extruding a polymer blend composition whereby a carbonate polymer is blended with an effective amount of a rubber-modified copolymer comprising a monovinylidene aromatic monomer, an ethylenically unsaturated nitnle monomer, and an ester of acrylic acid, especially n-butyl acrylate.
  • the invention involves molded or extruded articles of a polymer blend composition compnsing a carbonate polymer blended with an effective amount of a rubber- modified copolymer comprising a monovinylidene aromatic monomer, an ethylenically unsaturated nitnle monomer, and an ester of acrylic acid, especially n-butyl acrylate
  • the carbonate polymer blend compositions of the present invention are especially useful in the preparation of molded objects notably parts having large surfaces prepared by injection molding techniques and having predictable finished dimensions, good heat resistance, and good room temperature and low temperature impact resistance Such properties are particularly desired for exterior automotive applications such as door panels and fascia, or other automotive applications such as instrument panels, fenders, hoods, trunk lids, side cladding parts, mirror housings, cowl vent grills, interior tnm, etc.
  • These compositions can even find use m instrument housings such as for power tools or information technology equipment such as telephones, computers, copiers, hand held computers, personal data assistants, cell
  • FIG 1 is a drawing of an injection molded plaque showing the location of test specimens prepared parallel to the polymer flow
  • FIG.2 is a drawing of an injection molded plaque showing the location of test specimens prepared perpendicular to the polymer flow.
  • Suitable carbonate polymers employed in the present invention are u ell known in the literature and can be prepared by known techniques, for example several suitable methods are disclosed in US-A-3,028,365, US-A-4,529,7 1, and US-A-4,677,162
  • carbonate polymers preferably aromatic carbonate polymers can be prepared from one or more multihydnc compounds by reacting the multihydnc compounds, preferably an aromatic dihydroxy compound such as a diphenol, with a carbonate precursor such as phosgene, a haloformate or a carbonate ester such as diphenyl or dimethyl carbonate.
  • Preferred diphenols are 2.2-b ⁇ s(4-hydroxyphenyl)-propane, 1,1- b ⁇ s(4-hydroxyphenyl)- 1 -phenylethane, 3,3-b ⁇ s(para-hydroxyphenyl)-phthahde and bishydroxyphenylfluorene.
  • the carbonate polymers can be prepared from these raw matenals by any of several known processes such as the known mterfacial, solution or melt processes. As is well known, suitable chain terminators and/or branching agents can be employed to obtain the desired molecular weights and branching degrees.
  • the aromatic carbonate polymer of the present invention comprises one or more linear carbonate components, one or more branched carbonate components, or mixtures thereof.
  • the carbonate polymer may be derived from (1) two or more different dihydnc phenols or (2) a dihydnc phenol and a glycol or a hydroxy- or acid-terminated polyester or a dibasic acid in the event a carbonate copolymer or heteropolymer rather than a homopolymer is desired
  • carbonate polymer " ' included in the term "carbonate polymer " ' are the poly(ester- carbonates) of the type descnbed in US-A-3, 169,121, US-A-4, 156,069, and US-A-4,260,731
  • Also suitable for the practice of this invention are blends of two or more of the above carbonate polymers.
  • the polycarbonates of bisphenol-A are preferred.
  • molecular weight refers to weight average molecular weights (M w ) determined on the aromatic carbonate polymers using gel permeation chromatography (GPC) with a bisphenol A polycarbonate standard. Otherwise, viscometry or light scatte ⁇ ng can also be used to determine weight average molecular weight if similar results are obtained. It should be noted that vanous references refer to "viscosity average” molecular weight (M v ), which is not the same as “weight average” molecular weight but can be correlated or converted to M w values.
  • the aromatic carbonate polymer of the present invention should have a weight average molecular weight of at least 10,000, preferably at least 15,000, more preferably at least 19,000, even more preferably at least 22,000, even more preferably at least 28,000 and most preferably at least 32,000. It has been found that the weight average molecular weight of the aromatic carbonate polymer of the present invention should not be higher than 45.000, preferably not higher than 39,000, preferably not higher than 36,000, most preferably not higher than 32,000.
  • the aromatic carbonate polymer of the present invention should have a melt flow rate (MFR), determined under conditions of 300 °C and an applied load of 1.2 kilogram (300 "C/1.2 kg), of at least 0.1 grams per 10 minutes (g/10 mm.), preferably at least 1 g/10 mm., more preferably at least 3 g/10 mm , even more preferably at least 6 g/10 mm., and most preferably at least 10 g/10 min., and preferably no more than 200 g/10 mm., preferably no more than 80 g/10 mm., more preferably no more than 40 g/10 mm., even more preferably no more than 22 g/10 mm. and most preferably no more than 14 g/10 mm.
