CN1351618A - Method for producing thermoplastic molding materials using rubber solutions - Google Patents

Abstract

The invention relates to a method for producing ABS molding materials. According to this method, a solution containing rubber is produced first and the polymerization for producing the ABS molding compounds is then carried out in the presence of this solution containing rubber. Said solution containing rubber is produced by polymerizing diolefines in a solution of vinylaromatic monomers, in the presence of a catalyst containing the following: (a) at least one compound of the rare earth metals; (b) at least one organo-aluminum compound; and (c) optionally, a Lewis acid.

Description

Use rubber solutions to produce the method for thermoplastic composition

The present invention relates to the thermoplastic abs moulding compound and produce its method and relate to its purposes by the polyreaction in containing the solution of rubber.

Body and the solution polymerization process of producing the ABS moulding compound are known and are described in for example Houben-Weyl, organic chemistry method (Methoden der OrganischenChemie), Band 20/Teil 1,182-217 page or leaf, Georg Thieme Verlag, the Stuttgart.These methods relate to rubber are dissolved in vi-ny l aromatic monomers (for example vinylbenzene) and olefinically unsaturated nitriles monomer (for example vinyl cyanide) and the optional solvent and this monomer of polymerization.In polymerization process, at the polymers soln that contains rubber with do not contain between the polymers soln of rubber and be separated.The polymers soln that does not contain rubber has formed discrete discontinuous phase at first.Along with the carrying out of conversion of monomer, phase reversion takes place, the becoming mutually of polymers soln that does not promptly contain rubber becomes discontinuous phase than big and rubber solutions, and do not contain the polymers soln formation homogeneous phase of rubber.

The ABS moulding compound is by using known body, solution or suspension polymerization, the rubber solutions that utilization is produced by dissolved solids rubber in the presence of other monomer and optional solvent is produced with continuous, semicontinuous or batch production method polymerization, and uses known method of evaporating to separate.

The shortcoming of using body, solution or suspension process to produce the currently known methods of ABS is that solubility rubber is to use with solid form, wherein, it is dissolved in the vinylbenzene and/or the neutralization of other monomer and optional solvent is added in other processes of this polymerization process as rubber solutions then.In order can to dissolve, solid rubber must be cut into fritter and in dissolving tank, be dissolved in vinylbenzene and/or other monomer and optional solvent in.It is disadvantageous using the rubber of solid form, because these solubility rubber are preferably produced by solution polymerization process, wherein in polymerization process, be inertia and in polyreaction, itself do not have the aliphatics of reactive behavior and/or aromatic solvent as solvent and wherein after polymerization this solvent must choose wantonly and remove by distillation, in order that with the formed rubber of isolated in solid form.Further shortcoming is to have the Rubber processing of the rubber of high cold flow or high viscosity and store very difficulty.

Early existing people has carried out attempting producing diene polymer and has used these rubber solutions as intermediate product in as the vinyl aromatic compounds of solvent.

At US4, in 311,819, anionic initiator, for example butyllithium is used at vinylbenzene polymerization divinyl.According to the embodiment of this patent, might stop the SBR rubber that polyreaction obtains to be suitable for HIPS production down by divinylic monomer transformation efficiency as far back as about 25% or about 36%.About the shortcoming of this respect is that the most divinyl of introducing must be dissolved in solution in the vinylbenzene at rubber and is used for subsequently passing through fractionation by distillation before impact modified.

Another shortcoming is the use of anionic initiator, because formed styrene-butadiene copolymer (SBR) like this, it only can have slight control to microtexture based on butadiene unit.By adding properties-correcting agent, only might increase by 1,2 or 1, the trans unitary ratio of 4-, this causes the raising of the second-order transition temperature of polymkeric substance.Can not use anionic initiator to produce SBR with high-cis content, wherein 1, the 4-cis-content with respect to butadiene content, is to be higher than 40%, preferably is higher than 50%, especially preferably is higher than 60%.Further shortcoming is the following fact: formed SBR in the method, (BR) compares with the homopolymer polyhutadiene, improves the further raising that styrene content can cause second-order transition temperature.Yet if rubber is used for the impact modified of HIPS for example or ABS, the second-order transition temperature of the raising of rubber has adverse influence to the low-temperature performance of material, and the rubber that has lower glass transition temperatures like this is preferred.

US3299178 as right come requirement be used for vinylbenzene polymerization divinyl with form the homogeneous polyhutadiene based on TiCl ₄/ iodine/Al (iso-Bu) ₃Catalyst system.Yet, in nearer document, people such as Harwart, Plaste und Kautschuk, 24/8 (1977) 540, describe divinyl and the cinnamic copolyreaction of using same catalyst system, and described the suitability that catalyzer is used to produce polystyrene.Therefore this catalyst system is not suitable for producing diene polymer in the aromatic vinyl solvent.

