CN1150275C - Polycarbonate resin/ABS graft copolymer/SAN blends - Google Patents
Polycarbonate resin/ABS graft copolymer/SAN blends Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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Abstract
Thermoplastic resin blends containing an aromatic polycarbonate resin, an acrylonitrile-butadiene-styrene graft copolymer and a styrene-acrylonitrile having a reduced styrene-acrylonitrile oligomer content exhibit an improved balance of flow properties and ductility.
Description
Technical field
The present invention relates to the thermoplastic resin composition, more particularly, relate to the thermoplastic resin composition who comprises polycarbonate (" PC ") resin, acrylonitrile-butadiene-styrene (ABS) (" ABS ") graft copolymer and styrene-acrylonitrile (" SAN ") multipolymer.
Background technology
Polycarbonate resin is tough and tensile hard engineering thermoplasties, has good shock strength.But the flow characteristics of polycarbonate resin work in-process sometimes causes difficulty.Various prior arts are all attempted polycarbonate resin and other aggretion type properties-correcting agent blend are improved its flow characteristics, still keep the toughness and the shock-resistance of polycarbonate resin simultaneously.For example, ABS graft copolymer and polycarbonate resin blend had the low-cost blend of improveing processing characteristics with production, keep good shock-resistance simultaneously and (see United States Patent (USP) the 3rd, 130, No. 177, be published on Grabowski, and Plastics World, November 1977, pp.5-58).Yet the various further effort that improve polycarbonate resin/ABS graft copolymer blends flow characteristics all cause producing hard brittle material or produce undesirable low heat deflection temperature (HDT) (" HDT ").Produce that to have polycarbonate resin/ABS graft copolymer blends that good flowability characteristics has good low temperature ductility and high HDT simultaneously will be very useful, and conform with demand.
Summary of the invention
On the one hand, the present invention relates to the thermoplastic resin composition, it comprises:
(a) aromatic polycarbonate resin;
(b) acrylonitrile-butadiene-phenylethene grafted copolymer; With
(c) styrene-acrylonitrile copolymer of attenuating styrene-acrylonitrile oligomer.
Resin combination of the present invention demonstrates the improvement balance between a kind of flow characteristics and ductility.
On the other hand, the present invention relates to prepare thermoplastic resin composition's process, comprise aromatic polycarbonate resin, acrylonitrile-butadiene-phenylethene grafted copolymer and to have lowered the styrene-acrylonitrile copolymer of styrene-acrylonitrile oligomer admixed together.
In preferred embodiments, 100 parts by weight (" pbw ") in the thermoplastic resin composition, thermoplastic resin composition of the present invention comprises 40-95pbw, be more preferably 50-90pbw, the aromatic polycarbonate resin of 55-80pbw preferably, 3-58pbw, be more preferably 7-47pbw, preferably ABS graft copolymer and the 2-57pbw of 10-40pbw are more preferably 3-43pbw, preferably the SAN of 5-35pbw.
Aromatic polycarbonate resin
Aromatic polycarbonate resin component in the present composition comprises one or more aromatic polycarbonate resin.The aromatic polycarbonate resin that is suitable as the polycarbonate resin component among the thermoplastic resin composition of the present invention is a compound known, usually see United States Patent (USP) the 3rd about their preparation and the description of characteristic, 169, No. 121, the 4th, 487, No. 896, the 5th, 411, No. 999, its content of announcing separately is attached to herein by reference.
In preferred embodiments, aromatic polycarbonate resin component of the present invention is the product that dihydric phenol and the reaction of a kind of carbonate precursor obtain, and (I) is as follows for the structural formula of dihydric phenol:
HO-A-OH (I)
Wherein A is a divalent aromatic radical,
Carbonate precursor comprises according to the structural unit shown in the formula (II):
Wherein A as above defines.