  • MFR melt flow rate
  • the aromatic carbonate polymer of the present invention is present in an amount equal to or greater than 10 weight percent, preferably equal to or greater than 20 weight percent, more preferably equal to or greater than 30 weight percent, even more preferably equal to or greater than 40 weight percent, and most preferably equal to or greater than 50 weight percent based on the weight of the polymer blend composition.
  • the aromatic carbonate polymer of the present invention is present in an amount equal to or less than 90 weight percent, preferably equal to or less than 80 weight percent, more preferably equal to or less than 70 weight percent, even more preferably equal to or less than 60 weight percent, and most preferably equal to or less than 50 weight percent based on the weight of the polymer blend composition.
  • Suitable rubber-modified copolymers employed in the present invention compnse a monovinylidene aromatic and ethylenically unsaturated nitnle copolymer in a matnx or continuous phase and rubber particles dispersed in the matnx.
  • the matnx or continuous phase of the present invention is a copolymer compnsing polymenzed therein a monovinylidene aromatic monomer and an ethylenically unsaturated nitnle monomer or a copolymer comprising polyme ⁇ zed therein a monovinylidene aromatic monomer, an ethylenically unsaturated nitnle monomer and one or more vinyl monomer that can be copolymenzed with them.
  • Copolymer as used herein, is defined as a polymer having two or more monomers mterpolyme ⁇ zed. These compositions are genencally known as SAN-type or SAN since poly(styrene-acrylon ⁇ tnle) is the most common example.
  • the M w of the matnx copolymer is typically equal to or greater than 50,000, preferably equal to or greater than 80,000, and more preferably equal to or greater than 100.000.
  • the weight average M w of the matnx copolymer is typically equal to or less than 300,000, preferably equal to or less than to 240,000 and most preferably equal to or less than 180,000.
  • Monovinylidene aromatic monomers include but are not limited to those descnbed in
  • the monomer is of the formula.
  • Ar-C CH 2 wherein R is hydrogen or methyl, Ar is an aromatic nng structure having from 1 to 3 aromatic nngs with or without alkyl, halo, or haloalkyl substitution, wherein any alkyl group contains 1 to 6 carbon atoms and haloalkyl refers to a halo substituted alkyl group
  • Ar is phenyl or alkylphenyl, wherein alkylphenyl refers to an alkyl substituted phenyl group, with phenyl being most preferred.
  • Prefened monovinylidene aromatic monomers include, styrene, alpha-methylstyrene.
  • such monovinylidene aromatic monomer will constitute from an amount equal to or greater than 50 weight percent, preferably from an amount equal to or greater than 60 weight percent, more preferably from an amount equal to or greater than 65 weight percent, and most preferably from an amount equal to or greater than 70 weight percent based on the total weight of the matnx copolymer.
  • such monovinylidene aromatic monomer will constitute less than or equal to 95 weight percent, preferably less than or equal to 85 weight percent, more preferably less than or equal to 80 weight percent, and most preferably less than or equal to 75 weight percent based on the total weight of the matnx copolymer.
  • Unsaturated nit ⁇ les include, but are not limited to, acrylonitnle, methacrylonit ⁇ le, ethacrylomtnle, fumaromtnle and mixtures thereof.
  • the unsaturated nitnle is generally employed in the matnx copolymer in an amount equal to or greater than 5 weight percent, preferably in an amount equal to or greater than 10 weight percent, more preferably in an amount equal to or greater than 15 weight percent, and most preferably in an amount equal to or greater than 20 weight percent based on the total weight of the matnx copolymer.
  • the unsaturated nitnle is generally employed in the matnx copolymer m an amount less than or equal to 50 weight percent, preferably equal to or less than 45 weight percent, more preferably less than or equal to 35 weight percent, and most preferably less than or equal to 25 weight percent based on the total weight of the matnx copolymer
  • Other vmyl monomers may also be included m polymerized form m the matnx copolymer, including conjugated 1,3 dienes (for example butadiene, isoprene, etc ), alpha- or beta-unsaturated monobasic acids and denvatives thereof (for example, acrylic acid, methacrylic acid, etc., and the corresponding esters thereof such as methylacrylate, ethylacrylate, methyl methacrylate, etc), vmyl hahdes such as vinyl chlonde, vinyl bromide, etc., vmyhdene chlonde, vinyhdene bromide, etc.; vinyl
