CN1131278C - Shock-resistant thermoplastic moulding materials made of syndiotactic polystyrene and acrylate modifier - Google Patents

Shock-resistant thermoplastic moulding materials made of syndiotactic polystyrene and acrylate modifier Download PDF

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CN1131278C
CN1131278C CN99809629A CN99809629A CN1131278C CN 1131278 C CN1131278 C CN 1131278C CN 99809629 A CN99809629 A CN 99809629A CN 99809629 A CN99809629 A CN 99809629A CN 1131278 C CN1131278 C CN 1131278C
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weight
thermoplastic composition
film
vinylbenzene
component
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CN1312834A (en
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G·E·麦基
J·温施
F·拉姆斯泰纳
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BASF SE
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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
    • 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
    • C08L25/06—Polystyrene
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Abstract

Thermoplastic moulding materials comprises(A)30-99. 9 wt. % vinyl aromatic polymers with a syndiotactic structure,(B)0.1 - 70 wt. % rubber elastic particle-shaped graft polymers with(C)0 - 69.9 wt. % rubber elastic particle-shaped styrene/diene block copolymers, whereby the proportion of diene can be fully or partially hydrogenated and the particles of constituent(B) have a D(50)value ranging from 0.1-10 mu m and constituent(B)is different from constituent(C).

Description

The shock-resistant thermoplastic moulding compound that makes by syndiotactic polystyrene and acrylate modifier
Technical field
The present invention relates to thermoplastic composition.The invention still further relates to this thermoplastic composition and be used for the purposes of producd fibers, film or moulded product, and relate to prepared fiber, film and moulded product.
Background technology
The degree of crystallinity of syndiotactic polystyrene makes it have about 270 ℃ high fusing point, high rigidity and performances such as tensile strength, dimensional stability, low-k and high chemical resistance.Even also can keep its mechanical property characteristics being higher than under the temperature of second-order transition temperature.The method for preparing syndiotactic polystyrene in the presence of metalloscene catalyst is known, for example has a detailed description in EP-A 0 535 582.
The Application Areas of syndiotactic polystyrene is owing to its fragility is subjected to strict restriction.
Therefore be also referred to as the fragility of SPS below the hope reduction syndiotactic polystyrene, improve its shock strength simultaneously.
EP-A 755 972 has narrated impact modified SPS, uses on the other hand to make mixture from the segmented copolymer of vinylbenzene and hydrogenated butadiene and carry out modification, carries out modification with a kind of core/shell polymeric with butadiene polymer core on the other hand.But such properties-correcting agent can not be heat-resisting or weather-proof.The shock strength of this material is still not enough, and particularly owing to these reasons, they are not the desired solution that addresses this problem.
Summary of the invention
The purpose of this invention is to provide a kind of thermoplastic composition, said composition is composed of the following components:
A) vinylaromatic polymer of the syndiotactic structure of 50～95% weight,
B) the butyl polyacrylate polymkeric substance of the elastomer particles shape vinylbenzene of 5～50% weight or vinylbenzene and acrylonitrile grafting, the second-order transition temperature that constitutes the polymkeric substance of its sandwich layer is lower than-20 ℃, its condition be this graftomer be by microsuspension preparation and
C) the elastomer particles shape vinylbenzene-diene block copolymer of 0～35% weight, its diene part can be partially or completely hydrogenant, wherein B component) particulate D (50) is 0.3～7 μ m, and B component) be different from component C).
Another object of the present invention is a preparation SPS based thermoplastic moulding compound, and this composition has both high impact, high rigidity (Young's modulus) and good flowability (MVR, workability), and still can keep its weathering resistance.
We have found that the thermoplastic composition that adopts this paper to start definition has reached this purpose.
Found that also this thermoplastic composition is used for the purposes of producd fibers, film or moulded product, and prepared fiber, film and moulded product.
This novel thermoplastic composition comprises as component A) 30～99.9% weight, preferred 40～99% weight, the especially vinylaromatic polymer with syndiotactic structure of 50～95% weight.For purposes of the invention, " having syndiotactic structure " this expression formula is meant that this polymkeric substance mainly is syndyotactic, promptly by 13Together partly greater than 50%, be preferably greater than 60%mmmm five unit groups between C NMR mensuration.