As used herein; term " divalent aromatic radical " comprises that those contain the divalent radical of single aromatic ring; as phenylene; those contain the divalent radical of aromatic condensed ring system; as naphthalene; and those contain the divalent radical that is incorporated into two or more aromatic rings together by the non-aromatic bond, for example alkylene (alkylene), alkylidene group or alkylsulfonyl, wherein one or more positions that any one can be on aromatic ring by such as halogeno-group or (C1-C6) alkyl replace.
In preferred embodiments, A is according to the divalent aromatic radical shown in the chemical formula (III):
Suitable dihydric phenol comprises such as 2, two (4-hydroxyphenyl) propane (" dihydroxyphenyl propane "), 2 of 2-, two (3, the 5-dimethyl-4-hydroxyphenyl) propane of 2-, two (4-hydroxyphenyl) methane, 4, two (4-hydroxyphenyl) heptane, (3 of 4-, 5,3 ', 5 '-tetrachloro-4,4 '-dihydroxyphenyl) propane, 2,6-dihydroxy naphthlene, Resorcinol, 2, one or more in 4 '-dihydroxyphenyl sulfone.In highly preferred embodiment, dihydric phenol is a dihydroxyphenyl propane.
Carbonate precursor is one or more in carbonyl halide, carbonic ether or the haloformate.Suitable carbonyl halide comprises such as carbonyl bromide and carbonyl chloride.Suitable carbonic ether comprises such as diphenyl carbonate, dichlorophenyl carbonic ether, dinaphthyl carbonic ether, phenyltolyl carbonate and xylyl carbonate.Suitable haloformate comprises the two haloformate such as dihydric phenol (as Resorcinol) or dibasic alcohol (as ethylene glycol, neopentyl glycol).In highly preferred embodiment, carbonate precursor is a carbonyl chloride.
Suitable aromatic polycarbonate resin comprises linear aromatic polycarbonate resins and branched aromatic polycarbonate resins.Suitable linear aromatic polycarbonate resins comprises as the bisphenol-a polycarbonate resin.Suitable branched polycarbonate resin is a compound known, by multifunctional aromatic substance and dihydric phenol and carbonate precursor reaction generation branched polymer are prepared, usually see United States Patent (USP) the 3rd, 544, No. 514, the 3rd, 635, No. 895, the 4th, 001, No. 184, its content of announcing separately is attached to herein by reference.The polyfunctional compound is normally aromatic and contain at least three functional groups; these functional groups are carboxyl, carboxylic acid anhydride, phenols, haloformate or its mixture; for example 1; 1; 1-three (4-hydroxyphenyl) ethane, 1; 3,5-trihydroxybenzene, trimellitic acid 1,2-anhydride, trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic acid dianhydride, mellitic acid, mellitic acid acid anhydride, trimesic acid, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride.Preferred multifunctional aromatic substance is 1,1,1-three (4-hydroxyphenyl) ethane, trimellitic acid 1,2-anhydride or trimellitic acid or their haloformate derivative.
In preferred embodiments, the polycarbonate resin component among the present invention is to derive and next linear polycarbonate resin from dihydroxyphenyl propane and carbonyl chloride.
In preferred embodiments, the weight-average molecular weight of polycarbonate resin is about 10,000-200,000 gram/mole (" g/mol "); In another preferred embodiment, use gel permeation chromatography with respect to polystyrene standard, the weight-average molecular weight of polycarbonate resin is about 10,000-100,000 gram/mole (" g/mol ").This resin demonstrates the intrinsic viscosity of about 0.3-1.5 deciliter/gram representatively in 25 ℃ methylene dichloride.
The preparation method of polycarbonate resin is known, as interfacial polymerization, transesterify, solution polymerization or melt polymerization.
Copolycarbonate resin (copolyester-carbonate resins) is suitable as aromatic polycarbonate resin component of the present invention equally.The Copolycarbonate resin that is suitable as the aromatic polycarbonate resin component among the thermoplastic resin composition of the present invention is a compound known, usually see United States Patent (USP) the 3rd about their preparation and the description of characteristic, 169, No. 121, the 4th, 430, No. 484, the 4th, 487, No. 896, its content of announcing separately is attached to herein by reference.