  • the amount of such comonomers will generally be equal to or less than 20 weight percent, more preferably equal to or less than 10 weight percent and most preferably equal to or less than 5 weight percent based on the total weight of the matnx copolymer
  • Preferred alpha-unsaturated monobasic acid comonomer denvatives are prepared from acrylic acid.
  • the esters of acrylic acid preferably employed in the present invention are those which are capable of forming, when homopolyme ⁇ zed, a polymer having a glass transition temperature (T g ) of less than 0 °C, preferably less than -20 °C wherein T g is measured by the ASTM test method designated D3418-75.
  • T g is the temperature or temperature range at which a polymeric matenal shows an abrupt change in its physical properties, including, for example, mechanical strength T g can be determined by differential scanning calonmetry (DSC)
  • the acrylic acid ester is preferably an ester of acrylic acid with an alcohol having from 1 to 12, preferably 2 to 8 carbon atoms
  • Representative of such esters are ethylacrylate, ISO- propylacrylate.
  • n- Butylacrylate is the most preferred acrylic acid ester
  • the acrylic acid ester is employed in an amount from at least 0 01 percent by weight, preferably at least 0 1 percent by weight, more preferably at least 0 5 percent by weight, even more preferably at least 1 percent by weight, and most preferably at least 2 5 percent by weight based on the total weight of the matnx copolymer Generally, the acrylic acid ester is present in an amount less than or equal to 25 percent by weight, preferably less than or equal to 15 percent by weight, more preferably less than or equal to 12 percent by weight, even more preferably less than or equal to 10 percent by weight, and most preferably less than or equal to 5 percent by weight based on the total weight of the matnx copolymer
  • the matnx copolymer is present in an amount equal to or greater than 40 weight percent, preferably equal to or greater than 50 weight percent, more preferably equal to or greater than 60 weight percent, even more preferably equal to or greater than 70 weight percent, and most preferably equal to or greater than 75 weight percent based on the weight of the rubber-modified copolymer
  • the matnx copolymer is present in an amount equal to or less than 95 weight percent, preferably equal to or less than 90 weight percent, more preferably equal to or less than 85 weight percent, even more preferably equal to or less than 80 weight percent, and most preferably equal to or less than 75 weight percent based on the weight of the rubber-modified copolymer
  • vanous techniques suitable for producing rubber-modified copolymer are well known in the art Examples of these known polymenzation processes include bulk, mass-solution, or mass- suspension polymerization, these are generally known as mass polymenzation processes See, for example, US-A-3,660,535, US-A- US-A-3 ,243
  • the polymerization is conducted in one or more substantially linear, stratified flow or so- called "plug-flow" type reactor such as described in US-A-2,727,884, which may or may not comprise recirculation of a portion of the partially polymenzed product or, alternatively, in a stirred tank reactor wherein the contents of the reactor are essentially uniform throughout, which stirred tank reactor is generally employed in combination with one or more "plug-flow" type reactors
  • the temperatures at which polymerization is most advantageously conducted are dependent on a vanety of factors including the specific initiator and type and concentration of rubber, comonomers and reaction diluent, if any, employed.
  • polymerization temperatures from 60 to 160 °C are employed prior to phase inversion with temperatures from 100 to 190 °C being employed subsequent to phase inversion. Mass polymerization at such elevated temperatures is continued until the desired conversion of monomers to polymer is obtained. Generally, conversion of from 65 to 90, preferably 70 to 85, weight percent of the monomers added to the polymerization system (that is, monomer added in the feed and any additional stream, including any recycle stream) to polymer is desired.
  • the polymerization mixture is then subjected to conditions sufficient to cross-link the rubber and remove any unreacted monomer.
  • Such cross-linking and removal of unreacted monomer, as well as reaction of diluent, if employed, and other volatile materials is advantageously conducted employing conventional devolatilization techniques, such as introducing the polymerization mixture into a devolatilizing chamber, flashing off the monomer and other volatiles at elevated temperatures, for example, from 200 to 300 °C, under vacuum and removing them from the chamber.
  • the partially polymerized product can be suspended with or without additional monomers in an aqueous medium which contains a polymerized initiator and polymerization subsequently completed.
  • the rubber-modified monovinylidene aromatic copolymer is subsequently separated from the aqueous medium by acidification, centrifugation or filtration. The recovered product is then washed with water and dried.