US 5096970 and EP 304088 have described by using based on the phosphonic acids neodymium, organo-aluminium compound is as two (isobutyl-) aluminum hydride (DIBAH), with the method for in vinylbenzene, producing polyhutadiene based on the catalyzer of Lewis acid that contains halogen such as ethylaluminium sesquichloride, wherein need not further to add inert solvent, allow divinyl in vinylbenzene, react, obtain 1, the 4-cis-polybutadiene.Suggestion uses these rubber solutions to be used to produce impact modified polystyrene (HIPS).

People such as Kobayashi, J.Polym.Sci., Part A, Polym.Chem., 33 (1995) 2175 and 36 (1998) 241 have described catalyst system, and it is by halogenation acetate rare-earth salts, as Nd (OCOCCl ₃) ₃Or Gd (OCOCF ₃) ₃Form with three (isobutyl-) aluminium and diethylaluminum chloride, make it possible in the inert solvent hexane, carry out divinyl and cinnamic copolyreaction.Except having inert solvent, the shortcoming of these catalyzer is, be low to moderate in introducing under the cinnamic situation of about 5mol%, catalyst activity is reduced to and is lower than 10g polymkeric substance/mmol catalyzer/hr and along with the raising of styrene content, for the polymkeric substance butadiene unit 1 of polymkeric substance, the 4-cis-content obviously descends.

The solution of the rubber of describing in described patent publications in vinylbenzene has been used to produce HIPS, and this realizes by after removing unreacted divinylic monomer the solution of rubber in vinylbenzene being mixed with radical initiator.

On the other hand, this rubber is used for the matrix of vinyl cyanide/styrol copolymer (SAN) to produce ABS.Opposite with the production of HIPS, SAN matrix and polystyrene in ABS are incompatible.If also formed the homopolymer of solvent during the polymerization diolefine with rubber in the aromatic vinyl solvent, as polystyrene, then the uncompatibility of the vinyl aromatic hydrocarbons of SAN matrix and homopolymerization will cause the obviously impaired of material property in the production process of ABS.

WO97/38031 and WO98/07766 have described styrene/butadiene copolymers or polybutadiene homopolymer is the production of producing by the negatively charged ion mode in solution and be used for impact modified thermoplastic polystyrene moulding compound and polystyrene/vinyl cyanide moulding compound.A shortcoming is, adds inert solvent in the polymerization process of divinyl, makes the steam (it contains unreacted monomer and solvent) that produces after the degassing to separate to both expensive and drying, so that they are used further in the anionic polymerisation.

The objective of the invention is to develop a kind of by carrying out the method that the ABS moulding compound is produced in polymerization in containing the solution of rubber, when using appropriate catalyst, this method does not demonstrate above-mentioned shortcoming.This method should especially make rubber solutions might be directly used in the production of ABS moulding compound, promptly need not to separate and rubber is dissolved in the vinyl aromatic compounds again.

This purpose is to be realized by the solution of being produced by polymerization diolefine in the solution of vi-ny l aromatic monomers that contains rubber.

The invention further relates to and to contain

A) at least a rare earth compound,

B) at least a organo-aluminium compound and

C) Ren Xuan Lewis acid, catalyzer be used for polyreaction.

Be surprisingly found out that the method according to this invention can carry out under the situation of not adding inert solvent.

Employed rubber solutions obtains with continuous or discontinuous method.Formed polymkeric substance by this way, wherein the double bond content (with respect to butadiene content) at cis-position is greater than 90%, is preferably greater than 95% and have 1 of a side vinyl, 2 unitary content are extremely low (promptly＜2%), and wherein the second-order transition temperature of polymkeric substance is lower than-100 ℃.

The rubber solutions that uses is under-30-110 ℃ the temperature, preferably under under-20-100 ℃ the temperature, particularly preferably in 20-90 ℃ temperature, and the polymerization diolefine obtains in the presence of based on the catalyzer of rare earth compound and in the presence of as the vi-ny l aromatic monomers of solvent.

The preferred conjugated diolefine of using is, 1,3-butadiene for example, isoprene, 2,3-dimethylbutadiene, 2,4-hexadiene, 1,3-pentadiene and/or 2-methyl isophthalic acid, 3-pentadiene, preferred especially 1,3-butadiene.

The used molar ratio of catalyst component A and C can change on a large scale.

The molar ratio of component A and B component can be 1: 1-1: 1000, preferred 1: 3-1: 200, preferred especially 1: 3-1: 100.The molar ratio of component A and component C can be 1: 0.02-1: 15, preferred 1: 0.4-1: 5.During when aikyiaiurnirsoxan beta (III) with (IV) as B component, component C omits wholly or in part.