The Copolycarbonate resin comprises linear or randomly branched polymkeric substance, comprise repetition carbonate group, carboxylate group and aromatic carbocyclic group on the polymer chain of these polymkeric substance, wherein some carbonate group is directly to link to each other with the ring carbon atom of aromatic carbocyclic group at least.
In preferred embodiments, the Copolycarbonate resin Composition among the present invention is derived from carbonate precursor, at least a dihydric phenol and at least a dicarboxylic acid or dicarboxylic acid equivalent.In preferred embodiments, dicarboxylic acid is represented by molecular formula (IV):
Wherein A is alkylene, alkylidene group, cycloaliphatic radical or aryl, the substituted substituted phenylene in one or more positions on preferably non-substituted phenylene or the aromatic ring, and wherein each substituting group is (C1-C6) alkyl independently.The Copolycarbonate resin comprises second structural unit shown in first structural unit shown in the above-mentioned formula (II) and the formula V:
Wherein A ' as above defines.
Suitable carbonate precursor and dihydric phenol are top those materials of announcing.
Suitable dicarboxylic acid comprises, such as phthalic acid, m-phthalic acid, terephthalic acid, dimethyl terephthalic acid, oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dimethyl malonic acid, 1,12-dodecylic acid, suitable-1,4-cyclohexane dicarboxylic acid, anti--1,4-cyclohexane dicarboxylic acid, 4,4 '-two phenylformic acid, naphthalene-2, the 6-dicarboxylic acid.Suitable dicarboxylic acid equivalent comprises, such as acid anhydride, ester or the halide derivative of above-mentioned dicarboxylic acid, as Tetra hydro Phthalic anhydride, terephthalic acid dimethyl ester, succinic chloride.
In preferred embodiments, dicarboxylic acid is an aromatic dicarboxylic acid, preferably one or more in terephthalic acid and the m-phthalic acid.
In preferred embodiments, the ratio of ester bond and carbonic acid ester bond is to 0.9 ester bond/carbonic acid ester bond from 0.25 in the Copolycarbonate resin.
In preferred embodiments, it is about 10 that the Copolycarbonate multipolymer has, 000-200, the weight-average molecular weight of 000 gram/mole.
The preparation method of Copolycarbonate resin is known, as interfacial polymerization, transesterify, solution polymerization or melt polymerization.
The ABS graft copolymer
ABS graft copolymer component in the present composition comprises one or more ABS graft copolymers.The ABS graft copolymer that is suitable as the ABS graft copolymer component in the present composition is widely known by the people in the prior art.The ABS graft copolymer is the dispersion elasticity two-phase system mutually of a styrene-based-vinyl cyanide (SAN) multipolymer external phase and typical divinyl rubber base.With small amounts of styrene and acrylonitrile grafting to rubber particles so that two-phase is more compatible.
