CN1350560A - Method for producing thermoplastic molding material using rubber solutions - Google Patents

Abstract

The invention relates to a method for producing ABS and HIPS molding materials. According to this method, a solution containing rubber is produced first and the polymerization for producing the ABS and HIPS molding materials is then carried out in the presence of this solution containing rubber. The solution containing rubber is produced by polymerizing diolefines in a solution of vinyl aromatic monomers, in the presence of a catalyst containing the following: (A) at least one compound of the rare earth metals; (B) optionally, a cyclopentadine; and (C) at least one organo-aluminium compound.

Description

Adopt rubber solutions to produce the method for thermoplastic composition

The present invention relates to produce the method for ABS thermoplastics and high impact polystyrene (hereinafter to be referred as the HIPS=high impact polystyrene), wherein adopt a kind ofly be dissolved in the vinyl aromatic compounds, by be solvent with the vinyl aromatic compounds, by the random form aromatic vinyl/diene copolymers of transition-metal catalyst catalytic preparation, as rubber.

Body and the solution polymerization process of producing the ABS moulding compound are known, are described in Houben-Weyl, " modern organic chemistry " volume E20/ part 1, and in pp.182～217, Georg Thieme press, Stuttgart.The preparation of HIPS also is known, is described in Becker/Braun for example, " plastics handbook volume 4, " polystyrene ", pp.109～120, ISBN 3-446-18004-4,1996, Carl Hanser press; And " styrene polymer ", " polymer science and engineering complete works " volume 16, pp.1～246, the 2 edition, 1989, John Wiley ﹠amp; Sons.These methods relate to rubber are dissolved in vi-ny l aromatic monomers (as vinylbenzene) and olefinically unsaturated nitriles monomer (for example, vinyl cyanide), and randomly in the solvent and make and monomer polymerization.Between polymerization period, contain the polymers soln of rubber and do not contain between the polymers soln of rubber and occur being separated.Discrete, the discontinuous phase of the initial formation of polymers soln that does not contain rubber.Along with the carrying out of conversion of monomer, will occur changing mutually, the polymers soln that does not just contain rubber is phase-changed into bigger phase, and rubber solutions then becomes discontinuous phase, and the polymers soln that does not contain rubber simultaneously forms homogeneous phase.

In order to prepare ABS and HIPS moulding compound, use known body, solution or suspension polymerization, by continuous, semicontinuous in the presence of other monomers and optional solvent or prepare the rubber solutions that makes by dissolving off and on; And adopt known method of evaporating to separate.

The method shortcoming that many employing bodies, solution or suspension method are produced ABS and HIPS is, solubility rubber uses with solid form: they are dissolved in vinylbenzene and/or other monomers and the optional solvent, and then join with the rubber solutions form in the rest part of polymerization process.For reaching dissolving, solid rubber must be ground into fritter, and puts into and be dissolved in the dissolving vessel in vinylbenzene and/or other monomers and the optional solvents.It is disadvantageous using solid form rubber, because this kind solubility rubber preferably adopts solution polymerization production, wherein will be with a kind of inertia that in polymerization process, is, therefore originally in polyreaction, do not have active aliphatic series and/or aromatic solvent as solvent, and wherein this solvent randomly must distill again and shifts out after the polymerization, so that isolate the product rubber of solid form.Another shortcoming is, because rubber has higher cold flow tendency, highly is clamminess in other words, therefore processing and store all very difficult.

Carry out many trials, be intended to produce a kind of aromatic vinyl/diene copolymers as the solution in the vinyl aromatic compounds of solvent, and utilized this a little rubber solutions to produce ABS and HIPS moulding compound.

In US 4311819, adopt the anionic initiator such as butyllithium to carry out the polymerization of divinyl in vinylbenzene.Example according to this patent, by, when the starting point concentration of divinyl in vinylbenzene is about 35wt%, just stopped polyreaction at approaching about 25% o'clock as far back as the divinylic monomer transformation efficiency, perhaps simultaneously the divinylic monomer transformation efficiency is brought up to about 36% by butadiene concentration being brought up to about 55wt%, can obtain to be fit to the SBR rubber that HIPS production is used, so, just must first fractionation by distillation go out most of divinyl of introducing, could be used for the solution of this rubber in vinylbenzene impact-resistant modified subsequently.

The shortcoming of anionic initiator is that they make the telogenesis of styrene/butadiene copolymers (SBR) only allow with respect to butadiene unit the very limited control of microstructure enforcement.By adding properties-correcting agent, can only improve 1,2 or 1, the trans unitary ratio of 4-, and this will cause glass transition temperature of polymer to raise.Adopt the SBR of anionic initiator production can not reach higher cis-content, wherein have more than 40% with respect to butadiene content, preferred more than 50%, especially preferred 1 more than 60%, 4-cis-content.This point is why very unfavorable be because, in method, formed SBR, wherein compare with homopolymerization polyhutadiene (BR), the increase of styrene content will cause the further rising of second-order transition temperature.Yet if rubber is prepared to be used for, for example HIPS or ABS's is impact modified, and the rising of rubber second-order transition temperature will be to the low-temperature performance production disadvantageous effect of material, so preferred rubber has lower glass transition temperatures.

US 3299178 discloses a kind of based on TiCl ₄/ iodine/Al (isobutyl-) ₃Catalyst system, be used for divinyl and generate equal polyhutadiene in the vinylbenzene polymerization.Yet, the document of delivering thereafter, people such as Harwart, " plastics and rubber " 24/8 (1977) 540 has been described this divinyl and the cinnamic copolyreaction of adopting the same catalyst system, mentions this catalyzer again and is applicable to the preparation polystyrene.Therefore, this catalyst system is not suitable for preparing aromatic vinyl/diene copolymers in the aromatic vinyl solvent.

US 5096970 and EP 304088 describe a kind of method for preparing polyhutadiene in vinylbenzene, employing based on the phosphonic acids neodymium, based on organo-aluminium compound as two (isobutyl-) alanate (DIBAH) and based on the catalyzer of halogen-containing Lewis acid such as ethyl aluminium sesqui chloride, wherein need not further to add inert solvent, divinyl just can react in vinylbenzene and generate 1,4-cis-polyhutadiene.The shortcoming of this catalyzer is, it is low-down 1 that the rubber of acquisition has, and 2-unit content is lower than 1%.This is disadvantageous, because higher 1 in rubber, 2-content will be to rubber and polymeric matrix, as the homopolymerization of vinyl aromatic (co) hydrocarbon compound-or multipolymer, between the grafting performance produce favourable influence.

People such as Kobayashi, " polymer science magazine ", volume A, " a polymer chemistry piece of writing ", 33 (1995) 2175 and 36 (1998) 241, a kind of catalyst system has been described, by the rare earth halide metal acetate, as Nd (OCOCCl ₃) ₃Or Gd (OCOCF ₃) ₃, form jointly with the muriate of three (isobutyl-) aluminium and triethyl aluminum, can catalysis divinyl and the copolyreaction of vinylbenzene in the inert solvent hexane.Except having inert solvent, the shortcoming of this kind catalyzer also is, when cinnamic combination rate has just arrived about 5mol%, catalyst activity just has been reduced to and has been lower than 10g polymkeric substance/mmol catalyzer/h, and 1 of polymkeric substance, the 4-cis-content is along with the rising of styrene content significantly descends.

Rubber described in the above-mentioned patent disclosure is dissolved in the application of cinnamic solution in the HIPS preparation, all takes shifting out the unreacted divinylic monomer later on again with the solution of rubber in vinylbenzene and the way of radical initiator merging.

On the other hand, rubber also is used for vinyl cyanide/styrol copolymer (SAN) matrix and prepares ABS.Different with the preparation of HIPS, SAN matrix and polystyrene among the ABS are incompatible.When diene in the aromatic vinyl solvent during polymerization if except rubber, also generate the homopolymer of solvent, as polystyrene, SAN matrix and this ceridust base aromatic hydrocarbons incompatible performance during ABS prepares then with the obvious damage material.

WO 97/38031 and WO 98/07766 describe, in solution He in the presence of the inert solvent, prepare styrene/butadiene copolymers or polybutadiene homopolymer, prepare impact modified thermoplastic polystyrene moulding compound and polystyrene/vinyl cyanide moulding compound with it then with anionic catalyst.A shortcoming is, will add inert solvent during the polymerizing butadiene, causes and produce the steam that comprises unreacted monomer and solvent after the degassing, must their be separated and drying with loaded down with trivial details mode, they could be reused in the anionic polymerisation.

The purpose of this invention is to provide a kind of by in containing rubber solutions, carrying out the method that ABS and HIPS moulding compound are produced in polymerization, this method, when adopting appropriate catalyst, do not show above-mentioned various shortcoming, but also can change the ratio of styrene units in the dissolving rubber.

This method also will make used rubber solutions be directly used in production ABS and the HIPS moulding compound becomes possibility, that is, do not need the rubber separation is dissolved in the vinyl aromatic compounds then again.

Described purpose is reached by a kind of rubber solutions that contains, this solution be by diene in the solution of vi-ny l aromatic monomers, containing and carrying out the polymerization preparation in the presence of the catalyzer of following ingredients,

(A) at least a rare earth compound,

(B) randomly, at least a cyclopentadiene, and

(C) at least a organo-aluminium compound.

Be surprisingly found out that now the inventive method can be implemented under the situation that does not add inert solvent.

The rubber solutions that uses is to produce by the polymerization of conjugated diolefine in the aromatic vinyl solvent.By this method, generate a kind of multipolymer, wherein with regard to the selectivity of the content and the polymerization diene of vinyl-arene and diene, cis position double bond content and have 1 of a side vinyl for example, the polymkeric substance composition of 2-unit content all can change, wherein the second-order transition temperature of polymkeric substance is lower than-60 ℃, preferably is lower than-70 ℃.

The rubber solutions that uses can prepare like this: diene is in the presence of the catalyzer based on rare earth compound, in the presence of vi-ny l aromatic monomers as solvent, temperature at-30～100 ℃, preferably-20～90 ℃ temperature, especially preferably 20～80 ℃ temperature, adopt known continuous, semicontinuous or batch process method to carry out polymerization.

Spendable conjugated diolefine for example is a 1,3-butadiene, 1,3-isoprene, 2, and 3-dimethylbutadiene, 2,4-hexadiene, 1,3-pentadiene and/or 2-methyl isophthalic acid, 3-pentadiene or described monomeric mixture wherein are preferred with the 1,3-butadiene.

Certainly, except conjugated diolefine, also can use further unsaturated compound in addition, as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene and/or cyclopentenes, optimal ethylene, propylene, 1-butylene, 1-hexene and/or 1-octene, they can carry out copolymerization with described diene.

Catalyst component (A): (B): mol ratio (C) can be between 1: 0.01～1.99: 0.1～1000.The consumption of catalyst component (A) can be between 1 μ mol～10mmol, with respect to every 100g conjugated diolefine consumption; The aromatic vinyl compound consumption is the every 100g conjugated diolefine of a 50g～2000g consumption.

Component (A): (B): (C) mol ratio in catalyst system therefor is preferably between 1: 0.1～1.9: 3～500, and especially preferred 1: 0.2～1.8: 5～100.

The rare earth compound that can consider especially (component (A)) is to be selected from following those:

-rare earth alkoxide,

-rare earth metal phosphonate, rare earth metal phosphinates and/or phosphoric acid salt,

-rare earth carboxylates,

The complex compound of-rare earth metal and diketone and/or

The addition compound of-rare earth metal halide and oxygen or nitrogen donor compound.

Above-mentioned rare earth compound is described in greater detail in, for example among the EP 11 184.

Rare earth compound is those of 21,39 and 57～71 element based on ordination number especially.The preferred rare earth metal that uses is lanthanum, praseodymium or neodymium, or comprises the lucium one of at least of 10wt% element lanthanum, praseodymium or neodymium at least.Especially especially the preferred rare earth metal that uses is lanthanum or neodymium, these two again can with other rare earth metal blending.Lanthanum and/or neodymium proportion in this kind mixture especially preferably is 30wt% at least.

In the middle of the complex compound of rare earth alkoxide, phosphonate, phosphinates, phosphoric acid salt and carboxylate salt or rare earth metal and diketone, what can consider especially is that those exist organic group in compound, especially comprise 1～20 carbon atom, the line style of preferred 1～15 carbon atom or branched-alkyl residue, for example methyl, ethyl, n-propyl, normal-butyl, n-pentyl, sec.-propyl, isobutyl-, the tertiary butyl, 2-ethylhexyl, neo-pentyl, new octyl group, new decyl or new dodecyl.

In the middle of the rare earth alkoxide, what can enumerate for example is:

N-propyl alcohol neodymium (III), propyl carbinol neodymium (III), nonylcarbinol neodymium (III), Virahol neodymium (III), 2-Ethylhexyl Alcohol neodymium (III), n-propyl alcohol praseodymium (III), propyl carbinol praseodymium (III), nonylcarbinol praseodymium (III), Virahol praseodymium (III), 2-Ethylhexyl Alcohol praseodymium (III), n-propyl alcohol lanthanum (III), propyl carbinol lanthanum (III), nonylcarbinol lanthanum (III), lanthanum isopropoxide (III), 2-Ethylhexyl Alcohol lanthanum (III), preferred propyl carbinol neodymium (III), nonylcarbinol neodymium (III), 2-Ethylhexyl Alcohol neodymium (III).

The rare earth phosphonate, what can enumerate in the middle of phosphinates and the phosphoric acid salt for example is:

Dibutyl phosphonic acids neodymium (III), diamyl phosphonic acids neodymium (III), dihexyl phosphonic acids neodymium (III), diheptyl phosphonic acids neodymium (III), dioctyl phosphonic acids neodymium (III), dinonyl phosphonic acids neodymium (III), two dodecyl phosphonic acids neodymiums (III), dibutyl phospho acid neodymium (III), diamyl phospho acid neodymium (III), dihexyl phospho acid neodymium (III), diheptyl phospho acid neodymium (III), dioctylphosphinic acid(HDOP) neodymium (III), dinonyl phospho acid neodymium (III), two dodecyl phospho acid neodymiums (III), preferred dioctyl phosphonic acids neodymium (III) and dioctylphosphinic acid(HDOP) neodymium (III).

Suitable rare earth carboxylates is:

Propionic acid lanthanum (III), diethylacetic acid lanthanum (III), 2 ethyl hexanoic acid lanthanum (III), stearic acid lanthanum (III), phenylformic acid lanthanum (III), hexahydrobenzoic acid lanthanum (III), oleic acid lanthanum (III), branched paraffin carboxylic acid (versatate) lanthanum (III), lanthanum naphthenate (III), propionic acid praseodymium (III), diethylacetic acid praseodymium (III), 2 ethyl hexanoic acid praseodymium (III), stearic acid praseodymium (III), phenylformic acid praseodymium (III), hexahydrobenzoic acid praseodymium (III), oleic acid praseodymium (III), branched paraffin carboxylic acid's praseodymium (III), naphthenic acid praseodymium (III), propionic acid neodymium (III), diethylacetic acid neodymium (III), 2 ethyl hexanoic acid neodymium (III), stearic acid neodymium (III), phenylformic acid neodymium (III), hexahydrobenzoic acid neodymium (III), oleic acid neodymium (III), branched paraffin carboxylic acid's neodymium (III), neodymium naphthenate (III), preferred 2 ethyl hexanoic acid neodymium (III), branched paraffin carboxylic acid's neodymium (III), neodymium naphthenate (III).Branched paraffin carboxylic acid's neodymium is especially preferred.

In the middle of the complex compound of rare earth metal and diketone, what can enumerate is:

Methyl ethyl diketone lanthanum (III), methyl ethyl diketone praseodymium (III), methyl ethyl diketone neodymium (III), preferred methyl ethyl diketone neodymium (III).

In the middle of the addition compound of rare earth metal halide and oxygen or nitrogen donor compound, what can enumerate is:

Lanthanum trichloride (III) and tributyl phosphate, Lanthanum trichloride (III) and tetrahydrofuran (THF), Lanthanum trichloride (III) and Virahol, Lanthanum trichloride (III) and pyridine, Lanthanum trichloride (III) and 2-Ethylhexyl Alcohol, Lanthanum trichloride (III) and ethanol, praseodymium chloride (III) and tributyl phosphate, praseodymium chloride (III) and tetrahydrofuran (THF), praseodymium chloride (III) and Virahol, praseodymium chloride (III) and pyridine, praseodymium chloride (III) and 2-Ethylhexyl Alcohol, praseodymium chloride (III) and ethanol, Neodymium trichloride (III) and tributyl phosphate, Neodymium trichloride (III) and tetrahydrofuran (THF), Neodymium trichloride (III) and Virahol, Neodymium trichloride (III) and pyridine, Neodymium trichloride (III) and 2-Ethylhexyl Alcohol, Neodymium trichloride (III) and ethanol, lanthanum bromide (III) and tributyl phosphate, lanthanum bromide (III) and tetrahydrofuran (THF), lanthanum bromide (III) and Virahol, lanthanum bromide (III) and pyridine, lanthanum bromide (III) and 2-Ethylhexyl Alcohol, lanthanum bromide (III) and ethanol, praseodymium bromide (III) and tributyl phosphate, praseodymium bromide (III) and tetrahydrofuran (THF), praseodymium bromide (III) and Virahol, praseodymium bromide (III) and pyridine, praseodymium bromide (III) and 2-Ethylhexyl Alcohol, praseodymium bromide (III) and ethanol, neodymium bromide (III) and tributyl phosphate, neodymium bromide (III) and tetrahydrofuran (THF), neodymium bromide (III) and Virahol, neodymium bromide (III) and pyridine, neodymium bromide (III) and 2-Ethylhexyl Alcohol, neodymium bromide (III) and ethanol, preferably Lanthanum trichloride (III) and tributyl phosphate, Lanthanum trichloride (III) and pyridine, Lanthanum trichloride (III) and 2-Ethylhexyl Alcohol, praseodymium chloride (III) and tributyl phosphate, praseodymium chloride (III) and 2-Ethylhexyl Alcohol, Neodymium trichloride (III) and tributyl phosphate, Neodymium trichloride (III) and tetrahydrofuran (THF), Neodymium trichloride (III) and 2-Ethylhexyl Alcohol, Neodymium trichloride (III) and pyridine, Neodymium trichloride (III) and 2-Ethylhexyl Alcohol, Neodymium trichloride (III) and ethanol.

Especially especially the preferred rare earth compound that uses is branched paraffin carboxylic acid's neodymium, neodymium octoate and/or neodymium naphthenate.

Above-mentioned rare earth compound both can also can mix use individually.

The cyclopentadiene (component (B)) that uses is general formula (I), (II) or compound (III),

R wherein ¹～R ⁹For identical or different, or randomly link together or condense on general formula (I), (II) or cyclopentadiene (III), can represent hydrogen, C ₁～C ₃₀Alkyl group, C ₆～C ₁₀Aromatic yl group, C ₇～C ₄₀Alkylaryl group, C ₃～C ₃₀Silyl-group, wherein alkyl group can be saturated or single-or polyunsaturated, can comprise heteroatoms such as oxygen, nitrogen or halogen.This residue can especially be represented hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, aminomethyl phenyl, cyclohexyl, benzyl, trimethyl silyl or trifluoromethyl.

The example of cyclopentadiene is unsubstituted cyclopentadiene, methyl cyclopentadiene, the ethyl cyclopentadiene, the normal-butyl cyclopentadiene, tertiary butyl cyclopentadiene, the vinyl cyclopentadiene, the benzyl rings pentadiene, the benzyl ring pentadiene, the trimethyl silyl cyclopentadiene, 2-methoxy ethyl cyclopentadiene, 1,2-dimethyl cyclopentadiene, 1,3-dimethyl cyclopentadiene, the trimethylammonium cyclopentadiene, the tetramethyl-ring pentadiene, the tetraphenyl cyclopentadiene, the tetrabenzyl cyclopentadiene, the pentamethyl-cyclopentadiene, five benzyl rings pentadienes, ethyl tetramethyl-ring pentadiene, trifluoromethyl tetramethyl-ring pentadiene, indenes, 2-methyl indenyl, the trimethylammonium indenes, the hexamethyl indenes, seven methyl indenes, 2-methyl-4-phenyl indenyl, fluorenes or methyl fluorenes.

Cyclopentadiene also is both can also can mix use individually.

In the middle of the organo-aluminium compound (component (C)), what especially will consider is aikyiaiurnirsoxan beta (alumoxane) and/or aluminium organic radical (organyl) compound.

The aikyiaiurnirsoxan beta of using is aluminium/oxygen compound, just as known to those skilled in the art, is to contact with condensation component such as water by organo-aluminium compound to produce, and it constitutes general formula (Al (R) 0-) _nA class acyclic or a ring compound, wherein R can be identical or different, represents the alkyl group of line style or 1～10 carbon atom of side chain, it also can comprise heteroatoms in addition, as oxygen or halogen, n depends on condensation degree.R is represent methylidene, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-octyl or iso-octyl especially, especially preferable methyl, ethyl or isobutyl-.The example of the aikyiaiurnirsoxan beta that can enumerate is: methylaluminoxane, ethyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.

The aluminium organic radical compound that uses is general formula AlR ¹⁰ _3-dX _dCompound, wherein

R ¹⁰Can be identical or different, can represent C ₁～C ₃₀Alkyl group, C ₆～C ₁₀Aromatic yl group, C ₇～C ₄₀Alkylaryl group, wherein alkyl group can be saturated or single-or polyunsaturated, and can comprise heteroatoms, as oxygen or nitrogen,

X represents hydrogen or halogen, and

D represents 0～2 number.

General formula AlR ¹⁰ _3-dX _dOrgano-aluminium compound in the middle of especially can use: the butanolate of trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, diethyl aluminium hydride, hydrogenation di-n-butyl aluminium, diisobutylaluminium hydride, diethyl aluminum, diethyl aluminum ethylidene (dimethyl) amine and diethyl aluminum ethylidene (methyl) ether, preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diisobutylaluminium hydride.

Organo-aluminium compound equally also is individually or to mix use.

Also another kind of component (D) can be joined in the quite sophisticated catalyst component (A)～(C).This component (D) can be a conjugated diolefine, and it for example can be and will carry out the identical diene of polymeric subsequently under this catalyst action.Preferred divinyl and/or the isoprene of using.

If in catalyzer, add component (D), then the consumption of (D) preferably between, with respect to every 1mol component (A), 1～1000mol, especially preferred 1～100mol.Especially particularly preferably be, use the every 1mol component of 1～50mol (D) (A).

When producing rubber solutions, this catalyst consumption is 1 μ mol～10mmol, the preferred 10 μ mol～every 100g monomer of 5mmol rare earth compound.

Certainly, also can use this catalyzer any desired mixt each other.

Rubber solutions prepares in the presence of vi-ny l aromatic monomers, particularly exist---vinylbenzene, alpha-methyl styrene, alpha-methyl styrene dimer, p-methylstyrene, Vinylstyrene and/or other nuclear substituted ring-alkylated styrenes preferably have those of 2～6 carbon atoms in alkyl residue---in the presence of carry out.

Rubber solutions is especially particularly preferably in the existence preparation down as solvent of vinylbenzene, alpha-methyl styrene, alpha-methyl styrene dimer and/or p-methylstyrene.

These solvents can use individually or as mixture.

The consumption that is used as the vi-ny l aromatic monomers of solvent is generally 10 weight parts～2000 weight parts, preferred 30～1000 weight parts, and preferred especially especially 50～500 weight parts are with respect to the monomer of per 100 weight parts use.

Rubber solutions is preferably-20～90 ℃ temperature, especially preferably 20～80 ℃ temperature production.The inventive method can be in (0.1～12bar) enforcement under the not pressurization situation or under the pressure of raising.Produce and carry out serially or discontinuously, preferably by operate continuously.

Also can after polymerization, shift out solvent and/or unreacted monomer that a part is used, preferably by distillation, randomly under reduced pressure, so that obtain the polymer concentration of requirement.

Modified rubber thermoplastic composition of the present invention is by vi-ny l aromatic monomers and olefinically unsaturated nitriles monomer or passes through vi-ny l aromatic monomers, in the presence of one of above-mentioned rubber solutions and add under the monomeric situation of olefinically unsaturated nitriles, carry out radical polymerization preparation, wherein randomly also add further vi-ny l aromatic monomers also randomly in the presence of solvent, adopt known body, solution or suspension polymerization, by continuous, semicontinuous or intermittent mode operation.

The solution of styrene/butadiene copolymers in vinylbenzene as what can prepare as stated above, is preferred for modified rubber thermoplastic composition of the present invention and is used for the inventive method of its preparation.

The such rubber solutions of preferred use, wherein the styrene units content that has of dissolved styrene/butadiene copolymers is between 5～40mol%, especially preferred 10～30mol% and, for butadiene content, have 1, Unit 2, side chain vinyl just, content between 2～20mol%, especially preferred 4～15mol%, and 1,4-cis unit content, between 35～85mol%, especially preferred 45～85mol%, and its second-order transition temperature is lower than-60 ℃, especially preferably is lower than-70 ℃.

Radical polymerization only takes place separately, thereby perhaps randomly merges the vi-ny l aromatic monomers of the homogeneous phase (matrix phase) that generates moulding compound together with olefinically unsaturated nitriles monomer radical polymerization, use when producing rubber solutions for a kind of.Also can use nuclear substituted chloro-styrene class in addition with described monomer mixture form.

The olefinically unsaturated nitriles monomer is vinyl cyanide and methacrylonitrile preferably, and with vinyl cyanide for especially preferred.

Acrylic monomer or maleic acid derivatives also can use, its consumption accounts for the highest 30wt% of the total consumption of monomer, preferred the highest 20wt%: example is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) tert-butyl acrylate, and the maleimide that replaces of fumarate, itaconic ester, maleic anhydride, maleic acid ester, N-, advantageously, N-cyclohexyl-or N-phenylmaleimide, N-alkyl-phenyl maleimide for example, and even vinylformic acid, methacrylic acid, fumaric acid, methylene-succinic acid or their acid amides.

Vi-ny l aromatic monomers and olefinically unsaturated nitriles monomer in ABS moulding compound of the present invention proportion between 60～90wt%:40～10wt%, by matrix phase.Rubber content in the ABS moulding compound of the present invention is between 5～35wt%, and preferred 8～25wt% is a benchmark with the ABS moulding compound.

Rubber content in the HIPS moulding compound of the present invention is between 1～25wt%, and preferred 3～15wt% is a benchmark in the HIPS moulding compound.

Carry out in solvent under the situation of radical polymerization, the solvent that can consider is an aromatic hydrocarbons, as toluene, ethylbenzene, dimethylbenzene, and the mixture of ketone such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone and these solvents.Ethylbenzene, methyl ethyl ketone and acetone and composition thereof are preferred.

Advantageously, polyreaction causes with radical initiator, but also can take thermal initiation; The molecular weight of product polymkeric substance can be regulated by chain-transfer agent.

Suitable radical polymerization initiator is the grafting peroxide actives for free radical of decaying, as peroxycarbonate, peroxide two carbonic ethers, peroxide diacyl, peroxy ketal or peroxide dialkyl group and/or azo-compound or its mixture.Example is azo two isopropylformic acid dintrile, azo isopropylformic acid alkyl ester, the mistake PIVALIC ACID CRUDE (25) tert-butyl ester, crosses the sad tert-butyl ester, t-butylperoxyl benzoate, crosses the neodecanoic acid tert-butyl ester, mistake-(2-ethylhexyl) carbonic acid tert-butyl ester.The consumption of these initiators is 0.005～1wt% of monomer consumption.

Molecular weight can be regulated by the traditional chain transfer agent, as using mercaptan, alkene, for example uncle's lauryl mercaptan, n-dodecyl mercaptan, tetrahydrobenzene, terpinol, alpha-methyl styrene dimer; Its consumption is 0.05～2wt% of monomer consumption.

The inventive method can be implemented by discontinuous, semicontinuous and continuous mode.In continuous embodiment, rubber solutions, monomer and solvent randomly, can advantageously in continuously feeding, mixing, stirred-tank reactor, carry out polymerization in the 1st stage, stable state monomer conversion after changing mutually surpasses 10%, this radical polymerization can be proceeded to reach 30～90% until monomer conversion at least 1 further stage then, during mixing of materials occur in the placed in-line stirring tank of one or more operate continuouslys or occur in mixing, the plug flow reactor and/or in the combination of these 2 types of reactors.Residual monomer and solvent (for example can utilize traditional method, at heat exchange vaporizer, flash evaporator, line material vaporizer, thin-film evaporator, spiral gas exhauster, band kneading and the stirring of stripper plant, heterogeneous vaporizer) shift out, wherein also can adopt winding-up or entrainment agent, for example water vapour turns back in the technology then.Additive, stablizer, oxidation inhibitor, filler, lubricant all can add between polymerization period and between the polymkeric substance separation period.

Discontinuous and semi-continuous polymerzation reaction can be carried out in the mixing stirring tank of one or more placed in-line fillings or part filling, wherein rubber solutions, monomer and optional solvent, at first in the introducing equipment, then carrying out polymerization, is 30～90% until reaching described monomer conversion.

The mixing of the rubber solutions of introducing and dispersion can circulate continuously or discontinuously via mixing and shearing elements by slurry and improve.This kind loop reactor is known prior art, helps to establish rubber particle size.Yet more advantageously, between 2 independent reactors, arrange shearing elements, to avoid back-mixing, because back-mixing causes size-grade distribution to broaden.

Mean residence time is between 1～10h, preferred 2～6h.Polymerization temperature is between 50～180 ℃, preferred 70～170 ℃.

The rubber particle size of the thermoplastic composition of modified rubber of the present invention is diameter (weight average, d _W) between 0.1～10 μ m, preferred 0.1～2 μ m (ABS) or 0.1～10 μ m, preferred 0.2～6 μ m (HIPS).

Moulding compound of the present invention can pass through extrusion molding, injection moulding, calendering, blowing, compacting and sintering, is melted and is processed to form mo(u)lded item.

Embodiment

Measuring method

The determination of solution viscosity of rubber solutions adopts the Brookfield viscometer to carry out (model LVT, rotor 2, according to viscosity, rotating speed can transfer to fixed speed 6,12,30,60rpm for Brookfield RV, SyncroLectric) at 25 ℃ with 5wt% solution.

ABS：

Transformation efficiency is determined by going out solids content at 200 ℃ of evaporation measurements.Rubber content in the final product is then determined according to material balance.Gel content is that dispersion medium is measured with acetone.The limiting viscosity of soluble part is that solvent is measured with dimethyl formamide and 1g/L lithium chloride.Granularity and distribution thereof are according to US 5,166, and centrifugal determination is adopted in 261 description; In the range of variation of described method, the dispersion of rubber grain in Texacar PC is injected in Texacar PC/acetone (75: 25) mixture; Provided weight average (d _W), the average (d of area _A) and number average (d _N) granularity.Notched Izod impact strength (a _K-Izod) according to IS0 180/1A 23 ℃ of mensuration; Melt volume index (220 ℃ of MVI/10kg) measure according to DIN 53735.By on the NKS device with about 1 hertz frequency, adopt the dynamic mechanically of rheometer RDA II to measure about shearing modulus parameter G* (T)-150～200 ℃ temperature ranges, studied phase structure.Measured second-order transition temperature (T soft phase and matrix _g).Correction shearing modulus under having determined 23 ℃ again (G ' _Corr(RT)).Measuring test sample injection moulding under 240 ℃ of melt temperatures, 70 ℃ of conditions of die temperature of being adopted makes.

HIPS：

Shock strength (a _K-Izod) measure according to ISO 180/1U with-40 ℃ at 23 ℃; Tensile strength, extension at break, yielding stress and Young's modulus are measured according to DIN 53 455 and DIN53 457.Measuring test sample injection moulding under 200 ℃ of melt temperatures, 45 ℃ of conditions of die temperature of adopting makes.(MVI, 5kg) measures according to DIN53 735 the melt volume index by 220 ℃.

The rubber solutions preparation

Carry out polymerization at excluding air and moisture and under argon gas covers.Described in some embodiment, with polymkeric substance separating from styrene solution, purpose only is the polymkeric substance of producing is identified.This polymkeric substance certainly, also has some still to be stored in the styrene solution, does not separate out, so correspondingly accept further processing.The vinylbenzene that uses as the solvent of diene polymerization is at argon gas, CaH ₂Go up, 25 ℃ stir 24h, under 25 ℃ and decompression, steam then.The mensuration of styrene content adopts in the polymkeric substance ¹H-NMR spectroscopy; And the selectivity of polybutadiene content (1,4-cis, 1, trans and 1,2 content of 4-) is by the IR spectroscopy determining; Molecular weight adopts the GPC/ light scattering determining.

Example A～E

Ageing A～the C of catalyzer

In 300mL Schlenk pipe, with 5.3g divinyl, 1.88mL pentamethyl-cyclopentadiene and the solution of 217mL10% methylaluminoxane (MAO) in toluene, joining 38.4mL0.3125 M branched paraffin carboxylic acid neodymium (III) at 25 ℃ by barrier film (septum) (NDV) is dissolved in the solution of hexane, maintain 50 ℃ and stir 2h, be used for polymerization then.

Ageing D～the E of catalyzer

In 300mL Schlenk pipe, with 6.0g divinyl, 1.4mL indenes and the solution of 217mL10% methylaluminoxane (MAO) in toluene, joining 49.0mL0.245 M branched paraffin carboxylic acid neodymium (III) at 25 ℃ by barrier film (NDV) is dissolved in the solution of hexane, maintain 50 ℃ and stir 2h, be used for polymerization then.

Polymerization

Polyreaction is carried out in 40L has the steel reactor of anchor shape agitator (50rpm).At room temperature, be dissolved in to divinyl and add trimethyl aluminium (TMA) or the solution of triisobutyl aluminium (TIBA) in hexane in the cinnamic solution, as scavenging agent, this reaction soln is adjusted to 50 ℃ temperature in 45min, merges with the proper amt catalyst solution then.During the polyreaction, temperature of reaction maintains 50 ℃.After reaction times arrives, polymers soln is transferred to the 2nd reactor (80L reactor in 15min, anchor shape agitator, 50rpm), this polyreaction is by adding 3410g methyl ethyl ketone and 7.8g right-2, the phosphorous acid ester (Irgafos TNPP, Ciba-Geigy company) of 5-two-tert.-butyl phenol n-octyl propionate (Irganox 1076, Ciba-Geigy company) and 25.5g three (nonyl phenyl) and stopping.The unreacted divinyl is by being reduced to 200mbar with reactor pressure in 1h, and is reduced to 100mbar in 2h, and temperature maintenance is at 50 ℃, and shifts out.

Following table provides the performance of batch weight, reaction conditions and resulting polymers.

Example	????A	????B	????C	????D	????E
						Catalyst solution, m1	????166	????161	????161	????161	????166
NDV，mmol	????7.5	????7.3	????7.3	????7.0	????7.2
						Polymerization
Vinylbenzene, g	????18070	????16890	????17154	????16844	????16777
						Water content, ppm	????83	????30	????37	????12	????31
1,3-butadiene, g	????3003	????3700	????3703	????3701	????3700
						TMA(2M)，ml	????17	????5.6	????7	????-	????25.5
TIBA(2M)，ml	????-	?????-	????-	????73	????-
						Temperature, ℃	????50	????50	????50	????50	????50
Reaction times, h	????4.5	????3.25	????3	????3	????4.5
						Polymkeric substance
Solids content, wt%	????16.31	????16.29	????15.51	????19.2	????12.3
						Styrene content, mol%	????25.8	????15.6	????13.6	????12.4	????11.5
Butadiene content, mol%	????74.2	????84.4	????86.4	????87.6	????88.5
						1,4-cis, % a)	????57	????62	????64	????83	????n.d.
1,4-is trans, % a)	????35	????29	????26	????12	????n.d.
						1，2，??％ a)	????8	????9	????10	????5	????n.d.
η (5%, in the vinylbenzene), mPas	????46	????59	????78	????55	????148
						T g，℃	????-65	????-72	????-74	????-90	????n.d.
M n，kg/mol	????242	?????-	?????-	????165	????n.d.
						M w，kg/mol	????332	?????-	?????-	????279	????n.d.

^A)1,4-cis, 1, trans and 1, the 2 unitary content of 4-is for butadiene content in the polymkeric substance.The n.d.=undetermined

The preparation of ABS moulding compound

Embodiment 1-7

Solution I, by rubber solutions, vinylbenzene, vinyl cyanide, methyl ethyl ketone (MEK), right-2, (Irganox 1076 for 5-two-tert.-butyl phenol n-octyl propionate, Ciba-Geigy company) and alpha-methyl styrene dimer (AMSD) form, under 40 ℃, anchor shape agitator stir (150rpm), in the flat port grinding bottle of 5L (flat ground joint jar), mix.In a single day this solution be heated to 82～85 ℃, adds the initiator solution II that is made up of the methyl ethyl ketone and the mistake PIVALIC ACID CRUDE (25) tert-butyl ester (t-BPPIV) immediately in 4h in proportion.Controlled temperature during entire reaction makes this mixture keep refluxing slightly (82～85 ℃).Solution II adds beginning 2h later on, adds solution III in 1～2min, and it is made up of methyl ethyl ketone and alpha-methyl styrene dimer, and subsequently, agitator is set in 100rpm.After solution II adds, continue to stir 2h at 85 ℃, temperature is reduced to room temperature then again.This mixture is right-2 by adding, 5-two-tert.-butyl phenol n-octyl propionate (Irganox 1076, Ciba-Geigy company) and the solution of dithio propionic acid two lauryls (Irganox PS 800, Ciba-Geigy company) in methyl ethyl ketone, and stablized.Subsequently, solution outgases in the twin screw degassing extruder of laboratory and granulation.Pellet is injection molded to be the standard spillikin.

Following table provides formulation composition, polymerization result and ABS moulding compound characteristic.

Formulation is formed (all numerical value are unit without exception with the gram)

Embodiment	????1	????2	????3	????4	????5	????6	????7
								Solution I
Embodiment A	????1287.6	????1368.1	????-	????-	????-	????-	????-
								Embodiment B	????-	????-	????1357.5	????1261.7	????-	????-	????-
Embodiment C	????-	????-	????-	????-	????1413.5	????1413.5
								Embodiment D	????-	????-	????-	????-	????-	????-	????1029.3
Irganox?1076	????0.40	????0.43	????0.43	????0.40	????0.40	????0.40	????0.40
								Vinylbenzene	????359.9	????295.1	????313.9	????313.9	????254.0	????160.9	????366.5
Vinyl cyanide	????427.1	????423.9	????427.1	????427.1	????427.1	????395.3	????395.3
								MEK	????225.4	????212.9	????201.4	????297.2	????205.4	????330.4	????509
AMSD	????5.03	????2.49	????5.03	????3.35	????3.35	????3.10	????2.33
								Solution II
MEK	????150	????150	????150	????150	????150	????150	????150
								t-BPPIV(75％)	????6.98	????6.96	????7.01	????7.01	????7.01	????6.52	????6.47
Solution III
								MEK	????50	????50	????50	????50	????50	????50	????50
AMSD	????6.70	????5.82	????6.70	????5.03	????5.03	????6.20	????5.43
								Solution IV
MEK	????250	????250	????250	????250	????250	????250	????250
								Irganox?1076	????2.41	????2.42	????2.53	????2.41	????2.41	????2.26	????2.26
Irganox?PS?800	????3.62	????3.63	????3.79	????3.62	????3.62	????3.39	????3.39

The result:

Embodiment	????1	????2	????3	????4	????5	????6	????7
								Monomer conversion [%]	??59.8	??65.7	??61.3	??60.9	??63.2	??50.6	??61.0
Rubber content among the ABS [%]	??16.3	??16.0	??16.4	??16.1	??15.6	??19.9	??17.2
								Gel content [%]	??26.9	??29.9	??29.9	??30.2	??31.0	??35.5	??31.1
Graft(ing) degree	??0.65	??0.868	??0.821	??0.875	??0.985	??0.786	??0.811
								Limiting viscosity	??0.533	??0.640	??0.545	??0.575	??0.585	??0.502	??0.620
?MVR(220℃/10kg)[g/10′]	??4.1	??2.5	??2.8	??2.2	??1.8	??1.7	??2.4
								?d W[μm]	??0.874	??0.536	??0.603	??0.592	??0.838	??0.805	??0.622
?d A[μm]	??0.335	??0.201	??0.353	??0.328	??0.350	??0.358	??0.281
								?d N[μm]	??0.161	??0.109	??0.161	??0.157	??0.145	??0.140	??0.139

ABS moulding compound characteristic

Embodiment	????1	????2	????3	????4	????5	????6	????7
								Notched Izod impact strength is at 23 ℃ of [kJ/m 2]	???22.4	???23.5	???21.0	???21.7	???20.2	???23.4	???27.3
?T g, soft phase [℃]	???-62	???-60	???-70	???-70	???-72	???-73	???-88
								??T g, matrix [℃]	???109	???110	???110	???111	???111	???110	???108
??G′ corr(RT)[MPa]	???880	???865	???800	???790	???755	???660	???790

The preparation of HIPS moulding compound

Embodiment 8

The rubber solutions of example E is diluted to solids content 6% by adding vinylbenzene (stabilization).Add 0.5 weight part Vulkanox MB ^And 0.2 after the weight part alpha-methyl styrene dimer, in the glass autoclave of 2L band spiral shape agitator with this solution of purging with nitrogen gas 1200g 15 minutes.Temperature is brought up to 120 ℃ in 1h, mixture stirs (80rpm) 4.5h under this temperature.The highly viscous solution that obtains is poured in the withstand voltage aluminum die, carries out polymerization by following time/temperature program(me) subsequently:

2.5h，??125℃

1.5h，??135℃

1.5h，??145℃

1.5h，??165℃

2.5h，??225℃。

After the cooling, polymkeric substance is through pulverizing and outgas 20h under 100 ℃, vacuum.Injection moulding test sample in injection moulding machine.The mechanical data of bioassay standard spillikin.

The result:

Embodiment	????8
		?MVR[g/10′]	???7.3
?a k，23℃[kJ/m 2]	???58.4
		?a n，-40℃[kJ/m 2]	???48.9
Tensile strength [N/mm 2]	???37.5
		Extension at break [%]	???45.2
Yielding stress [N/mm 2]	???35.1
		Young's modulus [MPa]	???2350

Claims (22)

1. A method for preparing ABS and HIPS molding compositions, wherein I. First prepare the rubber-containing solution, and II. Polymerization is then carried out in the presence of the rubber-containing solution to produce the ABS and HIPS molding composition, It is characterized in that the rubber-containing solution is prepared by polymerizing dienes in a solution of vinyl aromatic monomers in the presence of a catalyst comprising, (A) at least one rare earth metal compound, (B) optionally, at least one cyclopentadiene, and (C) at least one organoaluminum compound. 2. The method for preparing ABS and HIPS molding compositions according to claim 1, characterized in that styrene, α-methylstyrene, α-methylstyrene dimer, p-methylstyrene, diethylene Phenylbenzenes, ring-substituted alkylstyrenes, preferably those having 2 to 6 carbon atoms in the alkyl residue, or mixtures thereof, are used as the vinylaromatic monomer. 3. The method for preparing ABS and HIPS molding compositions according to claim 1 or 2, characterized in that styrene, α-methylstyrene, α-methylstyrene dimer or mixtures thereof, are used as The vinyl aromatic monomer. 4. Process for preparing ABS and HIPS molding compositions as claimed in any one of claims 1 to 3, characterized in that conjugated dienes are used. 5. The method for preparing ABS and HIPS molding compositions according to any one of claims 1 to 4, characterized in that 1,3-butadiene, isoprene, 2,3-dimethylbutadiene , 2,4-hexadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene or mixtures thereof, especially preferably 1,3-butadiene, are used as the conjugated Diene. 6. The method for preparing ABS and HIPS molding compositions according to any one of claims 1 to 5, characterized in that rare earth metal alkoxides, phosphonates, phosphinates, phosphates, carboxylates, rare earth metals Complex compounds with diketones, or addition compounds of rare earth metal halides with oxygen or nitrogen donor compounds, are used as catalyst component (A). 7. The method for preparing ABS and HIPS molding compositions according to any one of claims 1 to 6, characterized in that the cyclopentadiene component (B) used is of the general formula (I), (II) or ( compounds of III),

wherein R ¹ to R ⁹ may be the same or different, or may be optionally connected together or fused to cyclopentadiene of general formula (I), (II) or (III), and may represent hydrogen, C ₁ -C ₃₀ alkyl group, C ₆ -C ₁₀ aryl group, C ₇ -C ₄₀ alkaryl group or C ₃ -C ₃₀ silyl group, wherein the alkyl group can be saturated or are mono- or polyunsaturated and may contain heteroatoms such as oxygen, nitrogen or halogens. 8. Process for preparing ABS and HIPS molding compositions according to any one of claims 1 to 7, characterized in that aluminum organocompounds, in particular aluminoxanes, are used as organoaluminum component (C). 9. Process for preparing ABS and HIPS molding compositions according to any one of claims 1 to 8, characterized in that conjugated dienes are added to the catalyst components (A) to (C). 10. The method for preparing ABS and HIPS molding compositions according to any one of claims 1 to 9, characterized in that the molar ratio of component (A) to component (B) is 1: 0.01 to 1: 1.99; The molar ratio of component (A) to component (C) is 1:0.1 to 1:1000. 11. Process for preparing ABS and HIPS molding compositions as claimed in any one of claims 1 to 10, characterized in that the rubber solution is obtained by polymerization of dienes without the addition of inert solvents. 12. Process for preparing ABS and HIPS molding compositions according to any one of claims 1 to 11, characterized in that the process is carried out in a continuous or discontinuous manner. 13. Process for preparing ABS and HIPS molding compositions according to any one of claims 1 to 12, characterized in that the rubber solution is prepared at a temperature of -30 to 100°C. 14. Process for preparing ABS and HIPS molding compositions as claimed in any one of claims 1 to 13, characterized in that the rubber solution is prepared without pressurization. 15. Process for the preparation of ABS and HIPS molding compositions according to any one of claims 1 to 14, characterized in that the rubber solution is prepared at a high pressure of 0.1 to 12 bar. 16. Process for preparing ABS and HIPS molding compositions according to any one of claims 1 to 15, characterized in that unsaturated nitrile monomers are used during the polymerization for the preparation of ABS molding compositions in the presence of rubber-containing solutions, Acrylonitrile or methacrylonitrile is preferred, acrylonitrile is especially preferred. 17. Process for preparing ABS and HIPS molding compositions according to any one of claims 1 to 16, characterized in that acrylic monomers or Maleic acid derivatives. 18. ABS and HIPS molding compositions, characterized in that they are obtainable by the process of any one of claims 1-17. 19. The ABS and HIPS molding composition according to claim 18, characterized in that the styrene content of the styrene/butadiene copolymer is between 5 and 40 mol %; 1,2 unit content, relative to butadiene, is 2 ~20mol%, while the 1,4-cis unit content is 35~85mol%. 20. An ABS or HIPS molding composition, which can be prepared by using a styrene/butadiene copolymer whose cis-position double bond content accounts for 35-85 mol% of the butadiene content. 21. Use of the ABS and HIPS molding compositions according to any one of claims 18 to 20 for the production of moldings and extruded articles. 22. Molded and extruded articles obtainable from the ABS or HIPS molding compositions according to any one of claims 1 to 20.