CN1446246A - Transparent rubber modified styrenics compositions - Google Patents
Transparent rubber modified styrenics compositions Download PDFInfo
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- CN1446246A CN1446246A CN 01813804 CN01813804A CN1446246A CN 1446246 A CN1446246 A CN 1446246A CN 01813804 CN01813804 CN 01813804 CN 01813804 A CN01813804 A CN 01813804A CN 1446246 A CN1446246 A CN 1446246A
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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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
Transparent ABS compositions useful for extrusion of clear films of a rubbery nature with good adhesion to other polymers and useful for unique molding grade clear compositions with high elongations to failure are provided. The ABS compositions utilize a styrene-butadiene rubber grafted to styrene-acrylonitrile graft phase with a methyl methacrylate and styrene-acrylonitrile rigid matrix phase where the calculated refractive index of the graft phase approximately matches that of the matrix phase in order to achieve transparent blends with ductility.
Description
Invention field
The present invention relates to the transparent styrenic polymer of rubber properties.More particularly, the present invention relates to transparent acrylonitrile-butadiene-styrene (ABS) polymkeric substance.
The description of association area
Acrylonitrile-butadiene-styrene (ABS) (ABS) plastics are rubber and thermoplastic composite, comprise all kinds of broad-spectrum graft copolymers, and this class material has the excellent balance between various mechanical propertys, work range, recyclability and the economy.Most of ABS products are by two phase composites of the graft ternary polymerization thing of the acrylonitrile-butadiene-styrene (ABS) in the continuous parent of vitreous state that is dispersed in styrene-acrylonitrile (SAN) multipolymer.Described graft ternary polymerization thing generally is made up of polybutadiene rubber core and grafted SAN shell, also have a spot of vinylbenzene and acrylonitrile grafting on rubber grain so that this two-phase is compatible.ABS has widely, and purposes is owing to optional majority kind The Nomenclature Composition and Structure of Complexes variable, to realize required performance balance.
The ABS production technique comprises three different polyreactions or stage.At first produce elastomerics (rubber) component, i.e. dienite, styrene butadiene or acrylonitrile butadiene copolymer.This stage can adopt water-base emulsion polymerization process or solution polymerization process to implement.In subordinate phase, with vinylbenzene and vinyl cyanide (50-90/10-50), optional also have other monomer copolymerization, and be grafted to described elastomerics and go up mutually, to obtain required consistency.ABS grafted rubber constituent can account for 10 to 90% weight.This stage can be adopted letex polymerization, bulk polymerization, or implements by suspension polymerization and/or emulsion-suspension polymerization.In the phase III, with second (grafting) stage at the same time or separately in operation steps independently with vinylbenzene and vinyl cyanide, optional also have other olefinic monomer copolymerization, forms the rigidity parent.In addition, this step also can comprise one or more following methods: letex polymerization, mass polymerization or suspension polymerization.Described SAN parent can account for 10 to 90% of described ABS graft composition weight.
In addition, based on the economy of producing, product performance or both considerations, can produce the ABS material by various known processing technologies as intermittent type, semibatch or successive polymerization.
In order to change the specified property of resulting polymers, can mix other monovinylidene aromatic compounds, ethylenic unsaturated nitrile and acrylate monomer, with as the supplementary component of various acrylonitrile-butadiene-styrene (ABS) components or replace various acrylonitrile-butadiene-styrene (ABS) components.The various physicalies of ABS plastic change with their production method to a certain extent, but depend on their composition under the more susceptible condition.Can satisfy the specific performance properties requirement by control monomer composition, microstructure, form or additive, and obtain the great material of difference.
Make transparent stage ABS by variety of way.Can be by vinylbenzene, vinyl cyanide and optional high-load methyl methacrylate-grafted be made transparent ABS to specific styrene butadiene rubbers (SBR) base material.Here the refractive index of dispersive rubber phase and rigidity external phase must mate well.Another kind method is to use the not enough little polybutadiene rubber particle of reflect visible light, and methyl methacrylate-styrene-acrylonitrile copolymer of being complementary of grafting refractive index and described polyhutadiene thereon.
It is the transparent cast film of the ABS plastic of 1 to 200 μ m that people's such as Schuman United States Patent (USP) the 5th, 017, No. 422 (1991) discloses thickness.This patent points out to use elastoprene, preferred polyhutadiene and grafted monomer, the graftomer of optimization styrene and vinyl cyanide is dissolved in the inert organic solvents by the solution with described ABS plastic and releasing agent, and then curtain coating originates from tread support membrane next life on upholder.The method of this use curtain coating technology shows that lasting demand is suitable for being extruded into the transparent ABS polymkeric substance of film or thin layer.
Though these methods have obtained transparency, in transparent ABS resin field, for concrete performance and potential advantageous property, still there are a large amount of unresolved and unsatisfied requirements.Need more economical, transparent ABS resin more cheaply, need to be extruded into film, especially be applicable to the transparent ABS resin of the film of laminate, transparent ABS film that need be good with the binding property of other transparent polymer also needs to have the molding graae transparent ABS composition of rubber property, ductility and high elongation at failure.