  • the rubbers include diene rubbers, ethylene propylene rubbers, ethylene propylene diene (EPDM) rubbers, acrylate rubbers, polyisoprene rubbers, halogen containing rubbers and mixtures thereof. Also suitable are interpolymers of rubber-forming monomers with other copolymerizable monomers.
  • the rubber may be a branched rubber, a linear rubber or mixtures thereof.
  • Branched rubbers, as well as methods for their preparation, are known in the art. Representative branched rubbers and methods for their preparation are described in Great Britain Patent No. 1,130,485 and in Macromolecules, Vol. II, No. 5, pg. 8, by R. N. Young and C. J. Fetters.
  • a preferred branch rubber is a radial or star-branched polymer, commonly referred to as polymers having designed branching.
  • Star-branched rubbers are conventionally prepared using a polyfunctional coupling agent or a polyfunctional initiator and have three or more polymer segments sometimes referred to as arms, preferably between three to eight arms, bonded to a single polyfunctional element or compound, represented by the formula (rubber polymer segment ⁇ Q wherein preferably, k is an integer from 3 to 8, and Q is a moiety of a polyfunctional coupling agent.
  • Organometallic anionic compounds are preferred polyfunctional initiators, particularly lithium compounds with Ci 6 alkyl, C 6 aryl, or Ci 2 o alkylaryl groups.
  • Tin-based and polyfunctional organic coupling agents are preferably employed; silicon-based polyfunctional coupling agents are most preferably employed.
  • Preferred rubbers are diene rubbers such as polybutadiene, polyisoprene, polypiperylene, and polychloroprene or mixtures of diene rubbers, that is, any rubbery polymers of one or more conjugated 1, 3-d ⁇ enes, with 1, 3-butad ⁇ ene being especially preferced.
  • Such rubbers include homopolymers and copolymers of 1, 3-butad ⁇ ene with one or more copolymenzable monomers, such as monovinylidene aromatic monomers as described hereinabove, styrene being preferred.
  • Preferred copolymers of 1, 3-butad ⁇ ene are block or tapered block rubbers of at least 30 weight percent 1,3-butad ⁇ ene rubber, more preferably from 50 weight percent, even more preferably from 70 weight percent and most preferably from 90 weight percent 1, 3-butad ⁇ ene rubber, and up to 70 weight percent monovinylidene aromatic monomer, more preferably up to 50 weight percent, even more preferably up to 30 weight percent, and most preferably up to 10 weight percent monovinylidene aromatic monomer, weights based on the weight of the 1, 3-butad ⁇ ene copolymer.
  • Linear block copolymers can be represented by one of the following general formulas.
  • S, Si, and S are non-elastic polymer blocks of a monovinylidene aromatic monomer, with equal or different molecular weights and B, Bi., and B are elastome ⁇ c polymer blocks based on a conjugated diene, with equal or different molecular weights.
  • the non-elastic polymer blocks have a molecular weight of between 5,000 and 250.000 and the elastomenc polymer blocks have a molecular weight of between 2,000 and 250.000.
  • Tapered portions can be present among the polymer blocks, S, Si, and S 2 and B, B b and Bi
  • the passage between the blocks B, Bi, and B 2 and S, Si, and S 2 can be gradual in the sense that the proportion of monovinylidene aromatic monomer in the diene polymer increases progressively in the direction of the non-elastomenc polymer block, whereas the portion of conjugated diene progressively decreases.
  • the molecular weight of the tapered portions is preferably between 500 and 30,000.
  • These linear block copolymers are descnbed for example in US-A-3,265,765 and can be prepared by methods well known in the art. Further details on the physical and structural charactenstics of these copolymers are given in B.C. Allport et al. "Block Copolymers", Applied Science Publishers Ltd., 1973.
  • the rubbers preferably employed m the practice of the present invention are those polymers and copolymers which exhibit a second order transition temperature, sometimes referred to as the glass transition temperature, for the diene fragment which is not higher than 0 °C and preferably not higher than —20 °C as determined using conventional techniques, for example ASTM Test Method D 746-52 T.
  • the rubber, with graft and/or occluded polymers if present, is dispersed in the continuous matrix phase as discrete particles.
  • the rubber particles comprise a range of sizes having a mono-modal distribution.
  • the average particle size of a rubber particle will, refer to the volume average diameter. In most cases, the volume average diameter of a group of particles is the same as the weight average.
  • the average particle diameter measurement generally includes the polymer grafted to the rubber particles and occlusions of polymer within the particles.