Component A) preferably form by the compound of general formula I: In the formula:
R 1Be hydrogen or C 1～C 4-alkyl,
R 2～R 6Be hydrogen, C independently of one another 1～C 12-alkyl, C 6～C 18-aryl or halogen, perhaps wherein 2 adjacent groups lump together and form 1 cyclic group that contains 4～15 carbon atoms, for example C 4～C 8-cycloalkyl or condense ring system.
The vinyl aromatic compounds of the preferred formula I that uses as give a definition, wherein
R 1Be hydrogen.
Particularly suitable substituent R 2～R 6Be hydrogen, C 1～C 4-alkyl, chlorine, phenyl, xenyl, naphthalene and anthracene.2 adjacent groups also can lump together and form 1 cyclic group that contains 4～12 carbon atoms, so naphthalene derivatives and anthracene derivant are the examples of formula I compound.
The example of the preferred compound of this type is: vinylbenzene, p-methylstyrene, to chloro-styrene, 2,4-dimethyl styrene, 4-vinyl biphenyl, vinyl naphthalene and vinyl anthracene.
Also can use the mixture of various vinyl aromatic compounds, but preferably only use a kind of vinyl aromatic compounds.
Particularly preferred vinyl aromatic compounds is vinylbenzene and p-methylstyrene.
Employed component A) also can be various mixtures, but preferably only use a kind of vinylaromatic polymer, particularly syndyotactic polystyrene (SPS) with vinylaromatic polymer of syndiotactic structure.
Vinylaromatic polymer with syndiotactic structure with and preparation method thereof itself be known, for example be described among the EP-A 535 582.Preparation procedure better is in the presence of metallocene complex and promotor the compound of general formula I to be reacted.Employed metallocene complex is pentamethyl-cyclopentadienyl titanous chloride, pentamethyl-cyclopentadienyl (trimethylammonium) titanium and pentamethyl-cyclopentadienyltitanium trimethylammonium thing preferably.
The molecular weight Mw (weighted average) of syndiotactic vinyl polymkeric substance is generally 5000～10,000,000g/mol, particularly 10,000～2,000,000g/mol.Molecular weight distribution M w/ M nBe generally 1.1～30, preferred 1.4～10.
The syndiotactic vinyl aromatic polymers A that other is possible) is based on the syndiotaxy star polymer of vi-ny l aromatic monomers.For example, this class star polymer is described in German patent application 196 34 375.5-44 early, walks to the 6th page of 25 row referring to page 2 21 especially, and embodiment.
Its core layer polymer is not formed by the divinylic monomer polymerization, but with few butadiene as linking agent, and better be by α, beta-unsaturated carboxylic acid, α, beta-unsaturated carboxylic acid ester or α, alpha, beta-unsaturated nitriles, for example vinylformic acid, methacrylic acid, acrylate, methacrylic ester, vinyl cyanide, methacrylonitrile or their mixture, and add linking agent if necessary, and carry out polymerization and the graftomer B that forms) better make as follows: make to aggregate into core layer polymer P KLiquid monomer or liquid monomer mixture M KMix with water and protective colloid.Polymerization starter also can be at this moment or not at this moment, disperses the back to add up to monomer, perhaps adds after this dispersion liquid heating again.Adopt powerful high-speed stirring to come to prepare the dispersion liquid of minimum monomer droplet water from this non-homogeneous mixture.The strong mixer of any design all is applicable to this purpose.Desirable granularity in this range of definition for example can go out a certain size particles number by shooting optical microphotograph photograph and number and measure.
Come initiated polymerization by heating this dispersion liquid.Polyreaction is carried out, up to based on M under the medium stirring dynamics that can further not cut apart drop KTransformation efficiency reach more than 50%, preferred more than 85% till.
In case after the polyreaction of grafting sandwich layer finishes, just use monomer M SProceed reaction by known mode own, by monomer M SPreparation is by polymer P SThe corresponding shell S that constitutes.Possible monomer M SBe the vinylbenzene or derivatives thereof, and acrylate, methacrylic ester, alpha-methyl styrene, vinyl cyanide and methacrylonitrile.Used monomer M SBe preferably 100% vi-ny l aromatic monomers, optimization styrene, or by 80% above weight, the vinylbenzene of preferred 85～95% weight and be no more than 20% weight, the mixture that the vinyl cyanide of preferred 5～15% weight constitutes.Graft reaction also can be in monomer M KTransformation efficiency in polyreaction is also incomplete, but is higher than 50%, preferably is higher than at 85% o'clock and begins.In the case, compare with the significantly synoptic diagram of core/shell polymeric under the sandwich layer monomer conversion situation at first fully, its transition from the shell to the sandwich layer is comparatively progressive.
If this graftomer has only 1 shell, this is normally enough, and then it is by material P SConstitute.In some cases, if especially the grafting sandwich layer is less, and if wish in particle, to introduce relatively large core layer polymer, then structure is P K-P S-P K-P SMany shells graftomer be recommendable, wherein inner shell also can be by other polymer P XConstitute, thereby so that improve and improve the performance of this graftomer.
Monomer M KUsually at 0～100 ℃, preferably disperse, and every kilogram of monomer is usually with 0.4～10kg water in room temperature.
Be applicable to that the protective colloid of stablizing this dispersion is a water-soluble polymers, the polymer beads that it can be sealed the monomer droplet and be formed by it, thus suppress its cohesion.
The protective colloid that is suitable for is a derivatived cellulose, as carboxymethyl cellulose and Walocel MT 20.000PV, and poly N-vinyl pyrrolidone, polyvinyl alcohol and polyethylene oxide, anionic polymer such as polyacrylic acid, and anionic polymer such as poly N-vinyl imidazoles.The consumption of these protective colloids preferably accounts for monomer M K0.1～5% weight of gross weight.Should not use low molecular weight surfactants when preparing graftomer of the present invention, as those tensio-active agents itself relevant with negatively charged ion or cationic soap, because can obtain polymer beads when using them, as resulting the sort of in letex polymerization than small particle size.But,, use the mixture of forming by protective colloid and soap more more favourable than using protective colloid separately for obtaining less granularity.
The polymerization starter that is suitable for is a free-radical generating agent, remarkable solvability is arranged in monomer especially and 25～150 ℃ transformation period is those free-radical generating agent of 10 hours (" 25～150 ℃ time 10 hour transformation period ") more fortunately.The example of possible initiator is superoxide such as lauroyl peroxide, persulphate, crosses the PIVALIC ACID CRUDE (25) tert-butyl ester and azo-compound such as Diisopropyl azodicarboxylate.Various different initiators all can be used for preparing grafting sandwich layer and grafting shell.The consumption of initiator is generally 0.1～2.5% weight of amount of monomer.
Reaction mixture preferably also can comprise buffer substance, as Na 2HPO 4/ NaH 2PO 4Or Trisodium Citrate/citric acid, so that make pH keep constant.In polymerization process, especially in the monomer M that forms shell SPolymerization process in also add molecular weight regulator usually, as Thiovanic acid ethylhexyl or uncle's lauryl mercaptan.
Make monomer M KPolymerization generates by P KThe temperature of the sandwich layer that constitutes is generally 25～150 ℃, is preferably 40～120 ℃.Shell is grafted to graft polymerization reaction on the sandwich layer generally at 25～150 ℃, preferably carries out at 50～120 ℃.The lower limit of these temperature ranges is equivalent to the decomposition temperature of employed each polymerization starter.
Graftomer B) comprises a second-order transition temperature and be lower than 0 ℃, preferably be lower than-10 ℃, more preferably less than-20 ℃ phase.Have this type second-order transition temperature possible polymkeric substance especially 50～100% weight by vinylformic acid C 2-C 36Alkyl ester such as ethyl propenoate, vinylformic acid n-propyl or isopropyl acrylate, or those polymkeric substance of preferred n-butyl acrylate and/or 2-EHA formation.Except these " soft " monomers, ratio is no more than " firmly " monomer of 50% weight, as methyl acrylate, methacrylic acid (C 1-C 12-alkyl) ester, vinylbenzene and alpha-methyl styrene, vinyl cyanide and methacrylonitrile etc. also is suitable for.These polymkeric substance generally form the sandwich layer of polymkeric substance, but also may form shell.
This base polymer that is generally core layer polymer is with being no more than 10% weight, the difunctionality or the polyfunctional monomer of preferred about 0.1～10% weight, for example divinyl or isoprene, the divinyl ester of dicarboxylic acid such as succsinic acid or hexanodioic acid, dibasic alcohol such as ethylene glycol or 1, the diallyl of 4-butyleneglycol or divinyl ether, the diester that acrylic or methacrylic acid and above-mentioned dibasic alcohol form, 1,4-Vinylstyrene or triallyl cyanurate make.Particularly preferably be the vinylformic acid tricyclodecenyl ester shown in the general formula I (vinylformic acid dihydro dicyclopentadienyl ester): And allyl acrylate and allyl methacrylate(AMA).
At graftomer B) in, the weight ratio of all shell summations and sandwich layer is about 0.05: 1～2.5: 1.Preferably the particulate mean diameter that especially walks to the described microsuspension method preparation of the 18th page of the 6th row for the 9th page the 25th by DE 19702733.4 is about 0.1～about 10 μ m, preferred 0.2～9 μ m, preferred especially 0.3～7 μ m.Mean diameter is D 50, wherein all particulate diameters of 50% weight less than, all particulate diameters of 50% weight then greater than with D 50Corresponding diameter.In order to characterize size-grade distribution, its width particularly is except D 50Also usually provide D outward, 10And D 90All particulate diameters of 10% weight are less than D 10, all particulate diameters of 90% weight are greater than D 10Diameter.Similarly, all particulate diameters of 90% weight less than, and all particulate diameters of 10% weight greater than with D 90Corresponding diameter.
B component) preferably has and substrate polymer, promptly with SPS (derivative) the compatible shell of part perhaps mutually.
B component in this novel moulding compound) content accounts for 0.1～70% of this moulding compound weight, and is preferred 1～60%, especially 5～50% weight.More preferably, the B component of 50% above number) be present in the moulding compound of the present invention with non-cohesion form.
By diene part can be the elastomeric component C that constitutes of hydrogenant vinylbenzene-diene block copolymer partially or completely) be known, for example can be referring to EP-A 755 972, and can buy from for example Shell Co. Ltd, its commodity are called Kraton G 1651.Other example is the Cariflex of Shell Co. Ltd -TR the trade mark, the Finaprene of Fina company The trade mark, and the Europrene of Enichem company The trade mark.
Component A), B) and summation C) be 100% weight.
If desired, can in this novel thermoplastic moulding compound, add the additive or the processing aid of common consumption, or its mixture.
Its example is the salt of nucleator such as carboxylic acid, organic sulfonic acid or organic phosphoric acid, preferred sodium benzoate, three (p-tert-butyl benzoic acid) aluminium, three aluminum benzoates, three (to the carboxymethyl phenylformic acid) aluminium and three caproic acid aluminium; Antioxidant such as phenol antioxidant, phosphorous acid ester or phosphinate, especially tricresyl phosphite (nonyl phenyl) ester; Stablizer such as sterically hindered phenol and quinhydrones.Also can make with lubricator and releasing agent, dyestuff, pigment and softening agent.
Can use organo phosphorous compounds such as phosphoric acid ester or phosphine oxide as fire retardant.
The example of phosphine oxide is triphenylphosphine oxide, oxidation trimethylphenyl phosphine, oxidation three (nonyl phenyl) phosphine, oxidation tricyclohexyl phosphine, oxidation tri-n-butyl phosphine, oxidation three n-hexyl phosphines, oxidation tri-n-octyl phosphine, oxidation three cyanoethyl phosphines, oxidation benzyl dicyclohexylphosphontetrafluoroborate, oxidation benzyl diphenylphosphine and oxidation phenyl di-n-hexyl phosphine.Particularly preferred triphenylphosphine oxide, oxidation tricyclohexyl phosphine, oxidation tri-n-octyl phosphine or the oxidation three cyanoethyl phosphines of being to use.
Possible phosphoric acid ester is alkyl-or phosphoric acid ester of replacing of aryl especially.Its example is two (dodecyl) phosphoric acid ester of phenyl, phenyl di neo-pentyl phosphoric acid ester, phenylethyl phosphoric acid hydrogen ester, phenyl two (3,5,5-trimethylammonium hexyl) phosphoric acid ester, ethyl-2-phenyl-phosphate, two (2-ethylhexyl) p-methylphenyl phosphoric acid ester, the trimethylphenyl phosphoric acid ester, three (xylyl) phosphoric acid ester, three basic phosphoric acid ester, two (2-ethylhexyl) phenyl phosphate ester, three (nonyl phenyl) phosphoric acid ester, two (dodecyl) p-methylphenyl phosphoric acid ester, three cresyl phosphoric acid ester, triphenylphosphate, the dibutyl phenyl phosphate ester, p-methylphenyl two (2,5,5-trimethylammonium hexyl) phosphoric acid ester and 2-ethylhexyl diphenyl phosphate.Particularly suitable phosphorus compound is each R those phosphoric acid ester that are aryl wherein.Triphenylphosphate, three (xylyl) phosphoric acid ester and three basic phosphoric acid ester are very particularly suitable.Also can use annular phosphate: the diphenyl pentaerythritol bisphosphate is particularly suitable here, also resorcinol diphosphate preferably.
Also can use the mixture of various different phosphate compounds.
In addition, this novel thermoplastic moulding compound also can comprise fibrous or granulated filler or their mixture.
Its example is carbon fiber, glass fibre, glassmat, glass gauze and granulated glass sphere, and potassium titanate palpus crystalline substance and aramid fiber, preferred glass fibers.Glass fibre can be starching with flooded coupler.These glass fibre can be with short glass fiber or silk thread (yarn) form adding continuously.Preferred glass fibre comprises the aminosilane slurry.
Also can use soft silica, magnesiumcarbonate, flint, mica, talcum, feldspar, Calucium Silicate powder or leaf silicate.
This novel thermoplastic moulding compound can make with following method: usually at 270～330 ℃ each component is mixed in mixing roll or the single screw extrusion machine in traditional mixing equipment such as kneader, spot uncle, but preferably use twin screw extruder.For obtaining moulding compound very uniformly, need brute force and mix fully.The blend order of each component can change, therefore can be with 2 kind, or words as desired, more kinds of components are carried out premix, but also all components can be mixed together.
This novel thermoplastic moulding compound also can be as stated above and other polymkeric substance such as atactic or isotactic homopolystyrene, vinylbenzene and comonomer be the multipolymer of vinyl cyanide, methacrylic ester and/or diphenylethlene for example, or with polymeric amide, polyester or polyphenylene oxide, or these mixture of polymers are carried out blend.
This novel thermoplastic moulding compound has high impact, high rigidity and good flowability (workability).Said composition is applicable to producd fibers, film or moulded product.
Embodiment
Embodiment
The preparation of SPS
The preparation of syndiotactic polystyrene (SPS)
In 1 round-bottomed flask of having set up inert conditions, add 9.2mol vinylbenzene (1000g) with nitrogen.This solution is heated to 60 ℃, mixes available from the diisobutylaluminium hydride DIBAH (1.0M cyclohexane solution) of Aldrich company available from the methylaluminoxane (MAO) (1.53M toluene solution) of Witco company and 20ml with 78.3ml then.The gained mixture again with 91.2mg[C 5(CH 3) 5] TiMe 3Mix.Make internal temperature remain on 60 ℃, allow this polymerization of mixtures 2 hours, add methyl alcohol then polyreaction is stopped.The resulting polymers methanol wash is carried out vacuum-drying at 50 ℃.With 1,2, the 4-trichlorobenzene is made solvent and is measured its molecular weight and molecular weight distribution at 135 ℃ with high temperature GPC method.Proofread and correct with mark in the polystyrene of narrow distribution.Molecular weight M w=322,100, Tile Width M w/ M n=2.1.With 13The syndiotaxy fraction that the C-NMR method is measured is greater than 96%.Transformation efficiency based on used styrene monomer is 84%.
The preparation of graft rubber
Used following starting raw material:
Vinylbenzene (St), vinyl cyanide (AN), butyl acrylate (BA) and derive from the vinylformic acid dihydro dicyclopentadienyl ester of BASF AG, during use without further purification.
Mowiol 8/88 available from Hoechst company is a kind of polyvinyl alcohol, is 8m Pa/s (first figure place) with 4% aqueous solution in the viscosity of 20 ℃ of mensuration by DIN 53015 methods.Its degree of hydrolysis is 88mol% (last 2 figure places).
The fill a prescription styrene-grafted butyl polyacrylate rubber of following usefulness (being designated as MS-1) and prepare as follows with vinylbenzene and vinyl cyanide (95: 5) grafted butyl polyacrylate rubber (being designated as MS-2):
Describe Shell Core
MS-1 40(100St) 60(98BA+2DCPA)
MS-2 40(95St+5AN) 60(98BA+2DCPA)
For the grafting shell that is made of vinylbenzene and vinyl cyanide, grafted monomer is formed corresponding change.
The graft rubber preparation
Under nitrogen protection, following mixture was stirred 20 minutes with 7000rpm with the Dispermat agitator.Dispermat is made by VMA-Getzman company, has equipped 1 toothed disk of 5cm.
Mixture is composed as follows:
1174.2g water
220.5g Mowiol 8/88 aqueous solution of 10% concentration
11.0g the emulsifier aqueous solution of 40% concentration
1080.5g n-butyl acrylate
22.1g vinylformic acid dihydro dicyclopentadienyl ester and
5.5g dilauroyl peroxide.
The 100g mixture of this emulsion mixture is joined 67 ℃ under nitrogen protection and carry out middling speed and stir in the glass flask of (250rpm), so the beginning polyreaction.Add remaining emulsion mixture with 180 fens clock times.Continue polymerization 60 minutes.Add Mowiol 8/88 aqueous solution of 2492.7g water and 454.7g 10% concentration then in this mixture, then add 1515.7g vinylbenzene, this monomer added as charging in 150 minutes.67 ℃ again through 150 minutes, again 70 ℃ through 210 minutes, polyreaction has just been finished.
The Microtac UPA150 type laser scanning measuring apparatus that the size-grade distribution of dispersion is made with Leeds and Northrup company.
The result:
Rubber MS-1 (shell that constitutes by 100% vinylbenzene)
D(10)：0.6μm
D(50)：1.0μm
D(90)：2.6μm
Rubber MS-2 (shell that constitutes by 95% vinylbenzene and 5% vinyl cyanide)
D(10)：0.3μm
D(50)：0.7μm
D(90)：1.2μm
Kraton G 1651
Kraton G 1651 is a kind of shell segmented copolymers with following structure:
Vinylbenzene-hydrogenated butadiene-styrene segmented copolymer.Vinylbenzene: rubber=32: 68.
The preparation of blend
SPS, when suitable, Kraton G 1651 fusion in a ZSK 30 type forcing machines, (MS-1 MS-2) directly pumps in this polymer melt with the MS dispersion to use single pump then.Water is extracted out along forcing machine by auxiliary screw rod, the final polymer melt is discharged, is cooled off and granulation from forcing machine.
The result
The results are shown in the appended table.
Explanation
Just as can be seen, (MS-1 MS-2) has obtained the own better properties combination than Kraton, as notched Izod impact strength, MVR, Young's modulus, yielding stress and rupture stress to use MSP rubber.The SPS composition properties of modified rubber
Experiment 1 2) 2 3 4 5
Prescription
SPS (% weight) 65 65 65 65 65
KratonG 1651 (% weight) 35 15 15
MS-1 (% weight) 35 20
MS-2 (% weight) 35 20
Young's modulus mPa 1596 2113 - 1990 1869
Yielding stress mPa 25.2 30.5 - 34.1 30.9
Rupture stress mPa 22.3 24.3 - 30.4 26.9
Elongation ％ 2.1 1.8 - 2.3 2.2
Extension at break ％ 0 0 - 0 0
MVR 290/5 cm 3/10min 48.5 71.6 80.5 65.2 75.3
Notched Izod impact strength 1) KJ/m 2 4 * 10 * 80mm sample mold temperature: 80 ℃ 6.0 4.4 2.4 6.5 4.9
Notched Izod impact strength 1) KJ/m 2 4 * 10 * 80mm sample mold temperature: 140 ℃ 3.6 3.4 2.7 4.0 2.6
1) according to DIN 53353 at 290 ℃ of polymer-melt temperatures 2) be not according to of the present invention

Claims (9)

1. thermoplastic composition, said composition is composed of the following components:
A) vinylaromatic polymer of the syndiotactic structure of 50～95% weight,
B) the butyl polyacrylate polymkeric substance of the elastomer particles shape vinylbenzene of 5～50% weight or vinylbenzene and acrylonitrile grafting, the second-order transition temperature that constitutes the polymkeric substance of its sandwich layer is lower than-20 ℃, its condition be this graftomer be by microsuspension preparation and
C) the elastomer particles shape vinylbenzene-diene block copolymer of 0～35% weight, its diene part can be partially or completely hydrogenant, wherein B component) particulate D (50) is 0.3～7 μ m, and B component) be different from component C).
2. as the desired thermoplastic composition of claim 1, the wherein B component of 50% above number) be present in this moulding compound with non-cohesion form.
3. as claim 1 or 2 desired thermoplastic compositions, wherein component C) content be 0～30% of this moulding compound weight.
4. the purposes that is used for producd fibers, film or moulded product as the desired thermoplastic composition of claim 1.
5. the purposes that is used for producd fibers, film or moulded product as the desired thermoplastic composition of claim 2.
6. the purposes that is used for producd fibers, film or moulded product as the desired thermoplastic composition of claim 3.
7. fiber, film or the moulded product that obtains by the desired thermoplastic composition of claim 1.
8. fiber, film or the moulded product that obtains by the desired thermoplastic composition of claim 2.
9. fiber, film or the moulded product that obtains by the desired thermoplastic composition of claim 3.
CN99809629A 1998-08-13 1999-07-20 Shock-resistant thermoplastic moulding materials made of syndiotactic polystyrene and acrylate modifier Expired - Fee Related CN1131278C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19836621.3 1998-08-13
DE19836621A DE19836621A1 (en) 1998-08-13 1998-08-13 Polystyrene-based thermoplastic molding composition used for producing fibers, films and articles comprises an elastomeric particulate graft polymer

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CN1312834A CN1312834A (en) 2001-09-12
CN1131278C true CN1131278C (en) 2003-12-17

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JP (1) JP2002522615A (en)
KR (1) KR20010072434A (en)
CN (1) CN1131278C (en)
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BR (1) BR9912886A (en)
CA (1) CA2340231A1 (en)
CZ (1) CZ2001540A3 (en)
DE (1) DE19836621A1 (en)
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DE10016280A1 (en) 2000-04-03 2001-10-04 Basf Ag Impact-resistant thermoplastic molding compositions made of syndiotactic polystyrene, glass fibers and acrylate impact modifier

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US5395890A (en) * 1987-09-14 1995-03-07 Idemitsu Kosan Co., Ltd. Styrene-based resin composition
JPH05271501A (en) * 1992-03-24 1993-10-19 Mitsubishi Rayon Co Ltd Polystyrenic resin composition having excellent impact resistance, heat resistance and weather resistance
EP0755972B1 (en) * 1995-07-24 1999-09-15 Rohm And Haas Company Styrenic polymer composition
DE19702733A1 (en) * 1997-01-27 1998-07-30 Basf Ag Thermoplastic molding compounds with high toughness

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DE19836621A1 (en) 2000-02-17
CA2340231A1 (en) 2000-02-24
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BR9912886A (en) 2001-05-08
KR20010072434A (en) 2001-07-31
EP1117737A1 (en) 2001-07-25
WO2000009608A1 (en) 2000-02-24
CZ2001540A3 (en) 2001-11-14
TR200100480T2 (en) 2001-07-23
CN1312834A (en) 2001-09-12

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