Summary of the invention
Therefore, need have especially rubber properties, with good low cost, the transparent extrusion molding ABS film of binding property of transparent polymer; Also need to have the molding graae transparent ABS composition of rubber properties.This class ABS resin is particularly useful, for example can be used for the shellproof laminate that preparation constitutes with other transparent polymer (as polycarbonate and acrylic polymers), and be used to prepare the various moulded partss that need other advantage of the transparency, high elongation at failure and ABS plastic.
For obtaining these advantages, the present invention adopts the high rubber handing-over branch phase of aryl ethylene-elastoprene base material (substrate)/aryl ethylene-vinyl nitrilation thing tectum (superstrate) base of modification, combine with aryl ethylene-vinyl nitrilation thing-vinyl esters of carboxylic acids parent rigidity, choose wantonly and other monomer or copolymer blended, obtain transparent blend, this blend can be extruded into have ductility and with the binding property good film of other transparent polymer.
The present invention mainly provides a kind of acrylonitrile-butadiene-styrene (ABS) (ABS) based composition, described composition comprises: a) derived from the parent of polymerisable aryl ethylene class material, polymerisable vinyl nitrilation thing class material and polymerisable vinyl esters of carboxylic acids class material, the amount of wherein said parent account for described composition total weight about 30 to about 70%, and the ratio of the gross weight of wherein said polymerisable aryl ethylene class material and polymerisable vinyl nitrilation thing class material and the weight of polymerisable vinyl esters of carboxylic acids class material is about 1.3 to about 1.7; B) comprise the graft copolymer of base material multipolymer and tectum multipolymer, the amount of wherein said graft copolymer accounts for about 30 to about 70% of described composition total weight; Wherein said base material multipolymer comprises that derived from about 0% to the polymerisable aryl ethylene class material of about 30% weight and about 70% multipolymer to the diene of about 100% weight, described weight percentage is based on the total weight of base material multipolymer; And wherein said tectum multipolymer comprises the multipolymer derived from polymerisable aryl ethylene class material and polymerisable vinyl nitrilation thing class material; The amount of wherein said base material multipolymer account for described graft copolymer weight about 40 to about 90%, and the amount of described tectum multipolymer accounts for about 10% to about 50% of described graft copolymer weight; The amount of wherein said base material multipolymer accounts for about 20 to about 45% of described composition total weight; The calculated value approximate match of the refractive index of wherein said multipolymer and the refractive index of described graft copolymer, thus clear composition obtained.More particularly, the invention provides a kind of acrylonitrile-butadiene-styrene (ABS) (ABS) based composition, described composition comprises: a) derived from the aryl ethylene monomer, vinyl nitrilation thing monomer and the monomeric parent of vinyl esters of carboxylic acids, the amount of wherein said parent accounts for about 30 to about 70% of described composition total weight, the aryl ethylene monomer of wherein said parent and the monomeric gross weight of vinyl nitrilation thing are about 1.3 to about 1.7 with the ratio of the monomeric weight of the vinyl esters of carboxylic acids of described parent, and the monomeric amount of the aryl ethylene of wherein said parent accounts for about 39.5 to about 53.5% of described parent gross weight, the monomeric amount of wherein said parent vinyl nitrilation thing account for described parent gross weight about 8.5 to about 19%, and the monomeric amount of the vinyl esters of carboxylic acids of wherein said parent accounts for about 37 to about 43.5% of described parent gross weight; B) comprise the graft copolymer of base material multipolymer and tectum multipolymer, the amount of wherein said graft copolymer accounts for about 30 to about 70% of described composition total weight; Wherein said base material multipolymer comprises the multipolymer derived from aryl ethylene monomer and diene monomers, wherein said base material multipolymer comprises that derived from about 0% to the aryl ethylene monomer of about 30% weight and about 70% multipolymer to the diene of about 100% weight, described weight percentage is based on the total weight of described base material multipolymer; And wherein said tectum multipolymer comprises that described weight percentage is based on the total weight of described tectum multipolymer derived from about 70 aryl ethylene monomer and the about 15 monomeric multipolymers of vinyl nitrilation thing to about 30% weight to about 85% weight; The amount of wherein said base material multipolymer account for described composition total weight about 20 to about 45%, and account for about 40 to about 90% of described graft copolymer weight; The amount of described tectum multipolymer accounts for about 10 to about 50% of described graft copolymer weight; C) particle diameter of wherein said base material multipolymer is less than 2400 (0.24 micron); And d) the calculated value approximate match of the refractive index of the refractive index of wherein said multipolymer and described graft copolymer, thus clear composition obtained.
The description of preferred embodiment
Found the high grafting rubbers of styrene butadiene rubbers/styrene-acrylonitrile (SBR/SAN) is combined (wherein making the calculated value of described grafting refractive index mutually and the refractive index approximate match of described parent phase) with rigidity parent derived from methyl methacrylate, vinylbenzene and vinyl cyanide, just can make the extrudable ABS transparent polymer of low haze of feature performance benefit with ductility and abs polymer.Found because this class SBR rubber-based abs polymer has good and binding property other polymkeric substance, low haze, the transparency and ductility, thereby can be used in particular for being extruded into the film that is used in the transparent polymer lamination product.