  • the average particle size of the rubber particles is equal to or greater than 0.01 micrometer ( ⁇ m), preferably equal to or greater than 0.15 ⁇ m, more preferably equal to or greater than 0.5 ⁇ m, and most preferably equal to or greater than 0.75 ⁇ m.
  • the average particle size of the rubber particles is equal to or less than 5 ⁇ m, preferably equal to or less than 2.5 ⁇ m, more preferably equal to or less than 1.5 ⁇ m, and most preferably equal to or less than 1 ⁇ m.
  • the volume average diameter can be determined by the analysis of transmission electron micrographs of the compositions containing the particles.
  • the rubber in the rubber-modified copolymer of the present invention is present in an amount equal to or greater than 5 weight percent, preferably equal to or greater than 10 weight percent, more preferably equal to or greater than 15 weight percent, even more preferably equal to or greater than 20 weight percent, and most preferably equal to or greater than 25 weight percent based on the weight of the rubber-modified copolymer.
  • the rubber in the rubber-modified copolymer of the present invention is present in an amount equal to or less than 60 weight percent, preferably equal to or less than 50 weight percent, more preferably equal to or less than 40 weight percent, even more preferably equal to or less than 30 weight percent, and most preferably equal to or less than 25 weight percent based on the weight of the rubber-modified copolymer.
  • the rubber-modified copolymer may also optionally contain one or more additives that are commonly used in polymers of this type.
  • Preferred additives of this type include, but are not limited to: stabilizers, antioxidants, impact modifiers, plasticizers, such as mineral oil, antistats, flow enhancers, mold releases, etc. If used, such additives may be present in an amount from at least 0.01 percent by weight, preferably at least 0.02 percent by weight, more preferably at least 0.05 percent by weight, more preferably at least 0.1 percent by weight, and most preferably at least 0.3 percent by weight based on the weight of the polymer blend composition.
  • the additive is present in an amount less than or equal to 5 percent by weight, preferably less than or equal to 2 percent by weight, more preferably less than or equal to 1 percent by weight, more preferably less than or equal to 0.5 percent by weight, and most preferably less than or equal to 0.3 percent by weight based on the weight of the polymer blend composition.
  • a low molecular weight additive having a surface tension of less than 30 dynes/cm (ASTM D1331, 25 °C) is included in the rubber-modified copolymer.
  • a low molecular weight silicone oil is used to improve impact properties as descnbed in US-A-3,703,491, which is herein incorporated by reference.
  • the silicone oil is polydimethylsiloxane having a viscosity of from 5 to 1000 centipoise (cp), preferably from 25 to 500 cp.
  • the composition typically contains the low molecular weight silicone oil from 0 01 to 5.0 weight percent, based on the total weight of the rubber-modified copolymer, preferably from 0.1 to 2.0 weight percent.
  • the effect of such silicone oil is enhanced by the incorporation of other additives such as wax and tallow, wherein each is also incorporated at a level of from 0.5 to 1.5 weight percent, based on the total weight of the rubber-modified copolymer.
  • fluonnated compounds such as a perfluoropolyether or a tetrafluoroethylene polymer can be used as the low molecular weight additive Mixtures of such additives can also be used.
  • the rubber-modified copolymer of the present invention preferably has a melt flow rate, determined under conditions of 220 °C and an applied load of 10 kg, equal to or greater than 0.1, more preferably equal to or greater than 1, more preferably equal to or greater than 5, and most preferably equal to or greater than 10 g/10 mm.
  • the melt flow rate of the rubber-modified copolymer is equal to or less than 100, preferably equal to or less than 50, more preferably less than or equal to 20, and most preferably equal to or less than 10 g/10 mm.
  • the rubber-modified copolymer of the present invention is present in an amount equal to or less than 90 weight percent, preferably equal to or less than 80 weight percent, more preferably equal to or less than 70 weight percent, even more preferably equal to or less than 60 weight percent, and most preferably equal to or less than 50 weight percent based on the weight of the polymer blend composition.
  • the rubber-modified copolymer of the present invention is present in an amount equal to or greater than 10 weight percent, preferably equal to or greater than 20 weight percent, more preferably equal to or greater than 30 weight percent, e ⁇ en more preferably equal to or greater than 40 weight percent, and most preferably equal to or greater than 50 weight percent based on the weight of the polymer blend composition.
  • the carbonate polymer blend composition compnses an impact modifier.
  • Preferable impact modifiers are rubber matenals having a T g equal to or less than 0 °C, preferably equal to or less than —10 °C, more preferably equal to or less than -20 °C, and most preferably equal to or less than —30 °C.