Three main method that can be used for preparing ABS comprise the combination of letex polymerization, body (bulk/mass) polymerization and suspension polymerization or these methods.Emulsion polymerization prepared ABS comprises two steps: polymerizing butadiene generates latex, will have other material to add subsequently; Vinyl cyanide and styrene polymerization, the grafting that takes place therebetween on the rubber generates SAN external phase simultaneously.During with emulsion polymerization prepared ABS, the content of rubber can change between about 10%-90% (weight) in the ABS grafts, and the SAN of about 10%-90% (weight) will be by grafting in the ABS graft composition.The ratio of vinylbenzene and vinyl cyanide was a variation in 50: 50 to 85: 15.When adopting letex polymerization, the size of latex particle changes in about 0.15-0.8 micron (by weight) scope, is preferably 0.3 micron.On the composition, rubber bodies can comprise polyhutadiene, styrene butadiene or perbutan, polyisoprene, EPM (ethylene/propylene rubber), EPDM rubber (the ethylene/propylene/diene rubber that comprises a small amount of diene, unconjugated double bond such as hexadiene-(1,5) or norbornadiene) and based on the C1-C8 alkyl acrylate crosslink propylene acid alkyl ester rubber of ethyl, butyl and ethylhexyl acrylate particularly.The grafting rubbers resin of one or more about 10%-90% (weight) and about 90%-10% (weight) all is an available.Last in polyreaction destroys latex emulsion and reclaim ABS.Take body to add man-hour, polyreaction is more suitable carries out in the styrene/acrylonitrile monomer, rather than carries out in water.Prefabricated rubber is dissolved in the preparation that monomer solution replaces rubber.Then rubber-monomer solution is delivered into reactor and carries out grafting/polyreaction.When adopting body or body-suspension polymerization, solubility rubber will change in about 5%-25% (weight) scope, and the diameter of dispersion rubber phase will change in about 0.5-10 micrometer range.The amount of used rubber is depended in the existence of the free SAN phase of big weight percent.
In order to replace being used in vinylbenzene and the acrylonitrile monemer in grafting or the non-graft resin, such as alpha-methyl styrene, p-methylstyrene,, two or the monomer of trihalogenated benzene ethene, alkyl methacrylate, alkyl acrylate, maleic anhydride, methacrylonitrile, maleimide, N-alkyl maleimide, N-aryl maleimide, alkyl or halo N-aryl maleimide can be used to replace vinylbenzene or vinyl cyanide, perhaps be added to wherein.As body processing, the rubber that is dissolved in monomer solution is used in suspension polymerization, but after SAN is aggregated to low the conversion, rubber/SAN/ monomer mixture will be suspended in the water, and polymerization is at this moment finished.
San copolymer
San copolymer component in the present composition comprises one or more san copolymers.Conventional san copolymer comprises the oligomer of about 0.1%-10% (weight), and wherein to refer generally to molecular weight be about 15,000 gram/moles or the SAN component that is lower than 15,000 gram/moles to oligopolymer.The more typical molecular weight that then is meant is about 10,000 gram/moles or the oligopolymer that is lower than 10,000 gram/moles.
Preferred san copolymer is meant that relative weight-average molecular weight is about 40,000 gram/mole-110,000 gram/mole, more select to be about 50,000 gram/moles-90,000 gram/mole, preferably be about 60, the SAN of 000 gram/mole-85,000 gram/mole, the wherein gel permeation chromatography of molecular weight with respect to narrow dispersed polystyrene standard.Typical san copolymer comprises about 10%-40% (weight), is more preferably about 15%-35% (weight), the vinyl cyanide of preferably about 20%-30% (weight), and the vinylbenzene with equal amount.
We find to shift out at least some and are positioned at the terminal low molecular weight substance (being at least some oligomers) that distributes from initial polymeric SAN, will reduce notched izod (notched Izod) ductile-brittle transition temperature (this temperature characterizes improved ductility).And, shift out at least some low molecular weight substances that are positioned at the end that distributes and only make mixing viscosity that small increase is arranged.Balance between like this, obtained viscosity-ductility just haves a great attraction.In addition,, can make polycarbonate/ABS/SAN blend have suitable mixing viscosity, simultaneously the characteristic of products obtained therefrom is changed in a very wide scope by selecting to shift out the amount of oligopolymer.Shifting out the low molecular weight substance that is positioned at the end that distributes also makes the Tg (and HDT) of blend raise.The rising of such Tg (and HDT) is to realize by the SAN that shifts to (moving to) higher molecular weight simply.
In composition of the present invention, the low molecular weight substance in the styrene-acrylonitrile copolymer component is that the minimizing of styrene-acrylonitrile oligomer can realize by any suitable manner.
In preferred embodiments, reduce the oligomer of the san copolymer component among the present invention with chemical fractional separation.In the prior art, suitable chemical fractionation technique is to be widely known by the people in this area.
In preferred chemical fractionation technique, san copolymer is dissolved in first solvent, methylethylketone for example, wherein high molecular san copolymer class and lower molecular weight SAN oligopolymer class are soluble, then second solvent such as Virahol or methyl alcohol are added this solution while stirring with extremely slow speed and produce with the precipitation that prevents high molecular san copolymer class, high molecular san copolymer class is soluble relatively in second solvent.The gained mixture will be divided into two-layer, and promptly first solvent layer and second solvent layer can make fractional separation gained high molecular san copolymer class be separated from first solvent layer by adding more second solvent.
Though shift out the preferred method of oligopolymer is chemical fractional separation, and this should not be considered as is limitation of the present invention.Other method also can be used to shift out oligopolymer, and these methods have also been contained in the present invention.And oligopolymer can at any time be moved out of.That is to say, shift out oligopolymer can be from the san copolymer component with before polycarbonate component is mixed, also can be after mixing, and shifts out both dual-purposes of oligopolymer before and after perhaps mixing.Other component
In addition, resin combination of the present invention comprises some additive, for example static inhibitor, weighting agent, colorant, dyestuff, antioxidant, thermo-stabilizer, ultraviolet absorbers, lubricant, fire retardant and other additive of being usually used in polycarbonate/ABS/SAN blend.
Can choose wantonly and be incorporated into the reaction product that the suitable static inhibitor that comes in the resin blend of the present invention includes but not limited to polyethylene oxide block copolymer and epoxy chloropropane, urethane, polymeric amide, polyester or polyether ester amides (polyetheresteramides).
Can choose the suitable weighting agent that is incorporated in the resin blend of the present invention wantonly and include but not limited to things such as talcum, glass fibre, lime carbonate, carbon fiber, potter's clay, silicon-dioxide, mica and conducting metal.
Suitable releasing agent can be chosen wantonly is incorporated into resin blend of the present invention.Product of the present invention can prepare by each component of the present composition is mixed to stir under the condition that is fit to the blend of formation component; for example adopt two roller mills, Banbury mixer, single screw rod or twin screw extruder to come melting mixing, make resulting composition become particle form then by methods such as granulation or grindings.
Several different methods such as blend of the present invention can be by injection moulding, extrude, rotational molding, blowing and thermoforming are fashioned into useful molding, for example the shell of computer and business machine, household implements etc.
Embodiment
Back to back embodiment has comprised various demonstration of the present invention.But it is illustrative that these embodiment only should be taken as, and should not be interpreted as having limited as the defined scope of the present invention of claims.
Embodiment
Used following abbreviation among the embodiment:
PC-1: absolute weight-average molecular weight is about the linear polycarbonate resin of 29,000 gram/moles;
PC-2: absolute weight-average molecular weight is about the linear polycarbonate resin of 24,000 gram/moles;
ABS: the acrylonitrile-butadiene-phenylethene grafted copolymer that contains have an appointment 50% (weight) divinyl and 50% (weight) styrene-acrylonitrile copolymer (75% (weight) vinylbenzene and about 25% (weight) vinyl cyanide).
SAN-1: weight-average molecular weight is about the multipolymer of 62,600 gram/moles relatively, wherein contains 75% (weight) vinylbenzene and 25% (weight) vinyl cyanide;
SAN-2: the SAN-1 of about 3.5% (weight) oligomer that shifts out by chemical fractional separation, its relative weight-average molecular weight is about 66,600 gram/moles;
SAN-3: the SAN-1 of about 7.0% (weight) oligomer that shifts out by chemical fractional separation, its relative weight-average molecular weight is about 71,500 gram/moles;
SAN-4: weight-average molecular weight is about the multipolymer of 87,600 gram/moles relatively, wherein contains have an appointment 75% (weight) vinylbenzene and 25% (weight) vinyl cyanide;
Embodiment 1-2 and comparing embodiment C1-C2
Each component is pressed the relative quantity (all in weight part) of showing the Table I defined mix the mixture that just obtains embodiment of the invention 1-2 and comparing embodiment C1-C2 respectively.The blend that will comprise the Table I ingredients listed mixes about one minute kind by Henschel method (Henshel blending), then this blend is added the funnel of forcing machine.In the experiment of typical small scale experiments chamber, adopt 20 millimeters forcing machines of 6 barrels of (six barrel) Welding Engineers under 320-400 rev/min, about 550 melt temperatures, mixture to be mixed.The gained mixture made a bet at about 525 °F compress into 28 tons of Engel shapers.Laboratory sample such as not specially provided for then thickness are 3.2 ± 0.2 millimeters.Measure notched izod according to the D256 experimental arrangement of American society standard (ASTM) and impact (Notched Izod impact).In certain temperature range, collect the notched izod data.Drop to 8 ft-lb/inches (ft-Ib/in) in striking energy and measure tough/crisp temperature when following.
With Goettfert capillary rheometer determining sample viscosity.Being determined in about 550 and about 100～6300 hertz range of frequency of viscosity carried out.
Use absolute weight-average molecular weight with respect to the gel permeation chromatography polycarbonate resin of absolute molecular weight polycarbonate standards.
SAN-1 and SAN-4 are conventional other SAN of level.During preparation SAN-2, get the SAN of about 300 gram SAN-1 classifications, it is dissolved in about 1.5 liters methylethylketone, more about 2.1 liters Virahol is added dropwise to this solution while stirring.Need keep slow speed to precipitate when adding Virahol to prevent polymkeric substance.Mixture was shelved about 1 hour.The upper strata is inclined to, obtain about 10.5 gram resistatess behind the concentrate drying.The polymkeric substance that will be dissolved in lower floor in stirrer slowly adds in the methyl alcohol and precipitates.Throw out is placed in the vacuum drying oven after filtering in about 40 ℃ of dried overnight, and several days subsequently in about 80 ℃ of dryings.
During preparation SAN-3, get the SAN of about 250 gram SAN-1 classifications, it is dissolved in about 1.25 liters methylethylketone, be added dropwise to about 1.3 liters Virahol again, as the preparation of SAN-2.The preparation of SAN-3 is the same with the preparation procedure of SAN-2.
The mixing viscosity of each mixture, notched izod is tough/result of crisp transition temperature, the Tg of polycarbonate phase and the following Table I of HDT shown in.
Table I
C1 C2 1 2
PC-1 36.8 36.8 36.8 36.8
PC-2 27.7 27.7 27.7 27.7
SAN-1 22.0 -- -- --
SAN-2 -- -- 22.0 --
SAN-3 -- -- -- 22.0
SAN-4 -- 22.0 -- --
ABS 13 13 13 13
Antioxidant and FLOW IMPROVERS 0.5 0.5 0.5 0.5
Characteristic
Notched izod is tough/crisp transformation temperature-10-38-25-35
Degree (℃)
(handkerchief-second is 100 to mix viscosity
209 293.1 226.6 257.9
Sec-1 measures down)
PC phase Tg (℃) 144.46 143.5 149.1 147.9
HDT(℃) 108 * 111 111
*The HDT of C2 does not survey
The foregoing description 1 and 2 and comparing embodiment C1 and C2 prove, by from the SAN component of polycarbonate/ABS/SAN blend, shifting out at least some oligopolymer, when keeping low relatively mixing viscosity, obtain attractive notched izod tough/crisp transition temperature is possible.
Though above-mentioned discussion comprises very detailed disclosing, still may be to disclosing various modifications for those of ordinary skill, all such modifications all should be considered in the scope of appending claims herein.