Abs polymer of the present invention comprises two-phase system.First comprises styrene butadiene rubbers (SBR) base material of high rubber mutually, is stained with the multipolymer of styrene-acrylonitrile (SAN) on it.This base material is commonly called " grafting phase ", and reason is the SAN physical adherence or is grafted on the described rubber by chemical reaction.Second preferably includes methyl methacrylate and the SAN that exists with polymethylmethacrylate (PMMA) form mutually, and it is commonly called " free rigidity phase ".The SBR/SAN grafting is dispersed in the polymkeric substance continuum of whole PMMA/SAN rigidity phase mutually.Rubber interface is the surface that forms the border between described grafting phase and rigidity phase.Grafted SAN as described rubber phase and the rigidity compatilizer between mutually, prevents that these two are non-misciblely separated mutually at this interface.
The used ABS analog thermoplastic resin of the present invention is vinyl nitrilation thing monomer, diene, aryl ethylene monomer and the monomeric graft copolymer of vinyl esters of carboxylic acids.Thus the applicant this with term " ABS class " or " acrylonitrile-butadiene-styrene (ABS) class " be defined as comprise various derived from as the set of vinyl nitrilation thing monomer, diene, aryl ethylene monomer and the vinyl esters of carboxylic acids polymer of monomers of following definition.Vinyl nitrilation thing monomer is defined by following structural formula at this:
Wherein R is selected from alkyl, bromine and the chlorine of hydrogen, 1 to 5 carbon atom.The monomeric example of vinyl nitrilation thing comprises vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, α-Lv Daibingxijing and Beta-bromo vinyl cyanide.Being used for diene of the present invention is defined by following structural formula at this:
Wherein each Q independently is selected from alkyl, bromine and the chlorine of hydrogen, 1 to 5 carbon atom.The example of diene comprises divinyl, isoprene, 1,3-heptadiene, methyl isophthalic acid, 3-pentadiene, 2,3-dimethylbutadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, chloro-butadiene, bromoprene, dichloro-divinyl, two bromo divinyl and composition thereof.The aryl ethylene monomer is defined by following structural formula at this:
Wherein each X independently is selected from alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxyl group, aryloxy and the halogen of hydrogen, 1 to 5 carbon atom, and wherein R is selected from alkyl, bromine and the chlorine of hydrogen, 1 to 5 carbon atom.The monomeric example of aryl ethylene that replaces comprises vinylbenzene, 4-vinyl toluene, dimethyl styrene, 3,5-diethylbenzene ethene, to t-butyl styrene, 4-n-propylbenzene ethene, alpha-methyl styrene, α-ethyl styrene, Alpha-Methyl-p-methylstyrene, para hydroxybenzene ethene, methoxy styrene, chlorostyrene, 2-methyl-4-chloro-vinylbenzene, bromostyrene, alpha-chloro vinylbenzene, alpha-brominated vinylbenzene, dichlorobenzene ethene, 2,6-dichloro--4-methyl-vinylbenzene, dibromo-benzene ethene, tetrachlorobenzene ethene and composition thereof.Vinyl esters of carboxylic acids monomer (α-, the ester of beta-unsaturated carboxylic acid) is defined by following structural formula at this:
Wherein J is selected from the alkyl of hydrogen and 1 to 8 carbon atom, and A is selected from the alkyl of 1 to 5 carbon atom.The monomeric example of vinyl esters of carboxylic acids comprises methyl methacrylate, methyl acrylate, Jia Jibingxisuanyizhi, ethyl propenoate, butyl methacrylate, butyl acrylate, propyl methacrylate, propyl acrylate, 2-EHA, methacrylic acid 2-ethylhexyl, ethylacrylic acid methyl esters (methyl ethacrylate) and composition thereof.
Should understand used " monomer " comprises that all are polymerisable, generally use in polyreaction monomer and copolymer analog materials, for example comprise monomer, be mainly a kind of monomeric homopolymer, two or more monomeric multipolymers, three kinds of monomeric terpolymers and physical mixture thereof.For example polymethylmethacrylate (PMMA) homopolymer can be used for forming described rigidity parent mutually with the mixture of styrene-acrylonitrile (SAN) multipolymer, perhaps can use methyl methacrylate-styrene-acrylonitrile (MMASAN) terpolymer.