  • Suitable rubbers include polymers such as acrylate rubbers, particularly homopolymers and copolymers of alkyl acrylates having from 4 to 6 carbons in the alkyl group; or polyolefin elastomers, particularly copolymers of ethylene, propylene and optionally a nonconjugated diene.
  • mixtures of the foregoing rubbery polymers may be employed if desired.
  • the impact modifier is a grafted homopolymer or copolymer of butadiene that is grafted with a polymer of styrene and methyl methacrylate.
  • Some of the preferred rubber- containing matenals of this type are the known methyl methacrylate, butadiene, and styrene-type (MBS-type) core/shell grafted copolymers having a T g equal to or less than 0°C and a rubber content greater than 40 percent, typically greater than 50 percent.
  • graft polymerizing styrene and methyl methacrylate and/or equivalent monomers in the presence of a conjugated diene polymer rubber core, preferably a butadiene homo- or co-polymer.
  • the grafting monomers may be added to the reaction mixture simultaneously or in sequence, and, when added in sequence, layers, shells or wart-like appendages can be built up around the substrate latex, or core
  • the monomers can be added in vanous ratios to each other.
  • impact modifiers useful in the compositions of this invention are those based generally on a long-chain, hydrocarbon backbone, which may be prepared predominantly from various mono- or dialkenyl monomers and may be grafted with one or more styrenic monomers
  • a few olefmic elastomers which illustrate the vanation in the known substances which would suffice for such purpose are as follows, butyl rubber; chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber; an olefin polymer or copolymer such as ethylene/propylene copolymer, ethylene/styrene copolymer or ethylene/propylene/ diene copolymer, which may be grafted with one or more styrenic monomers; neoprene rubber; nitnle rubber, polybutadiene and polyisoprene
  • the impact modifier is preferably present in an amount of at least 1 percent by weight, preferably at least 2 percent by weight, more preferably at least 5 percent by weight, even more preferably at least 10 percent by weight, and most preferably at least 15 percent by weight based on the weight of the carbonate polymer blend composition.
  • the impact modifier is present in an amount less than or equal to 50 percent by weight, preferably less than or equal to 40 percent by weight, more preferably less than or equal to 30 percent by weight, even more preferably less than or equal to 25 percent by weight, and most preferably less than or equal to 20 percent by weight based on the weight of the carbonate polymer blend composition
  • the carbonate polymer blend composition of the present invention can be employed in mixtures, alloys or blends with other polymer and/or copolymer resins, for example, mixtures with polysulfones, polyethers, polyether lmide, polyphenylene oxides or polyesters.
  • the claimed carbonate polymer blend compositions may also optionally contain one or more additives that are commonly used in carbonate polymer blend compositions of this type.
  • Preferred additives of this type include, but are not limited to: fillers, reinforcements, ignition resistant additives, stabilizers, colorants, antioxidants, antistats, flow enhancers, mold releases, nucleating agents, etc
  • Preferred examples of additives are fillers, such as, but not limited to talc, clay, wollastonite, mica, glass or a mixture thereof.
  • ignition resistance additives such as, but not limited to halogenated hydrocarbons, halogenated carbonate oligomers, halogenated diglycidyl ethers, organophosphorous compounds, fluo ⁇ nated olefins, antimony oxide and metal salts of aromatic sulfur, or a mixture thereof may be used.
  • compounds which stabilize polymer blend compositions against degradation caused by, but not limited to heat, light, and oxygen, or a mixture thereof may be used. If used, such additives may be present in an amount from at least 0 01 percent by weight, preferably at least 0.1 percent by weight, more preferably at least 1 percent by weight, even more preferably at least 2 percent by weight, and most preferably at least 5 percent by weight based on the weight of the carbonate polymer blend composition.
  • the additive is present m an amount less than or equal to 25 percent by weight, preferably less than or equal to 20 percent by weight, more preferably less than or equal to 15 percent by weight, even more preferably less than or equal to 12 percent by weight, and most preferably less than or equal to 10 percent by weight based on the weight of the carbonate polymer blend composition.