Claims (11)
1. the method for preparing the thermoplastic resin composition, comprise the content that lowers oligopolymer in the styrene-acrylonitrile copolymer by chemical fractional separation, and with aromatic polycarbonate resin, acrylonitrile-butadiene-phenylethene grafted copolymer with to have a styrene-acrylonitrile copolymer that has reduced oligomer admixed together, wherein said oligopolymer is that molecular weight is the component in the styrene-acrylonitrile copolymer that is not more than 15,000 gram/moles.
2. the process of claim 1 wherein that styrene-acrylonitrile copolymer has the weight-average molecular weight of 40,000 gram/moles-110,000 gram/mole.
3. the method for claim 2, wherein styrene-acrylonitrile copolymer has the weight-average molecular weight of 50,000 gram/moles-90,000 gram/mole.
4. the method for claim 3, wherein styrene-acrylonitrile copolymer has the weight-average molecular weight of 60,000 gram/moles-85,000 gram/mole.
5. the process of claim 1 wherein that aromatic polycarbonate resin has the weight-average molecular weight of 10,000 gram/moles-200,000 gram/mole.
6. the method for claim 5, wherein aromatic polycarbonate resin comprises two or more aromatic polycarbonate resin.
7. the method for claim 5, wherein aromatic polycarbonate resin comprises the aromatic polycarbonate resin with 29,000 gram/mole weight-average molecular weight.
8. the method for claim 5, wherein aromatic polycarbonate resin comprises the aromatic polycarbonate resin with 24,000 gram/mole weight-average molecular weight.
9. the process of claim 1 wherein that the thermoplastic resin composition comprises by said composition in 4 weight parts of the 100 weight parts acrylonitrile-butadiene-styrene copolymer to 59 weight parts.
10. the process of claim 1 wherein that the thermoplastic resin composition comprises by said composition in 5 weight parts of the 100 weight parts acrylonitritrile-styrene resin to 46 weight parts.
11. the method for claim 10, acrylonitritrile-styrene resin wherein comprise the vinyl cyanide of the 10%-40% that accounts for the multipolymer gross weight by weight and the vinylbenzene of 60%-90%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17794798A | 1998-10-23 | 1998-10-23 | |
| US09/177,947 | 1998-10-23 |
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| Publication Number | Publication Date |
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| CN1331727A CN1331727A (en) | 2002-01-16 |
| CN1150275C true CN1150275C (en) | 2004-05-19 |
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| CNB998147001A Expired - Fee Related CN1150275C (en) | 1998-10-23 | 1999-08-03 | Polycarbonate resin/ABS graft copolymer/SAN blends |
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| EP (1) | EP1129138A1 (en) |
| JP (1) | JP2002528589A (en) |
| KR (1) | KR20010075652A (en) |
| CN (1) | CN1150275C (en) |
| TW (1) | TWI227723B (en) |
| WO (1) | WO2000024829A1 (en) |
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| JP4679929B2 (en) * | 2005-02-24 | 2011-05-11 | テクノポリマー株式会社 | Infrared transparent thermoplastic resin composition and molded article using the same |
| DE102009005762A1 (en) * | 2008-12-23 | 2010-06-24 | Bayer Materialscience Ag | Impact modified polycarbonate compositions |
| US7999037B2 (en) * | 2008-12-31 | 2011-08-16 | Sabic Innovative Plastics Ip B.V. | Polycarbonate compositions |
| CN101787190B (en) * | 2009-09-21 | 2012-05-23 | 深圳市科聚新材料有限公司 | Flame-retarding environment-friendly high-intensity PC-AS composite material and preparation method thereof |
| KR101409660B1 (en) * | 2010-08-16 | 2014-06-19 | 주식회사 엘지화학 | Heat-resistant ABS resin composition having high impact strength and colorability |
| KR101400694B1 (en) * | 2010-12-31 | 2014-05-29 | 제일모직주식회사 | Thermally conductive thermoplastic resin composition having good electro-conductivity and molded articles thereof |
| CN102219979A (en) * | 2011-04-01 | 2011-10-19 | 肖智雄 | Improved and modified ABS material and laboratory basic equipment storing cabinet produced by material |
| KR101486563B1 (en) * | 2011-12-29 | 2015-01-26 | 제일모직 주식회사 | Thermoplastic resin composition and molded product using the same |
| CN102807746B (en) * | 2012-08-17 | 2014-05-28 | 东莞市信诺橡塑工业有限公司 | High-hardness and high-flowability PC/PMMA/AS (polycarbonate/polymethyl methacrylate/acrylonitrile-styrene copolymer) alloy and preparation method thereof |
| KR20140086738A (en) | 2012-12-28 | 2014-07-08 | 제일모직주식회사 | Resin compositions and articles including the same |
| CN103342886B (en) * | 2013-07-19 | 2015-08-26 | 上海锦湖日丽塑料有限公司 | A kind of spraying PC/ABS alloy material and preparation method thereof |
| US10138364B2 (en) | 2014-01-28 | 2018-11-27 | Ineos Styrolution Group Gmbh | Thermoplastic molding compounds with optimized flowability-toughness ratio |
| KR20160067675A (en) | 2014-12-04 | 2016-06-14 | 주식회사 엘지화학 | Thermoplastic Resin Composition and Molded Article Thereof |
| AU2017100888B4 (en) * | 2016-06-30 | 2018-03-22 | Ptt Global Chemical Public Company Limited | Polycarbonate composition with improved mechanical properties |
| JP6270927B2 (en) * | 2016-07-08 | 2018-01-31 | 日本エイアンドエル株式会社 | Plating resin composition and plating molded product |
| KR102018714B1 (en) | 2016-12-30 | 2019-09-04 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article using the same |
| KR102311952B1 (en) * | 2018-09-21 | 2021-10-14 | 주식회사 엘지화학 | Thermoplastic resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2550355B2 (en) * | 1987-07-14 | 1996-11-06 | 宇部サイコン株式会社 | Thermoplastic resin composition |
| US4855357A (en) * | 1988-10-12 | 1989-08-08 | General Electric Company | Low-temperature impact blends of polycarbonate, graft copolymer and rigid copolymer |
| FR2659975B1 (en) * | 1989-12-20 | 1993-04-30 | Borg Warner Chemical Europ Bv | MOLDING COMPOSITIONS BASED ON POLYCARBONATE RESIN AND STYRENE / ACRYLONITRILE COPOLYMER AND BASED ON POLYCARBONATE RESIN, STYRENE / ACRYLONITRILE COPOLYMER AND ACRYLONITRILE / STYRENE RESIN. |
| DE4216758A1 (en) * | 1992-05-21 | 1993-11-25 | Bayer Ag | Polycarbonate ABS molding compounds |
| NL9300069A (en) * | 1993-01-14 | 1994-08-01 | Gen Electric | Polymer blend composed of an aromatic polycarbonate, a polyalkylene terephthalate and a graft copolymer. |
| JPH08127686A (en) * | 1994-09-09 | 1996-05-21 | Nippon G Ii Plast Kk | Polycarbonate resin composition |
-
1999
- 1999-08-03 CN CNB998147001A patent/CN1150275C/en not_active Expired - Fee Related
- 1999-08-03 KR KR1020017004984A patent/KR20010075652A/en not_active Application Discontinuation
- 1999-08-03 WO PCT/US1999/017810 patent/WO2000024829A1/en not_active Application Discontinuation
- 1999-08-03 EP EP99937797A patent/EP1129138A1/en not_active Withdrawn
- 1999-08-03 JP JP2000578388A patent/JP2002528589A/en not_active Withdrawn
- 1999-10-11 TW TW088117488A patent/TWI227723B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| EP1129138A1 (en) | 2001-09-05 |
| CN1331727A (en) | 2002-01-16 |
| JP2002528589A (en) | 2002-09-03 |
| KR20010075652A (en) | 2001-08-09 |
| TWI227723B (en) | 2005-02-11 |
| WO2000024829A1 (en) | 2000-05-04 |
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