Also can use various monomers as above-mentioned listed monomeric replenish or as its quid pro quo, so that composition disclosed herein is done further modification.Usually, but can be in the scope of not damaging objects and advantages of the present invention with the monomer compounding of component of the present invention and one or more copolymerization.For example, can be used as SBR replenish or the rubber phase of quid pro quo can comprise polyhutadiene, perbutan, polyisoprene, EPM and EPR rubber (ethylene/propylene rubber), EPDM rubber (ethylene/propene/non-conjugated diene rubber) and based on vinylformic acid C
1-C
8Crosslink propylene acid alkyl ester rubber, particularly ethyl propenoate, butyl ester and the ethylhexyl of alkyl ester, they use separately or two or more type hybrid are used.In addition, described rubber can comprise block or random copolymers.As replenishing or quid pro quo of vinylbenzene that is used for described graft resin or parent resin and acrylonitrile monemer, can use to comprise following various monomers: the vinyl esters of carboxylic acids class, as vinylformic acid, methacrylic acid and methylene-succinic acid; Acrylic amide is as acrylamide, Methacrylamide and normal-butyl acrylamide; α-, β-unsaturated dicarboxylic acid acid anhydride, as maleic anhydride and itaconic anhydride; α-, the imide of β-unsaturated dicarboxylic acid, as maleimide, N-methyl maleimide, N-ethyl maleimide, N-aryl maleimide and halogenated N-alkyl, N-aryl maleimide, the polymethylmethacrylate of imidization (poly-glutarimide); Beta-unsaturated ketone is as ethenyl methyl ketone and methyl isopropenyl ketone; Alpha-olefin is as ethene and propylene; Vinyl ester is as vinyl-acetic ester and vinyl stearate base ester; Vinyl and vinylidene halide are as the muriate and the bromide of vinyl and vinylidene; The fused aromatic rings structure of vinyl substituted is as vinyl naphthalene and vinyl anthracene; Also has pyridine.These monomers can use separately or two or more mix use.
Preferred described acrylonitrile-butadiene-styrene (ABS) class (ABS) thermoplastic resin is based on the high rubber graft copolymer of SBR with SAN/PMMA parent phase.The preferred rubber amount is about 20 to about 45%.Preferred this ABS composition comprises: a) derived from aryl ethylene monomer, vinyl nitrilation thing monomer and the monomeric parent of vinyl esters of carboxylic acids, the amount of wherein said parent accounts for about 30 to about 70%, more preferably from about 35 to about 50%, most preferably from about 38 to about 47% of described composition total weight; B) comprise the graft copolymer (grafting mutually) of base material multipolymer and tectum multipolymer, wherein said base material multipolymer comprises the multipolymer derived from aryl ethylene monomer and diene, described tectum multipolymer comprises that derived from aryl ethylene monomer and the monomeric multipolymer of ethanoyl nitrile compound the amount of wherein said graft copolymer accounts for about 30 to about 70%, more preferably from about 50 to about 65%, most preferably from about 53 to about 62% of described composition total weight; With c) wherein said parent refractive index mutually roughly the same with the calculated value of described grafting refractive index mutually (be matching difference about 0.005 or littler scope in).The refractive index of described each phase can easily calculate based on weight percentage and their refractive indexs separately of each component, for example:
The refractive index of divinyl, vinylbenzene, vinyl cyanide and methyl methacrylate polymer is respectively 1.515,1.591,1.515 and 1.491.
The ratio of Butadiene is 85: 15, and the calculated value that obtains refractive index thus is (0.85 * 1.515)+(0.15 * 1.591)=～1.526.
S among the grafting SAN: AN is 80: 20, and the calculated value that obtains refractive index thus is (0.80 * 1.591)+(0.20 * 1.515)=～1.576.
65% styrene butadiene rubbers (B: S=85: 15) and 35% grafting SAN (S: AN=80: the calculated value of the refractive index of graft copolymer 20) is (0.65 * 1.526)+(0.35 * 1.576)=～1.544.
In above example, parent must have the refractive index of mutually roughly the same with graft rubber (in ± 0.005 scope) mutually.60% PMMA and the parent refractive index mutually of 40% SAN (75% vinylbenzene and 25% vinyl cyanide) are about 1.539, therefore are complementary with grafting refractive index mutually, and difference is in 0.005.
Preferred described rigidity parent makes can easily change the ratio of PMMA/SAN and can make described parent phase economically derived from the mixture of PMMA and SAN like this.Perhaps can use the MMASAN ter-polymers.(promptly preferred existence accounts for about 56.5% to about 63% aryl ethylene-vinyl nitrilation thing of described parent gross weight and about 37% to about 43.5% vinyl esters of carboxylic acids to the ratio (for example ratio of san copolymer and PMMA homopolymer) that preferred aryl groups ethene adds vinyl nitrilation thing and vinyl esters of carboxylic acids to about 1.7 for about 1.3, and preferred the existence accounts for about 39.5% to 53.5% aryl ethylene of described parent gross weight and about 8.5% to about 19% vinyl nitrilation thing), more preferably from about 1.4 (promptly exist about 58.5% to about 61.5% the aryl ethylene-vinyl nitrilation thing that accounts for described parent gross weight to about 1.6, about vinyl esters of carboxylic acids of 38.5% to 61.5%, about 41% to about 52.5% aryl ethylene and about 9 to about 18.5% vinyl nitrilation thing), most preferably 1.5 (promptly there is about 60% the aryl ethylene-vinyl nitrilation thing that accounts for described parent gross weight, about 40% vinyl esters of carboxylic acids exists about 42% to about 51% the aryl ethylene account for described multipolymer gross weight and about 9 to about 18% vinyl nitrilation thing).
Preferred described graft copolymer is derived from aryl ethylene-elastoprene base material multipolymer.Preferred described graft copolymer comprises about 40% to about 90% base material multipolymer and about 10% to about 60% tectum multipolymer, more preferably from about 55% to about 75% base material multipolymer and about 25% to about 45% tectum multipolymer, most preferably from about 65% base material multipolymer and about 35% tectum multipolymer, wherein percentage ratio is based on the total weight of described graft copolymer.Preferred described base material multipolymer comprise account for described base material multipolymer gross weight about 0% to about aryl ethylene component of 30%, more preferably 10 to 20%, most preferably 15%; Account for described base material multipolymer gross weight about 70% to about 100%, more preferably from about 80 to about diene component of 90, most preferably from about 85%.Preferred described tectum multipolymer comprises about 70% to about 85% aryl ethylene component and about 15% to about 30% vinyl nitrilation thing component, more preferably from about 75% to about 85% aryl ethylene component and about 15% to about 25% vinyl nitrilation thing component, most preferably from about 75% to about 80% aryl ethylene component and about 20% to about 25% vinyl nitrilation thing component, wherein percentage ratio is based on the total weight of described tectum multipolymer.Described tectum can be chosen wantonly and comprise the vinyl esters of carboxylic acids component, as methyl methacrylate.
The weight average particle diameter of described grafting phase preferably less than 2400 (0.24 micron), be more preferably less than 1600 (0.16 micron), most preferably less than 1200 (0.12 micron).Usually, the particle diameter of rubber can influence the best grafting level of graft copolymer.For given weight percentage, the rubber grain that particle diameter is bigger with being equal in weight is compared, and the less rubber grain of particle diameter will provide the bigger grafted surface-area that is used for, and grafting density also can correspondingly change.Usually, the preferred less bigger higher superstrate/substrate ratio of particle utilization of rubber grain is to obtain roughly suitable result.
The vinyl esters of carboxylic acids that is preferably used as a kind of component of parent phase of the present invention comprises the methyl methacrylate that exists with polymethylmethacrylate (PMMA) form.Be used in combination with SAN by the PMMA that can buy, be easy to utilize, make it possible to regulate more neatly methyl methacrylate, can use the different PMMA of molecular weight and have PMMA of modified monomer etc. at the composition percentage ratio of parent in mutually.As known in the art, PMMA can prepare by methyl methacrylate monomer is aggregated into homopolymer.The PMMA homopolymer only exists with its pure state in theory, and the commodity of buying are generally homopolymer and one or more methyl methacrylates and vinylformic acid C
1-C
4The mixture of the multipolymer of alkyl ester (as ethyl propenoate).This commodity PMMA multipolymer contains methyl methacrylate and about 1% one or more vinylformic acid C to about 30% weight
1-C
4Alkyl ester is suitable as vinyl esters of carboxylic acids precursor components of the present invention.The multipolymer that also comprises PMMA and a spot of one or more copolymerisable monomers is as the multipolymer of methyl methacrylate and vinylbenzene and/or vinyl cyanide.
Can by various blend methods well known in the art with described grafting and described parent mutually homopolymer, multipolymer and/or terpolymer solidify, blend and gel, form the ASA blend polymer.
Can choose wantonly make with lubricator, metal release agent (metal release agent) or releasing agent.Preferred lubricant and releasing agent are the low-carbon-ester of ethylenebisstearamide, quadrol bis-stearamides, butyl stearate, barium stearate, calcium stearate, docosoic acid calcium, calcium laurate, Zinic stearas, zinc laurate, aluminum stearate, Magnesium Stearate, glycerine, mineral oil, whiteruss, various wax, higher fatty acid amides, higher fatty acid, the polyol ester and the polysiloxane group releasing agent of lipid acid.
Can choose wantonly in forming process or form the back and add as following additive: the pigment of thermo-stabilizer and ultra-violet stabilizer, antioxidant, lubricant, glidant, releasing agent or metal release agent, static inhibitor, fire retardant and fireproofing agent, softening agent, filler, pigment, dyestuff, special-effect, dropping liquid inhibitor (drip suppressant), inorganic additives and mineral filler, toughener etc. toward described resin is middle mutually.
Thermoplastic abs composition of the present invention provides the transparent composition of the ductility with rubber properties, this composition can be used for being extruded into have rubber property, with the binding property good film of polycarbonate and acrylic acid or the like material, the cost effective method of the goods of a kind of preparation as shellproof polymkeric substance lamination product is provided.Described thermoplastic compounds also can be used for providing the molding graae transparent composition of uniqueness, and this composition has high elongation at failure owing to having rubber properties.Described composition is characterised in that mist degree is 10 or lower, and notched izod impact strength is 0.8ft-lb/in (42.7j/m) or higher.
Following examples illustrate ABS preparation of compositions of the present invention and purposes.These embodiment make any qualification to the spirit and scope of the present invention unintentionally.
The United States Patent (USP) of all references all is attached to herein thus by reference herein.
Embodiment
Following examples illustrate the use of the suitable ABS composition of representing with weight part (preparation 1 and preparation 2), and with the various preparations that only use SAN (preparation 3) or PMMA (preparation 4) relatively, the advantage of described composition on performance.
With described transparent ABS composition molding and extrude to carry out performance evaluation according to the ASTM standard.In twin screw extruder and Banbury mixer, adopting and do not adopting under commercial lubricant or the metal release agent and carry out compounding.The mist degree of the injection moulding disk by measuring 0.125 inch thick sample and the optical property that transmittance is estimated described composition.Test the notched izod impact property of various compositions according to ASTMD256.Measure tensile strength and elongation according to ASTM-D638.Measure the kapillary melt viscosity according to ASTM-D3835.
HGR is the SBR/SAN graft copolymer (calculated value of refractive index is about 1.544) of the styrene-acrylonitrile (calculated value of refractive index is about 1.576) of 65% styrene butadiene rubbers (calculated value of refractive index is about 1.526) and 35%, wherein said styrene butadiene rubbers contains 85% divinyl and 15% vinylbenzene, and described grafted styrene-acrylonitrile contains 80% vinylbenzene and 20% vinyl cyanide.The median size of described grafting phase is 800 (0.08 microns).
SAN is the styrene-acrylonitrile copolymer of 75% vinylbenzene and 25% vinyl cyanide, and its weight-average molecular weight is 100,000.PMMA is the polymethylmethacrylate available from the V920 by name of Rohm and Haas, and the refractive index through measuring 60/40 SAN/PMMA mixture is about 1.539.
The agent of commodity in use Zinic stearas metal release.
Table I
Preparation 1234
HRG 61.5 53.8 53.8 53.8
SAN (pellet) 23.1 27.7 46.2
PMMA 15.4 18.5 46.2
Zinic stearas 1.0 1.0 1.0 1.0
Performance
Mist degree 6.06 4.92 38.75 37.55
Notched izod impact strength 1.6 1.0 1.0 1.5
Tensile strength (psi) 3,588 4,153 4,140 3840
Elongation % 157 149 107 132
Viscosity (pool) 500F 2,933 2,205 2,168 2058
1000/s
Specific embodiments disclosed herein is not intended to the present invention is made qualification or should not think limitation of the invention.Those skilled in the art can easily not depart from replacement, modification and the equivalent form of value that visualizes under the principle of the invention described preferred embodiment after understanding the present invention, the present invention will cover all these replacements, modification and the equivalent form of value.For example (but being not limited to), those skilled in the art obviously can be appreciated that and can adopt various other monomers, comprises that various aryl ethylenes, vinyl nitrilation thing, diene and vinyl esters of carboxylic acids monomer come the present invention is modified.
Claims (17)
1. an acrylonitrile-butadiene-styrene (ABS) (ABS) based composition, it comprises:
A) derived from aryl ethylene monomer, vinyl nitrilation thing monomer and the monomeric parent of vinyl esters of carboxylic acids, the amount of wherein said parent accounts for about 30 to about 70% of described composition total weight;
B) the aryl ethylene monomer of wherein said parent and the monomeric gross weight of vinyl nitrilation thing are about 1.3 to about 1.7 with the ratio of the monomeric weight of the vinyl esters of carboxylic acids of described parent, and the monomeric amount of the aryl ethylene of wherein said parent accounts for about 39.5 to about 53.5% of described parent gross weight, the monomeric amount of wherein said parent vinyl nitrilation thing account for described parent gross weight about 8.5 to about 19%, and the monomeric amount of the vinyl esters of carboxylic acids of wherein said parent accounts for about 37 to about 43.5% of described parent gross weight;
C) comprise the graft copolymer of base material multipolymer and tectum multipolymer, the amount of wherein said graft copolymer accounts for about 30 to about 70% of described composition total weight;
D) wherein said base material multipolymer comprises the multipolymer derived from aryl ethylene monomer and diene monomers, wherein said base material multipolymer comprises that derived from about 0% to the aryl ethylene monomer of about 30% weight and about 70% multipolymer to the diene of about 100% weight, described weight percentage is based on the total weight of described base material multipolymer; And wherein said tectum multipolymer comprises that described weight percentage is based on the total weight of described tectum multipolymer derived from about 70 aryl ethylene monomer and the about 15 monomeric multipolymers of vinyl nitrilation thing to about 30% weight to about 85% weight;
E) amount of wherein said base material multipolymer account for described composition total weight about 20 to about 45%, and account for about 40 to about 90% of described graft copolymer weight; The amount of described tectum multipolymer accounts for about 10 to about 50% of described graft copolymer weight;
F) particle diameter of wherein said base material multipolymer is less than 2400 (0.24 micron); And
G) the calculated value approximate match of the refractive index of the refractive index of wherein said multipolymer and described graft copolymer, thus clear composition obtained.
2. an acrylonitrile-butadiene-styrene (ABS) (ABS) based composition, it comprises:
A) derived from the parent of polymerisable aryl ethylene class material, polymerisable vinyl nitrilation thing class material and polymerisable vinyl esters of carboxylic acids class material, the amount of wherein said parent account for described composition total weight about 30 to about 70%, and the ratio of the gross weight of wherein said polymerisable aryl ethylene class material and polymerisable vinyl nitrilation thing class material and the weight of polymerisable vinyl esters of carboxylic acids class material is about 1.3 to about 1.7;
B) comprise the graft copolymer of base material multipolymer and tectum multipolymer, the amount of wherein said graft copolymer accounts for about 30 to about 70% of described composition total weight; Wherein said base material multipolymer comprises that derived from about 0% to the polymerisable aryl ethylene class material of about 30% weight and about 70% multipolymer to the diene of about 100% weight, described weight percentage is based on the total weight of described base material multipolymer; And wherein said tectum multipolymer comprises the multipolymer derived from polymerisable aryl ethylene class material and polymerisable vinyl nitrilation thing class material;
C) amount of wherein said base material multipolymer account for described graft copolymer weight about 40 to about 90%, and the amount of described tectum multipolymer accounts for about 10% to about 50% of described graft copolymer weight; The amount of wherein said base material multipolymer accounts for about 20 to about 45% of described composition total weight;
D) the calculated value approximate match of the refractive index of the refractive index of wherein said multipolymer and described graft copolymer, thus clear composition obtained; With
E) wherein described ABS resin is extruded into film.
3. the ABS composition of claim 2, the amount of the polymerisable aryl ethylene class material of wherein said parent accounts for about 39.5 to about 53.5% of described parent gross weight, the amount of the polymerisable vinyl nitrilation thing class material of wherein said parent account for described parent gross weight about 8.5 to about 19%, and the amount of the polymerisable vinyl esters of carboxylic acids class material of wherein said parent accounts for about 37 to about 43.5% of described parent gross weight.
4. the ABS composition of claim 2, wherein said base material multipolymer comprises that derived from about 0% to the polymerisable aryl ethylene class material of about 30% weight and about 70% multipolymer to the diene of about 100% weight, described weight percentage is based on the total weight of described base material multipolymer; And wherein said tectum multipolymer comprises that derived from about 70 to the polymerisable aryl ethylene class material of about 85% weight and about 15 multipolymers to the polymerisable vinyl nitrilation thing class material of about 30% weight, described weight percentage is based on the total weight of described tectum multipolymer.
5. the ABS composition of claim 2, wherein said base material multipolymer comprises the particle less than 2400 (0.24 micron).
6. the ABS composition of claim 2, wherein said polymerisable aryl ethylene class material comprises vinylbenzene, described polymerisable vinyl nitrilation thing class material comprises vinyl cyanide, and described diene comprises divinyl, and described polymerisable vinyl esters of carboxylic acids class material comprises methyl methacrylate.
7. the ABS composition of claim 2, the polymerisable vinyl nitrilation thing class material of the polymerisable aryl ethylene class material of wherein said parent and described parent comprises san copolymer, described polymerisable vinyl esters of carboxylic acids class material comprises the PMMA homopolymer, and described diene comprises divinyl.
8. the ABS composition of claim 2, the polymerisable aryl ethylene class material of wherein said parent, polymerisable vinyl nitrilation thing class material and polymerisable vinyl esters of carboxylic acids class material comprise the MMASAN terpolymer, and described diene comprises divinyl.
9. the ABS composition of claim 2, wherein with described film with other polymkeric substance lamination.
10. the ABS composition of claim 2, wherein with described film with other polymkeric substance lamination to form shellproof laminate.
11. the ABS composition of claim 6, wherein with described film with being selected from following polymkeric substance lamination: the physical mixture of carbonate polymer, acrylic polymers and these polymkeric substance and blend.
12. the ABS composition of claim 2, wherein said ABS resin also comprises the metal release agent.
13. the ABS composition of claim 12, wherein said metal release agent are selected from the low-carbon-ester of ethylenebisstearamide, quadrol bis-stearamides, butyl stearate, barium stearate, calcium stearate, docosoic acid calcium, calcium laurate, Zinic stearas, zinc laurate, aluminum stearate, Magnesium Stearate, glycerine, mineral oil, whiteruss, wax, higher fatty acid amides, higher fatty acid, the polyol ester and the polysiloxane group releasing agent of lipid acid.
14. the ABS composition of claim 2, wherein said ABS resin are characterised in that mist degree is 10 or lower, and notched izod impact strength is 0.8ft-lb/in or higher.
15. the ABS composition of claim 2, wherein said tectum multipolymer also comprise polymerisable vinyl esters of carboxylic acids class material.
16. an acrylonitrile-butadiene-vinyl cyanide (ABS) composition, it mainly is grouped into by following one-tenth:
A) derived from the parent of polymerisable aryl ethylene class material, polymerisable vinyl nitrilation thing class material and polymerisable vinyl esters of carboxylic acids class material, the amount of wherein said parent accounts for about 30 to about 70% of described composition total weight; The gross weight of wherein said polymerisable aryl ethylene class material and polymerisable vinyl nitrilation thing class material is about 1.3 to about 1.7 with the ratio of the weight of described polymerisable vinyl esters of carboxylic acids class material, and the amount of wherein said polymerisable aryl ethylene class material accounts for about 39.5 to about 53.5% of described parent gross weight, the amount of wherein said polymerisable vinyl nitrilation thing class material account for described parent gross weight about 8.5 to about 19%, and the amount of wherein said polymerisable vinyl esters of carboxylic acids class material accounts for about 37 to about 43.5% of described parent gross weight;
B) derived from the graft copolymer of base material multipolymer and tectum multipolymer, the amount of wherein said base material multipolymer accounts for about 40 to about 90% of described graft copolymer weight; The amount of described tectum multipolymer accounts for about 10 to about 50% of described graft copolymer weight;
C) wherein said base material multipolymer comprises that derived from about 0% to the polymerisable aryl ethylene class material of about 30% weight and about 70% multipolymer to the diene of about 100% weight, described weight percentage is based on the total weight of described base material multipolymer; And wherein said tectum multipolymer comprises that derived from about 70 to the polymerisable aryl ethylene class material of about 85% weight and about 15 multipolymers to the polymerisable vinyl nitrilation thing class material of about 30% weight, described weight percentage is based on the total weight of described tectum multipolymer;
D) amount of wherein said base material multipolymer accounts for about 20 to about 45% of described composition total weight;
E) the calculated value approximate match of the refractive index of the refractive index of wherein said multipolymer and described graft copolymer, thus clear composition obtained; With
F) wherein described ABS resin is extruded into film.
17. the ABS composition of claim 15, wherein said tectum multipolymer also comprise polymerisable vinyl esters of carboxylic acids class material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59409900A | 2000-06-14 | 2000-06-14 | |
| US09/594,099 | 2000-06-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1446246A true CN1446246A (en) | 2003-10-01 |
Family
ID=24377512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01813804 Pending CN1446246A (en) | 2000-06-14 | 2001-04-25 | Transparent rubber modified styrenics compositions |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1297070A1 (en) |
| CN (1) | CN1446246A (en) |
| WO (1) | WO2001096469A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508817B (en) * | 2008-12-17 | 2011-09-28 | 安徽科聚新材料有限公司 | High-light ABS alloy and method for producing the same |
| CN102089685B (en) * | 2008-07-16 | 2013-07-24 | 3M创新有限公司 | Multilayer optical film layer comprising blend of methyl methacrylate polymer and styrene acrylonitrile polymer |
| CN112710869A (en) * | 2020-12-09 | 2021-04-27 | 华中光电技术研究所（中国船舶重工集团公司第七一七研究所） | Harmonic oscillator rigid shaft identification device and method based on additional electrostatic rigidity principle |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100428639B1 (en) * | 2002-02-28 | 2004-04-28 | 주식회사 엘지화학 | Multi-layered transparent sheet for exterior |
| US20050282000A1 (en) * | 2004-06-16 | 2005-12-22 | General Electric Company | Multilayer composites with special visual effects |
| WO2008032907A1 (en) * | 2006-09-12 | 2008-03-20 | Cheil Industries Inc. | Transparent abs resin composition having excellent impact strength and flowability |
| KR20110076753A (en) * | 2009-12-29 | 2011-07-06 | 제일모직주식회사 | Thermoplastic resin composition and molded product using the same |
| US8691915B2 (en) | 2012-04-23 | 2014-04-08 | Sabic Innovative Plastics Ip B.V. | Copolymers and polymer blends having improved refractive indices |
| CN102863732A (en) * | 2012-09-12 | 2013-01-09 | 江苏安格特科技发展有限公司 | Low-temperature impact-resistant extrusion-grade acrylonitrile butadiene styrene (ABS) alloy material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113798A (en) * | 1975-09-11 | 1978-09-12 | Monsanto Company | Transparent ABS polyblends |
| US4083896A (en) * | 1976-07-22 | 1978-04-11 | Monsanto Company | Transparent polyblends |
| DE3719849A1 (en) * | 1987-06-13 | 1988-12-22 | Bayer Ag | ABS PLASTIC FILMS BY THE MOLDING PROCESS |
| DE69501584T2 (en) * | 1994-11-21 | 1998-09-10 | Gen Electric | Impact-modified compositions based on copolymers of alpha-alkyl vinyl aromatics and vinyl cyanide |
| JP2001521966A (en) * | 1997-10-31 | 2001-11-13 | ザ ダウ ケミカル カンパニー | Rubber-modified monovinylidene aromatic polymer blend |
-
2001
- 2001-04-25 WO PCT/US2001/013300 patent/WO2001096469A1/en active Application Filing
- 2001-04-25 EP EP01928850A patent/EP1297070A1/en not_active Withdrawn
- 2001-04-25 CN CN 01813804 patent/CN1446246A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102089685B (en) * | 2008-07-16 | 2013-07-24 | 3M创新有限公司 | Multilayer optical film layer comprising blend of methyl methacrylate polymer and styrene acrylonitrile polymer |
| CN101508817B (en) * | 2008-12-17 | 2011-09-28 | 安徽科聚新材料有限公司 | High-light ABS alloy and method for producing the same |
| CN112710869A (en) * | 2020-12-09 | 2021-04-27 | 华中光电技术研究所（中国船舶重工集团公司第七一七研究所） | Harmonic oscillator rigid shaft identification device and method based on additional electrostatic rigidity principle |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1297070A1 (en) | 2003-04-02 |
| WO2001096469A1 (en) | 2001-12-20 |
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