  • Preparation of the carbonate polymer blend compositions of this invention can be accomplished by any suitable mixing means known in the art, including dry blending the individual components and subsequently melt mixing, either directly in the extruder used to make the finished article (for example, the automotive part), or pre-mixmg in a separate extruder (for example, a Banbury mixer). Dry blends of the compositions can also be directly injection molded without pre- melt mixing.
  • the carbonate polymer blend compositions of this invention are thermoplastic When softened or melted by the application of heat, the carbonate polymer blend compositions of this invention can be formed or molded using conventional techniques such as compression molding, injection molding, gas assisted injection molding, calendenng, vacuum forming, thermoformmg, extrusion and/or blow molding, alone or in combination.
  • the carbonate polymer blend compositions can also be formed, spun, or drawn into films, fibers, multi-layer laminates or extruded sheets, or can be compounded with one or more organic or inorganic substances, on any machine suitable for such purpose.
  • fabricated articles include extenor automotive applications such as door panels and fascia, or other automotive applications such as instrument panels, fenders, hoods, trunk lids, side cladding parts, minor housings, cowl vent gnlls, etc.
  • extenor automotive applications such as door panels and fascia
  • automotive applications such as instrument panels, fenders, hoods, trunk lids, side cladding parts, minor housings, cowl vent gnlls, etc.
  • These compositions can even find use in instrument housings such as for power tools or information technology equipment such as telephones, computers, copiers, hand held computers, personal data assistants, cell phones, etc.
  • Example 1 The composition of Example 1 was prepared by mixing polycarbonate resin pellets, ABS pellets and other additives in a plastic bag. The dry blended mixture was feed to a APV 30 millimeter fully intermeshmg co-rotating twin screw extruder. The following were the compounding conditions on the APV extruder: Barrel temperature: 240°C; Melt temperature: 285°C; Screw speed: 250 rotations per minute (RPM); Torque: 62 to 70 percent; Die pressure: 32 to 37 bar; and Vacuum: 0.4.
  • the extrudate was cooled in the form of strands and comminuted as pellets.
  • the extrudate was cooled in the form of strands and comminuted as pellets.
  • the pellets were dned in an air draft oven for 4 hours at 100°C and then were used to prepare 80 mm x 80 mm x 3 mm plaques on a 80 ton Demag injection molding machine having the Barrel temperature profile: 260°C, 265°C, 270°C and 280°C at the nozzle; Mold temperature: 80°C; Injection pressure/time: 15.8 MPa/3 sec; Hold pressure/time: 6.9 MPa, 6.2 MPa 2 sec, 5.2 MPa/2 sec, and 4.5 MPa/2 sec; and cooling time: 25 sec.
  • Example 1 The formulation content of Example 1 is given in Table 1 below in parts by weight of the total composition. In Table 1 :
  • PC is a bisphenol-A polycarbonate homopolymer having a melt flow rate of 10 under conditions of 300°C and 1.2 kg commercially available as CALIBRETM 200-10 polycarbonate resin from Dow Chemical;
  • ABS is a mass polymenzed ABS with 20 percent acrylonit ⁇ le, 15 percent polybutadiene rubber, and 1.5 percent n-butyl acrylate having a Vicat softening temperature of 96.5°C and a melt flow rate of 4.5 g/10 min. at 220°C and an applied load of 10 kg commercially available as MAGNUMTM 3904 ABS resm from Dow Chemical;
  • IRGANOXTM 1076 is a phenolic antioxidant available from Ciba Geigy;
  • Carbon black concentrate is a carbon black concentrate available as TAXA Z320 from Wilson.
  • MFR melt flow rate was determined according to ISO 1 133 on a Zwick 4106 plastometer at 260°C and an applied load of 5 kg;
  • “Flexural Modulus” was determined in accordance with ISO 178. Testing was performed using a Zwick 1455 mechanical tester at a rate of 2 millimeter per minute (mm/min.),
  • HDT heat deflection temperature was determined on a Ceast HDT 300 Vicat machine according to ISO 75 where test specimens were unannealed and tested under an applied pressure of 0.45 and 1.82 megapascals (MPa);
  • VST' Vicat softening temperature was determined on a Ceast HDT 300 Vicat machine in accordance with ISO 306 at 50° per hour and 5 kg; and "Dart” instrumented impact was determined according to ISO 6603 using a J&B instrumented impact tester with a 23.246 kg weight at a rate of 4.4 meter/second (m/s) at 23°C and — 30°C; and
  • Izod impact resistance as measured by the Notched Izod test was determined according to ISO 180/1 A at 23°C and — 30°C. Test specimens measured 10 mm x 80 mm x 4 mm. The specimens were notched with a notcher to give a 250 micrometer radius notch. A Zwick 5110 Izod impact testing unit was used._Anisotropy of impact was performed on bars cut from a 80 mm x 80 mm x 3 mm plaque (1) having an injection point (2) and a film gate (3). Test bars parallel (“II") to flow were cut from the middle of the plaque (20) and from the side of the plaque (21) (Fig. 1). Test bars perpendicular to flow ('ML”) were cut from the middle of the plaque (30) and from the side of the plaque near the gate (31) (Fig. 2);