Especially the rare earth compound (component (A)) that needs to consider is to be selected from following these:

-rare earth alkoxide,

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

-rare earth carboxylates,

The coordination 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, and among the EP 11184.

This rare earth compound is especially based on the element with ordination number 21,39 and 57-71.The preferred rare earth metal that uses is a lanthanum, praseodymium or neodymium or contain at least a lucium in element lanthanum, praseodymium or the neodymium of 10wt.% at least.Very particularly preferably the rare earth metal of Shi Yonging is lanthanum or neodymium, it so that can with other rare earth metal blending.Lanthanum and/or the neodymium ratio in this mixture is 30wt% at least especially preferably.

Especially admissible rare earth alkoxide, phosphonate, phosphinates, the coordination compound of phosphoric acid salt and carboxylate salt or rare earth metal and diketone is more such: wherein the organic radical that in this compound, exists especially contain have 1-20 carbon atom, the linearity or the branched-alkyl residue of preferred 1-15 carbon atom, as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, sec.-propyl, isobutyl-, the tertiary butyl, the 2-ethylhexyl, neo-pentyl, new octyl group, new decyl or new dodecyl.

The rare earths alkoxide that can mention for example is:

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

The rare earth phosphonate that can mention, phosphinates and phosphoric acid salt for example are:

Neodymium (III) dibutyl phosphonate, neodymium (III) diamyl phosphonate, neodymium (III) dihexyl phosphonate, neodymium (III) diheptyl phosphonate, neodymium (III) dioctyl phosphonate, neodymium (III) dinonyl phosphonate, the two dodecyl phosphonates of neodymium (III), neodymium (III) dibutyl phosphinates, neodymium (III) diamyl phosphinates, neodymium (III) dihexyl phosphinates, neodymium (III) diheptyl phosphinates, neodymium (III) dioctylphosphinic acid(HDOP) salt, neodymium (III) dinonyl phosphinates, the two dodecyl phosphinates of neodymium (III), preferred neodymium (III) dioctyl phosphonate and neodymium (III) dioctylphosphinic acid(HDOP) salt.

Suitable rare earth carboxylates is:

Lanthanum (III) propionic salt, lanthanum (III) diethylacetic acid salt, lanthanum (III) 2-ethyl-hexanoate, lanthanum (III) stearate, lanthanum (III) benzoate, lanthanum (III) naphthenic acid salt, lanthanum (III) oleate, lanthanum (III) Visa hydrochlorate (versatat), lanthanum (III) naphthenate, praseodymium (III) propionic salt, praseodymium (III) diethylacetic acid salt, praseodymium (III) 2-ethylhexoate, praseodymium (III) stearate, praseodymium (III) benzoate, praseodymium (III) naphthenic acid salt, praseodymium (III) oleate, praseodymium (III) Visa hydrochlorate, praseodymium (III) naphthenate, neodymium (III) propionic salt, neodymium (III) diethylacetic acid salt, neodymium (III) 2-ethyl-hexanoate, neodymium (III) stearate, neodymium (III) benzoate, neodymium (III) naphthenic acid salt, neodymium (III) oleate, neodymium (III) Visa hydrochlorate, neodymium (III) naphthenate, preferred neodymium (III) 2-ethylhexoate, neodymium (III) Visa hydrochlorate, neodymium (III) naphthenate.Neodymium Visa hydrochlorate is particularly preferred.

The rare earth metal that can mention and the coordination compound of diketone are:

Lanthanum (III) acetylacetonate, praseodymium (III) acetylacetonate, neodymium (III) acetylacetonate, preferred neodymium (III) acetylacetonate.

The addition compound of the rare earth metal halide that can mention and oxygen or nitrogen donor compound for example 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, preferred 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.

Very particularly preferably the rare earth compound of Shi Yonging is neodymium Visa hydrochlorate, neodymium octylate and/or neodymium naphthenate.

Above-mentioned rare earth compound not only can separately and but also can mix use.

Be selected from trialkylaluminium, dialkyl aluminum hydride and/or the aikyiaiurnirsoxan beta of following general formula (I)-(IV) as the compound of organoaluminum B component:

AIR ₃(I)，??????HAIR ₂(II)，

In the general formula (I)-(IV) of B component, each R can be identical or different and be meant have 1-10 carbon atom, the linearity and the branched-alkyl residue of preferred 1-4 carbon atom, the cycloalkyl residues with 3-20 carbon atom is meant 1-50 with aromatic yl residue and n with 6-20 carbon atom.The example of general formula (I) and suitable aluminum alkyls (II) is: trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, three ring octyl group aluminium, diethyl aluminum hydride, di-n-butyl alanate and diisobutyl alanates.Triethyl aluminum, triisobutyl aluminium and diisobutyl alanate are preferred.

The aikyiaiurnirsoxan beta that can mention (III) and example (IV) are methylaluminoxane, ethyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.

This aluminum alkyls can use or mix mutually use separately.

So-called Lewis acid is as component C.The example that can mention is that wherein atoms metal belongs to the organo-metallic halogenide of 3a or 4a family, and the halogenide of the element of the 3a of periodictable, 4a and 5a, as Handbook of Chemistry ﹠amp; Physics (chemistry and physics handbook), the 45th edition, described in the 1964-65.Below these especially can be mentioned:

The dibrominated aluminium trimethide, methylaluminium dichloride, dibrominated aluminium triethyl, ethylaluminium dichloride, dibrominated butyl aluminium, dichloride butyl aluminium, bromination dimethyl aluminium, chlorodimethylalumiu, bromination diethyl aluminum, diethylaluminum chloride, bromination dibutyl aluminium, chlorination dibutyl aluminium, tribromide aluminium trimethide (Methylaluminiumsesquibromid), tri-chlorination aluminium trimethide, tribromide aluminium triethyl, ethylaluminium sesquichloride, alchlor, butter of antimony, antimony pentachloride, silicon tetrachloride, METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane, ethyl trichlorosilane, diethyl dichlorosilane, chlorotriethyl silane, vinyl trichloro silane, divinyl dichlorosilane, the trivinyl chlorosilane, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride.

Diethylaluminum chloride, ethylaluminium sesquichloride, ethylaluminium dichloride, bromination diethyl aluminum, tribromide aluminium triethyl and/or dibrominated aluminium triethyl are preferred the uses.

Aluminum compound (being expressed as B component) and halogen or halogen compounds, for example the reaction product of triethyl aluminum and bromine or triethyl aluminum and Butyryl Chloride also can be used as component C.In this case, this reaction can be carried out separately, and the amount that maybe will react needed alkylaluminium cpd is added to as in the needed amount of B component.

Ethylaluminium sesquichloride, Butyryl Chloride and butyl bromide are preferred.

During when aikyiaiurnirsoxan beta (III) with (IV) as B component, component C omits wholly or in part.

Also other component D can be joined among the respond well catalyst component A-C of evidence.This component D can be a conjugated diolefine, and it is identical with the diolefine of using this polymerization catalyst subsequently.Divinyl and/or isoprene are preferred the uses.

If component D is joined in this catalyzer, the amount of D preferably 1 arrives 1000mol (with respect to the component A of 1mol), preferred especially 1 to 100mol.Very particularly preferably, for 1mol component A, use the D of 1-50mol.

When producing this rubber solutions, this catalyzer be with 1 μ mol for the 100g monomer to 10mmol, preferred 10 μ mol are to the amount use of the rare earth compound of 5mmol.

Certainly also might use these catalyzer with any form of mixtures each other.

This rubber solutions is in the presence of vi-ny l aromatic monomers, especially at vinylbenzene, alpha-methyl styrene, alpha-methyl styrene dimer, p-methylstyrene is produced in the presence of Vinylstyrene and/or other ring-alkylated styrenes (preferably having 2-6 carbon atom in alkyl residue).

This rubber solutions is special preferably at the vinylbenzene as solvent, and alpha-methyl styrene is produced under alpha-methyl styrene dimer and/or p-methylstyrene exist.Vinylbenzene, alpha-methyl styrene and/or alpha-methyl styrene dimer and their mixture are very particularly preferred.

This solvent can use separately or use as mixture.

As the amount of the vi-ny l aromatic monomers of solvent normally 10g to 2000g, preferred 100 to 1000g, very particularly preferably 200 arrive 500g, for the used monomer of 100g.

This rubber solutions is preferably produced under 20 to 90 ℃ temperature especially preferably at-20 to 100 ℃.This reaction can not have pressure or carry out under elevated pressure (0.1-12 crust).This production process is continuous or discontinuous carrying out, preferred operate continuously.

Also might remove the solvent for use and/or the unreacted monomer of a part after polyreaction, preferably utilize distillating method, choose wantonly under reduced pressure, this is in order that obtain required polymer concentration.

Thermoplastic composition according to modified rubber of the present invention is preferably produced by vi-ny l aromatic monomers and the monomeric Raolical polymerizable of olefinically unsaturated nitriles.According to the present invention, this reaction is by using with known body, solution or suspension polymerization continuous, semicontinuous or the intermittent mode operation, in the presence of a kind of above-mentioned rubber solutions, add the olefinically unsaturated nitriles monomer and randomly add other vi-ny l aromatic monomers and choose wantonly and in the presence of solvent, carry out.

By the above method produce at vinylbenzene, the polyhutadiene solution in alpha-methyl styrene and/or alpha-methyl styrene dimer and their mixture is preferred for modified rubber thermoplastic composition neutralization of the present invention and is used for method according to production said composition of the present invention.

The vi-ny l aromatic monomers that carries out Raolical polymerizable with the olefinically unsaturated nitriles monomer and therefore form the homogeneous phase (matrix phase) of moulding compound is to be used to produce those of rubber solutions.Nuclear substituted chlorostyrene can use as mixture with these monomers in addition.

The olefinically unsaturated nitriles monomer is vinyl cyanide and methacrylonitrile preferably, and wherein vinyl cyanide is particularly preferred.

And, Acrylic Acid Monomer or maleic acid derivatives can be with the 30wt.% at the most of monomer total amount, the amount of preferred 20wt.% is at the most used: example is (methyl) methyl acrylate, (methyl) vinylformic acid ethyl ester, (methyl) vinylformic acid tertiary butyl ester, the ester of fumaric acid, the ester of methylene-succinic acid, maleic anhydride, the maleic acid ester class, N-substituted maleimide amine is ideally as N-cyclohexyl-or N-phenylmaleimide, N-alkyl phenyl maleimide, and vinylformic acid, methacrylic acid, fumaric acid, methylene-succinic acid or their acid amides.

Vi-ny l aromatic monomers and the monomeric ratio of olefinically unsaturated nitriles are 60-90wt.%:40-10wt.% in ABS moulding compound according to the present invention, with respect to matrix phase.Rubber content is 5-35wt.% in ABS moulding compound of the present invention, and preferred 8-25wt.% is with respect to the ABS moulding compound.

For the situation of carrying out Raolical polymerizable in solvent, admissible solvent is an aromatic hydrocarbon, as toluene, and ethylbenzene, dimethylbenzene and ketone such as acetone, butanone, pentanone, the mixture of methyl-n-butyl ketone and these solvents.Ethylbenzene, butanone and acetone and their mixture are preferred.

Polyreaction causes by radical initiator ideally, but also can be undertaken by type of heating; The molecular weight of the polymkeric substance that obtains can be regulated by molecular weight regulator.

The initiator appropriate that is used for radical polymerization is the grafting peroxide actives that resolves into free radical; as peroxycarbonate (Peroxycarbonate); peroxy dicarbonate; diacyl peroxide, peroxidation aldehyde (Perketale) or dialkyl peroxide and/or azo-compound or their mixture.Example is azo two isopropylformic acid dintrile, and azo isopropylformic acid alkyl esters is crossed the PIVALIC ACID CRUDE (25) tertiary butyl ester, crosses sad tertiary butyl ester, and t-butyl perbenzoate is crossed the neodecanoic acid tertiary butyl ester, crosses (2-ethylhexyl) carbonic acid tertiary butyl ester.These initiators are to use with the amount of 0.005-1wt.%, for monomer.

Can be by using the common molecular weight regulator such as the mercaptan of the amount of 0.05-2wt.% for monomer, alkene, uncle's lauryl mercaptan for example, n-dodecyl mercaptan, tetrahydrobenzene, terpinol, the alpha-methyl styrene dimer is regulated molecular weight.

The method according to this invention can be carried out with discontinuous, semicontinuous and successive mode.In the successive embodiment, this rubber solutions, monomer and optional solvent can be ideally after being higher than 10% phase reversion under the stable state monomer conversion, carry out polyreaction in fs in the tank reactor of continuously feeding, mixing and stirring, then at blended simultaneously, the polyreaction that free radical causes continues in the stirring pot type of one or more placed in-line other operate continuouslys or is mixing in the plug flow reactor and/or proceed to the monomer conversion of 30-90% at least one additional phase in the combination of two types of reactors.Residual monomer and solvent can be by using usual way (for example at the heat exchange vaporizer, flash evaporator, the line type vaporizer, thin-film evaporator, the screw rod vaporizer, have and mediate and the heterogeneous vaporizer of stirring-type of extraction plant) remove (wherein also might use whipping agent or entrainment agent, for example water vapor) and turn back in this method.Can in polymerization process and in the sepn process of polymkeric substance, add additive, stablizer, antioxidant, filler, lubricant.

One or more placed in-line be full of or the mixing stirring-type jar of part filling in carry out discontinuous and semi-continuous polyreaction, wherein rubber solutions, monomer and optional solvent are introduced into and are aggregated to the described monomer conversion of 30-90% at first.

The mixing of the rubber solutions of being introduced and dispersion can be by mixing and shearing device and improve via the continuous or discontinuous circulation of slurry is pumped into.Annular-pipe reactor is well known in the prior art and can be used for determining the granularity of rubber.Yet better is two the shearing device to be set between the reactor independently, and to avoid returning mixing, the latter will cause the broadening of size-grade distribution.

Mean residence time is 1-10 hour, preferred 2-6 hour.This polymerization temperature is 50 to 180 ℃, preferred 70 to 170 ℃.

Modified rubber thermoplastic composition according to the present invention has diameter (weight average, d _w) be 0.1-10 μ m, the rubber particle size of preferred 0.1-2 μ m.

Can pass through extrusion molding according to moulding compound of the present invention, injection moulding, calendering, blowing, compacting and sintering method are processed into moulded product by thermoplastic.

Embodiment

Measuring method

The soltion viscosity of rubber solutions is measured (Brookfield RV, SyncroLectric, LVT type to 5wt.% solution by using Bu Luoke Field (Brookfield) viscometer under 25 ℃, mandrel 2 can be set rotating speed to 6,12 according to viscosity, 30, the fixed speed of 60Upm).

Measure transformation efficiency by evaporating back mensuration solids content down at 200 ℃.Rubber content in final product is measured from mass balance.Gel content is to measure in the acetone as dispersion medium.The limiting viscosity of soluble fraction is that the LiCl with dimethyl formamide+1g/L measures as solvent.According at US5, the centrifugal method described in 166,261 is measured granularity and size-grade distribution; Different with described method, with the mixture of the dispersion injection propylene carbonate/acetone (75: 25) of rubber grain in propylene carbonate; Explained weighed average (d _W), area average (d _A) and quantity mean value (d _N).Measure notched Izod impact strength (a according to ISO 180/1A down at 23 ℃ _K-Izod) and according to DIN 53735 measure melt volume indexes (220 ℃ of MVI/10kg).Use the RDA II of Rheometrics company, in-150-200 ℃ temperature range and under the frequency of about 1Hz, by the shearing modulus parameter G on NKS ^*(T) kinetics, mechanical measuring means are investigated phase structure.Measure the second-order transition temperature (Tg) of soft phase and matrix phase.Also be determined at correction shearing modulus under 23 ℃ (G ' korr. (RT)).Under the die temperature of 240 ℃ melt temperatures (Massetemperatur) and 70 ℃, the moulded product of injection moulding processing is measured.

The production of rubber solutions

Excluding air and steam carry out polyreaction with argon atmosphere.According to described method in certain embodiments, isolating polymer in the solution from be dissolved in vinylbenzene, this only is the purpose that characterizes the polymkeric substance that obtains in order to reach.This polymkeric substance also can need not to separate in the solution that just is stored in the vinylbenzene certainly, and correspondingly further processing.Vinylbenzene molecular sieve drying as the solvent of the polyreaction of diolefine.Measure polyhutadiene (1,4-cis, 1,4-is trans and 1,2-content) and the microtexture of the polystyrene that forms by Raolical polymerizable by infrared spectrum analysis.

Embodiment A-D

Polyreaction is carried out in the 40L steel bomb that anchor stirrer (100Upm) is housed.At room temperature in the following order catalyst component is joined in the solution of divinyl in vinylbenzene: 1) diisobutyl alanate (DIBAH, as 3.2 volumetric molar concentration solution in hexane), 2) neodymium Visa hydrochlorate (NDV, as 0.24 volumetric molar concentration solution in hexanaphthene), 3) ethylaluminium sesquichloride (EASC is as 0.1 volumetric molar concentration solution in hexane).Add after the last component, temperature is increased to 65 ℃.In polymerization process, keep temperature of reaction at 65-70 ℃.In Embodiment C and D, only initial the introducing with in a single day being elevated to after 65 ℃ in temperature of the part in the divinyl consumption (40%) introduced remainder in 1 hour in polymerization process.After the reaction times finishes, polymers soln is transferred to second reactor (80L reactor, anchor stirrer, 100Upm) and by the butanone of interpolation 500g and the p-2 of 18g, (Irganox 1076 for 5-two-tert.-butyl phenol propionic acid octyl group ester, Ciba Geigy) and the tricresyl phosphite of 18g-(nonyl phenyl) ester (Irgatos TNPP, Ciba Geigy) stop polyreaction.By in 1 hour, the pressure in the reactor being reduced to 200 millibars and in 2 hours, be reduced to 100 millibars and remove unreacted divinyl under 50 ℃.

Provided batch weight in the following table, the reaction conditions and the polymer properties that obtains.

Embodiment	????A	????B	????C	????D
					Polymerizing condition
Vinylbenzene [kg]	????16.9	????16.9	????16.9	????16.9
					Divinyl [kg]	????4.25	????4.25	????4.9	????4.9
DIBAH[mmol]	????300	????320	????320	????270
					EASC[mmol]	????5.4	????5.4	????6.5	????6.5
NDV[mmol]	????8.0	????8.0	????9.8	????9.8
					Temperature [℃]	????60	????70	????65	????63
Time [min]	????390	????165	????150	????240
					Rubber solutions
BR content [wt.%]	????14.3	????16.7	????20.9	????18.9
					PS content [wt.%]	????0.6	????1.5	????1.4	????0.8
Rubber
					Cis content [%] a)	????96	????96	????96	????96
1,2 content [%) a)	????1	????1	????1	????1
					T g[℃]	????-108	????-109	????-110	????-109
Viscosity (5% solution) [mPas]	????83	????41	????39	????58

^A)1,4-cis and Unit 1,2 are with respect to the content of polyhutadiene.

The production of the ABS moulding compound of embodiment 1-6

By rubber solutions, vinylbenzene, vinyl cyanide, butanone (MEK), p-2, the solution I that 5-two-tert.-butyl phenol propionic acid octyl group ester (Irganox 1076, Ciba Geigy) and alpha-methyl styrene dimer (AMSD) are formed is mixed with anchor stirrer (150Upm) down at 40 ℃ in the flat ground joint still of the 5L that anchor stirrer and reflux exchanger are housed.After this solution is heated to 82-85 ℃, in 4 hours, add the initiator solution II that forms by butanone and mistake PIVALIC ACID CRUDE (25) tertiary butyl ester (t-BPPIV).The mode of (82-85 ℃) is controlled the temperature of entire reaction so that mixture leniently refluxes.After solution II is added beginning two hours, the solution III in that interpolation in 1-2 minute is made up of butanone and alpha-methyl styrene dimer is set in 100Upm with agitator then.After the reinforced end of solution II, continue down to stir other 2 hours, then temperature is reduced to room temperature at 85 ℃.This mixture is that 5-two-tert.-butyl phenol propionic acid octyl group ester (Irganox 1076, Ciba Geigy) and the solution of dithio propionic acid dilauryl ester (Irganox PS 800, Ciba Geigy) in butanone are stablized by interpolation p-2.This solution then in ZSK-laboratory twin screw devolatilization forcing machine (Eindampfschnecke) by devolatilization and granulation.This pellet is injection molding little of formation standard.

Following table has shown the composition of prescription, the characteristic of polymeric result and ABS moulding compound.

The composition (all values are pressed g) of prescription

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
							Solution I
Embodiment A	????932.2	????932.2	????-	????-	????-	?????-
							Embodiment B	????-	????-	????820.4	????-	????-	?????-
Embodiment C	????-	????-	????-	????712.5	????-	?????-
							Embodiment D	????-	????-	????-	?????-	????755	????755
Irganox?1076	????0.3	????0.3	????0.3	????0.3	????0.3	????0.3
							Vinylbenzene	????415.4	????415.4	????544.6	????645.9	????608.2	????608.2
Vinyl cyanide	????408	????408	????408	????408	????408	????408
							MEK	????544.4	????544.4	????527	????533.6	????528.9	????528.9
AMSD	????1.6	????0.8	????2.4	????4.8	????2.4	????4.8
							Solution II
MEK	????150	????150	????150	????150	????150	????150
							t-BPPIV(75％)	????6.4	????7.42	????7.42	????7.46	????7.46	????7.46
Solution III
							MEK	????50	????50	????50	????50	????50	????50
AMSD	????9.6	????4.8	????7.2	????4.8	????7.2	????4.8
							Solution IV
MEK	????250	????250	????250	????250	????250	????250
							Irganox?1076	????2.22	????2.22	????2.22	????2.22	????2.22	????2.22
Irganox?PS?800	????3.33	????3.33	????3.33	????3.33	????3.33	????3.33

The result

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
							Monomer conversion [%]	?56.1	??62.7	??58.4	??55.6	??57.4	??56.2
Rubber content in ABS [%]	?14.0	??12.8	??13.5	??14.1	??13.8	??14.0
							Gel content [%]	?27.0	??27.1	??26.7	??28	??30.4	??28.8
Graft(ing) degree	?0.93	??1.117	??0.972	??0.983	??1.211	??1.059
							Limiting viscosity	?0.551	??0.674	??0.576	??0.514	??0.561	??0.529
MVR(220℃/10kg) [g/10′]	?5.5	??2.6	??5.2	??10.5	??4.9	??7.6
							d w[μm]	?1.094	??0.993	??0.249	??0.566	??0.502	??0.480
d a[μm]	?0.353	??0.252	??0.113	??0.134	??0.205	??0.157
							d n[μm]	?0.140	??0.103	??0.072	??0.082	??0.115	??0.090

The characteristic of ABS moulding compound

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
							Notched Izod impact strength, 23 ℃ of [kJ/m 2]	???23.0	???18.6	???21.2	??24.8	???25.6	??26.8
The soft phase of Tg-[℃]	???-106	???-108	???-107	??-105	???-104	??-104
							Tg-matrix [℃]	???110	???110	???106	??108	???108	??108
G′ korr.(RT)[MPa]	???915	???970	???915	??870	???860	??835

Claims (23)

1. produce the method for ABS moulding compound, wherein

I. at first produce the solution contain rubber and

II. containing the polyreaction of producing the ABS moulding compound in the presence of this solution of rubber then,

Be characterised in that this solution that contains rubber is that the polymerization diolefine is produced in containing in the presence of the catalyzer of following component by the solution at vi-ny l aromatic monomers:

A) at least a rare earth compound,

B) at least a organo-aluminium compound and

C) Ren Xuan Lewis acid.

2. according to the method for the production ABS moulding compound of claim 1, be characterised in that vinylbenzene, alpha-methyl styrene, the alpha-methyl styrene dimer, p-methylstyrene, Vinylstyrene, ring-alkylated styrenes, or their mixture is as this vi-ny l aromatic monomers.

3. according to the method for the production ABS moulding compound of claim 1 and 2, be characterised in that vinylbenzene, alpha-methyl styrene, alpha-methyl styrene dimer or their mixture are as this vi-ny l aromatic monomers.

4. according to the method for the production ABS moulding compound of claim 1-3, be characterised in that the use conjugated diolefine.

5. according to the method for the production ABS moulding compound of claim 1-4, be characterised in that 1,3-butadiene, isoprene, 2, the 3-dimethylbutadiene, 2, the 4-hexadiene, 1,3-pentadiene, the 2-methyl isophthalic acid, 3-pentadiene or their mixture are as conjugated diolefine.

6. according to the method for the production ABS moulding compound of claim 1-5, be characterised in that the alkoxide of rare earth metal, phosphonate, phosphinates, phosphoric acid salt, carboxylate salt, the addition compound of the coordination compound of rare earth metal and diketone or rare earth metal halide and oxygen or nitrogen donor compound is as catalyst component A.

7. according to the method for the production ABS moulding compound of claim 1-6, be characterised in that trialkylaluminium, dialkyl aluminum hydride or aikyiaiurnirsoxan beta are as this organoaluminum B component.

8. according to the method for the production ABS moulding compound of claim 1-7, be characterised in that atoms metal wherein belongs to the organo-metallic halogenide of the 3a of periodictable or 4a family as component C.

9. according to the method for the production ABS moulding compound of claim 1-8, be characterised in that the 3a of periodictable, the halogenide of the element of 4a or 5a family is as component C.

10. according to the method for the production ABS moulding compound of claim 1-9, be characterised in that conjugated diolefine is added among the catalyst component A to C.

11. according to the method for the production ABS moulding compound of claim 1-10, the mol ratio that is characterised in that component A and B component is 1: 1-1: 1000 and the mol ratio of component A and component C be 1: 0.02-1: 15.

12. the method according to the production ABS moulding compound of claim 1-11 is characterised in that the use catalyzer, it contains

A) at least a rare earth compound and

B) aikyiaiurnirsoxan beta.

13. the method according to the production ABS moulding compound of any one among the claim 1-12 is characterised in that to need not to add inert solvent, obtains rubber solutions by the polymerization diolefine.

14. the method according to or multinomial production ABS moulding compound among the claim 1-13 is characterised in that it is to carry out continuously or discontinuously.

15. the method according to the production ABS moulding compound of claim 1-14 is characterised in that this rubber solutions is to produce under-30 to 110 ℃ temperature.

16., be characterised in that this rubber solutions is to produce under the situation that does not have pressurization according to the method for the production ABS moulding compound of claim 1-15.

17., be characterised in that this rubber solutions is to produce under the rising pressure of 0.1-12 crust according to the method for the production ABS moulding compound of claim 1-16.

18., be characterised in that in the polymerization process of in the presence of containing the solution of rubber, producing the ABS moulding compound and use unsaturated nitrile monomer according to the method for the production ABS moulding compound of claim 1-17.

19. the method according to the production ABS moulding compound of claim 1-18 is characterised in that other use 30% Acrylic Acid Monomer or maleic acid derivatives at the most, with respect to monomeric total amount.

20.ABS moulding compound is characterised in that they can be by using according to one or multinomial method acquisition among the claim 1-19.

21. according to the ABS moulding compound of claim 20, the content that is characterised in that on cis-position two keys be greater than 90% and 1,2 unitary content with side vinyl be to be lower than 2%.

22. be used to produce the purposes of this moulded product according to the ABS moulding compound of claim 20 and 21.

23. the moulded product that can obtain from ABS moulding compound according to claim 20.