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

La présente invention concerne une composition à base de mélange de polymères contenant un polymère de carbonate aromatique et un copolymère aromatique monovinylidénique modifié au caoutchouc. On améliore le comportement anisotrope de la composition à base de mélange de carbonate en copolymérisant un ester d'acide acrylique, par exemple, n-butylacrylate, avec le copolymère aromatique.
PCT/US2001/001653 2000-03-17 2001-01-18 Composition a base de melange de polymeres de carbonate WO2001070884A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001227946A AU2001227946A1 (en) 2000-03-17 2001-01-18 Carbonate polymer blend composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US52763000A 2000-03-17 2000-03-17
US09/527,630 2000-03-17

Publications (1)

Publication Number Publication Date
WO2001070884A1 true WO2001070884A1 (fr) 2001-09-27

Family

ID=24102288

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/001653 WO2001070884A1 (fr) 2000-03-17 2001-01-18 Composition a base de melange de polymeres de carbonate

Country Status (2)

Country Link
AU (1) AU2001227946A1 (fr)
WO (1) WO2001070884A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2657294A1 (fr) 2012-04-27 2013-10-30 Bayer MaterialScience AG Compositions de PC/ABS stables au traitement
WO2019185627A1 (fr) 2018-03-28 2019-10-03 Covestro Deutschland Ag Composition et masse de moulage thermoplastique pour la fabrication de corps façonnés dotés d'une brillance augmentée

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830878A (en) * 1970-12-18 1974-08-20 Mitsubishi Rayon Co Weather-and impact-resistant resin composition comprising a graft copolymer containing multi-layer polymer particles and a rigid resin
GB2196341A (en) * 1986-10-17 1988-04-27 Mobay Corp Polycarbonate molding composition
EP0462475A2 (fr) * 1990-06-21 1991-12-27 Bayer Ag Compositions de moulage thermostables comprenant des polycarbonates, des polyesters ou polyestercarbonates aromatiques, des polymères greffés et des polysulfures d'arylène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830878A (en) * 1970-12-18 1974-08-20 Mitsubishi Rayon Co Weather-and impact-resistant resin composition comprising a graft copolymer containing multi-layer polymer particles and a rigid resin
GB2196341A (en) * 1986-10-17 1988-04-27 Mobay Corp Polycarbonate molding composition
EP0462475A2 (fr) * 1990-06-21 1991-12-27 Bayer Ag Compositions de moulage thermostables comprenant des polycarbonates, des polyesters ou polyestercarbonates aromatiques, des polymères greffés et des polysulfures d'arylène

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2657294A1 (fr) 2012-04-27 2013-10-30 Bayer MaterialScience AG Compositions de PC/ABS stables au traitement
WO2013160373A1 (fr) 2012-04-27 2013-10-31 Bayer Materialscience Ag Compositions de pc/abs stables au traitement
WO2019185627A1 (fr) 2018-03-28 2019-10-03 Covestro Deutschland Ag Composition et masse de moulage thermoplastique pour la fabrication de corps façonnés dotés d'une brillance augmentée
CN111954687A (zh) * 2018-03-28 2020-11-17 科思创知识产权两合公司 用于生产具有提高的光泽度的模制品的组合物和热塑性模塑料
US11485855B2 (en) 2018-03-28 2022-11-01 Covestro Intellectual Property Gmbh & Co. Kg Composition and thermoplastic moulding compound for production of moulded articles having elevated gloss
CN111954687B (zh) * 2018-03-28 2022-12-27 科思创知识产权两合公司 用于生产具有提高的光泽度的模制品的组合物和热塑性模塑料

Also Published As

Publication number Publication date
AU2001227946A1 (en) 2001-10-03

Similar Documents

Publication Publication Date Title
CA2398807C (fr) Melanges polymeres de carbonate a ecoulement ameliore
EP1222218B1 (fr) Compositions copolymeres aromatiques ameliorees a base de monovinylidene, polymerisees en masse et modifiees au caoutchouc
JPH0733473B2 (ja) 充填剤入りポリマーブレンド
CA2019883A1 (fr) Resine thermoplastique
CA2382071C (fr) Melanges de polymeres de carbonates a ecoulement ameliore
US4511693A (en) Polycarbonate/addition polymer blends
KR100816474B1 (ko) 웰드강도가 우수한 폴리카보네이트계 열가소성 수지 조성물
CA2059849C (fr) Composition resinique du type polycarbonate
KR100873499B1 (ko) 폴리카보네이트계 수지 조성물 및 플라스틱 성형품
WO2001070884A1 (fr) Composition a base de melange de polymeres de carbonate
JPH0395245A (ja) 熱可塑性樹脂組成物
CA1204895A (fr) Melanges au polycarbonate, a resistance accrue aux chocs
AU634549B2 (en) Blends based on styrene copolymers having improved impact strength at low temperatures
JPH0575019B2 (fr)
WO2004076546A1 (fr) Compositions polymeres resistant a l'ignition
JPH08199056A (ja) 低光沢成形物品製造用の熱可塑性組成物
CA1262497A (fr) Melanges de polycarbonate et de polymeres d'addition
CN113939562A (zh) 热塑性树脂组合物及由其形成的模制品
JPH03287658A (ja) ポリカーボネート樹脂組成物
JPH02140264A (ja) 熱可塑性樹脂組成物
JPH0616737A (ja) 変性ビニル系重合体およびその組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP