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WO1997038031A1 - Procede en continu pour la fabrication de produits moulables thermoplastiques - Google Patents

Procede en continu pour la fabrication de produits moulables thermoplastiques Download PDF

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Publication number
WO1997038031A1
WO1997038031A1 PCT/EP1997/001669 EP9701669W WO9738031A1 WO 1997038031 A1 WO1997038031 A1 WO 1997038031A1 EP 9701669 W EP9701669 W EP 9701669W WO 9738031 A1 WO9738031 A1 WO 9738031A1
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WO
WIPO (PCT)
Prior art keywords
styrene
reaction zone
rubber
butadiene
production
Prior art date
Application number
PCT/EP1997/001669
Other languages
German (de)
English (en)
Inventor
Hermann Gausepohl
Wolfgang Fischer
Wolfgang Loth
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP97920616A priority Critical patent/EP0832141A1/fr
Priority to JP9535823A priority patent/JPH11507984A/ja
Publication of WO1997038031A1 publication Critical patent/WO1997038031A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers

Definitions

  • the invention relates to an essentially two-stage process for the production of tough modified, thermoplastic molding compositions, in particular impact modified styrene homopolymers and copolymers in solution.
  • the invention relates in particular to the production of styrene-acrylonitrile polymers.
  • styrene is also to be understood below to mean its technical equivalents, vinyltoluene, tert-butylstyrene, p-methylstyrene, ethylstyrene or ⁇ -methylstyrene.
  • butadiene is also intended for isoprene, dimethylbutadiene, pentadiene -1.3 or hexadiene-1.3.
  • Impact-resistant polystyrene is usually produced thermally or with radical-forming initiators in a series of reactors (a so-called cascade). Polybutadiene in styrene and i.a. dissolved in a solvent such as ethylbenzene and the solution fed to a cascade from at least two reaction zones. Many process variants have been described and are also practiced technically; typical processes are described, for example, in US Pat. Nos. 2,727,884 or 3,903,202.
  • GB-A-1 013 205 proposed a process in which the rubber is first polymerized in cyclohexane. This solvent is exchanged for styrene and then polymerized in the usual way. The disadvantage of this process is that an additional solvent is used which has to be removed before the subsequent radical polymerization.
  • EP-A-334 715 therefore proposes a method which is to avoid this disadvantage. First of all, polybutadiene is produced in ethylbenzene, the common auxiliary solvent for styrofoamisation. After the active chains have been broken off, part of the solution is then diluted with preheated styrene and prepolymerized to a solids content of 30%. The polymerization is finally brought to an end in further reactors.
  • EP-A-334 715 is also disadvantageous because, owing to the high viscosity of the dissolved polybutadiene, only dilute rubber solutions can be used, ie a large amount of solvent is required. This leads to high expenditure of energy and apparatus for the removal and cleaning of the solvent. If, as proposed, ethylbenzene is used as the solvent, its regulating action also leads to polymers with a molecular weight which is too low and thus to inferior products.
  • EP-A-059 231 describes a process in which a styrene-butadiene block copolymer is anionically pre-formed and the free-radical polymerization of styrene is carried out in the presence of this block copolymer.
  • the styrene-butadiene copolymer is first polymerized up to a conversion of at most 30%.
  • the excess butadiene is then distilled off, since the presence of butadiene, as in the aforementioned case, would bring about crosslinking in the radical polymerization. Again, the necessary removal of the butadiene practically does not allow the process to be carried out continuously.
  • a styrene-butadiene block copolymer ("block rubber”) is polymerized anionically in a reaction zone which at least in its - in the working direction - last section from a reactor with plug flow, i.e. consists of a tubular reactor, the reaction product from this zone - possibly after chain termination (quenching) or coupling - is mixed with styrene or, in the case of the production of copolymers - with styrene and the selected comonomer and the mixture in a known manner radically polymerized.
  • block rubber styrene-butadiene block copolymer
  • Immediate subject matter of the invention is a process for the production of the production of toughened styrene polymers, in particular toughened styrene homo- and styrene-acrylonitrile copolymers in solution in two stages, with a styrene-butadiene block copolymer in a first reaction zone by anionic copolymerization of butadiene and styrene is produced and fed directly to a second reaction zone in which the desired styrene homopolymer or copolymer is prepared by radical polymerization or copolymerization.
  • This process is designed according to the invention in such a way that a first reaction zone is provided which, at least in its - in the working direction - last section from a reactor with plug flow, i.e. a tubular reactor.
  • the process according to the invention is also expediently designed such that the target product obtained after the second reaction zone, i.e. an impact-modified styrene homo- or copolymer is fed to a degassing device operated under reduced pressure and the vapors obtained are condensed, preferably purified by distillation, dried and fed back to the first reaction zone.
  • a degassing device operated under reduced pressure and the vapors obtained are condensed, preferably purified by distillation, dried and fed back to the first reaction zone.
  • the vapors can be recycled without time-consuming separation of solvent and residual styrene if the monomer in the second zone is reacted to such an extent that the ratio of monomer to solvent in the Vapors are less than or equal to the monomer / solvent ratio in the approach for the production of the rubber.
  • a simple distillation is sufficient to remove, for example, oligomeric components and stopping agents.
  • the last traces of impurities are removed by cleaning the distillate with a drying agent such as aluminum oxide or molecular sieve.
  • the target product is an impact resistant styrene copolymer, e.g. with acrylonitrile
  • the comonomer will first be separated off and the vapors will then be returned to the first reaction zone. This is usually easy to do because of the favorable spacing of the boiling points.
  • Conversion of styrene or styrene and selected comonomer in the last reaction zone is carried out to such an extent that no more styrene is recycled with the solvent than is used for the (anionic) production of a styrene-butadiene block copolymer.
  • a conversion of styrene of about 90 to 95% must be achieved. Otherwise, it would have to be continuously thinned and the amount of solvent circulating continuously increased.
  • An advantage of the process is that it is possible to produce impact-modified polystyrene molding compositions continuously in solution in a single polymerization section with only monomeric feedstocks.
  • Another advantage is the use of styrene-butadiene block rubber as an impact modifier, which results in a reduced proportion of butadiene polymer and thus high stability and resistance of the process product to e.g. Weather and light (yellowing).
  • a reaction zone 1 ie a reactor
  • a reaction zone 1 ie a reactor
  • the pipe section is equipped, for example, with a static mixing element.
  • a static mixing element for example, a suitably equipped simple pipe reactor or a tube bundle heat exchanger.
  • Suitable static mixers are known and are described, for example, in Chem. Eng. Commun. , Vol 36 pp. 251-267 or Chem. Eng. Technol. 13 (1990), pp. 214-220.
  • the currently available mixers of type SMX or SMXL Gabr. Sulzer, Wmterthur,
  • Kenics mixers Choer Ltd. West Meadows, Great Britain
  • SMR reactors Sulzer
  • reaction zone 1 a reaction vessel 1 or a tower reactor with a downstream tube zone can also be used as reaction zone 1, this also expediently also provided with a static mixing element, with conventional tower reactors already having properties which achieve an approximate plug flow. It is only essential that the reaction mixture is subjected to a plug flow under polymerization conditions before it leaves reaction zone 1 until the residual diene content, e.g. is below 1000, preferably below 500 and particularly preferably below 100 ppm. This is achieved by a tubular reactor with static mixers.
  • the reaction in zone 1 can be carried out isothermally, adiabatically or partially adiabatically.
  • the absolutely dry solvent and the required amount of stabilizer-free, dried monomer (styrene) and a suitable initiator solution (e.g. see-butyllithium) are metered in continuously in the desired ratio at the entrance to reaction zone 1.
  • Pure butadiene is metered in downstream (lb).
  • a styrene-butadiene block copolymer is obtained.
  • the living chain ends are broken off with a protic solvent or coupled with a suitable coupling agent (lc). Since the monomers fed to the second reaction stage are polymerized by free radicals, they do not have to be cleaned particularly strictly; the stabilizers and traces of water present in the monomers which are fed to the second reaction stage are therefore often sufficient to terminate the living chain ends of the first reaction stage. Coupling can give three-block or star block copolymers with correspondingly favorable properties.
  • the rubber solution obtained at the end of reaction zone 1 is fed to reaction zone 2, in which polymerization is carried out in a conventional manner by free radicals.
  • temperatures in the range from 50 to 150 ° C. or preferably from 70 to 120 ° C. are expediently selected.
  • reaction zone 1 is expediently divided into a number of segments in order to be able to freely select the temperature control in each segment.
  • Initiator can also be replenished downstream. This method is e.g. advantageous if you want to obtain rubbers with a broad or bimodal molecular weight distribution or if you want to influence the block lengths.
  • the concentration of the (finished) rubber solution can be varied within wide limits. However, it is limited by the viscosity of the solution and by economic factors. A final concentration of 5-60% by weight is preferred, but preferably 20 to 45% by weight.
  • the rubber solution prepared in reaction zone 1 is fed to a second reaction zone with the addition of monomers and, if appropriate, radical initiators and conventional auxiliaries.
  • This second reaction zone generally consists of at least two stirrers, for example two stirrers or two stirred tower reactors, or combinations of these units.
  • Such devices are e.g. in U.S. Patents 3,396,311 and 3,868,434 or DE-A-1,769,118 and 1,770,392.
  • the polymer solution finally obtained is freed of volatile constituents (residual monomers, solvents and possibly oligomers) in so-called degassing devices at temperatures of 190-320 ° C.
  • degassing devices at temperatures of 190-320 ° C.
  • custom-built extruders or evaporators operated under reduced pressure are customary. Description of the input materials
  • Suitable solvents for the production of the rubbers and the thermoplastic molding composition are aliphatic, cycloaliphatic, aromatic hydrocarbons with 4 to 12 carbon atoms or mixtures thereof. Suitable are e.g. Pentane, hexane, heptane, octane, cyclohexane, methylcylohexane, benzene, alkylbenzenes such as toluene, xylene or ethylbenzene. It is essential that these solvents are free of proton-active substances. They should therefore be distilled before use and dried over aluminum oxide or molecular sieve.
  • organolithium compounds are primarily used. Ethyllithium, propyllithium, isopropyllithium, n- or see-butyllithium, t-butyllithium, phenyllithium, hexyldiphenyllithium, hexamethylenedilithium and butadienyllithium or isoprenyldilithium may be mentioned as examples.
  • the dosage depends on the desired molecular weight, but is generally in the range of 0.002-5 mol%, based on the monomers. Suitable diene monomers for the production of the rubber are, in addition to butadiene, in principle all dienes which are used for the production of rubber and for themselves or together with vinylaromatic
  • dienes are butadiene, isoprene, dimethylbutadiene, 1,3-pentadiene or 1,3-hexadiene and styrene, vinyltoluene, t-butylstyrene, p-methylstyrene, ethylstyrene or ⁇ -methylstyrene for vinylaromatic compounds.
  • Linear or star block copolymers with a sharp or smeared transition of type (SB) n , SBS, BSB or (SB) mX, (BS) m X, (SBS) mX are used as block rubbers.
  • BOD BOD
  • the molecular weight of the blocks should be in the range from 1000 to 500,000 and preferably in the range from 20,000 to 300,000.
  • Block lengths and sequence length distribution of block copolymers can be influenced in the usual way by selecting the ratio of initiator and monomer and, if appropriate, by dividing the addition of the initiator over several metering points along reaction zone 1.
  • the total styrene content is 3 to 85, preferably 10 to 60, and particularly preferably 10 to 45% by weight.
  • the 1,2-vinyl content (short chain branches) of the Diene blocks, based on the total content of olefinic double bonds, should be less than 30%.
  • Preferred block copolymers are composed of styrene or ⁇ -methylstyrene and butadiene or isoprene. Both block S and block B can represent a statistical sequence of an alkadiene and a vinyl aromatic compound. Preferred block copolymers are made up of styrene or ⁇ -methylstyrene and butadiene or isoprene.
  • the glass transition temperatures of the diene-containing segments of the rubber produced should be below -20 ° C, preferably below -40 ° C.
  • the statistical structure is achieved by simultaneous addition of both monomers for block S and block B and addition of small amounts of Lewis bases such as dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, alkali metal salts of primary, secondary and tertiary alcohols or by tertiary amines such as pyridine, tributylamine. These connections are generally used in amounts of 0.1 - 5 vol.%.
  • Alkolates such as potassium tetrahydrolinaloate are required in an amount of 3 to 10%, based on the initiator used.
  • Multi-functional compounds such as aldehydes, ketones, esters, anhydrides or polyfunctional epoxides can be used to couple the rubbers.
  • Proton-active substances or Lewis acids such as e.g. Water, alcohols, aliphatic or aromatic carboxylic acids as well as inorganic acids, e.g. Carbonic acid or boric acid.
  • the glass transition temperatures of the diene-containing segments should be below -20, preferably below -40 ° C, i.e. these segments should have rubber-elastic properties.
  • styrene In addition to styrene, ⁇ -methylstyrene, tert-butylstyrene, vinyltoluene, p-methylstyrene or diphenylethylene are also suitable as monomers for the production of the impact-resistant thermoplastic molding compositions. These can be copolymerized in a conventional manner with aliphatic vinyl compounds such as acrylonitrile, (meth) acrylates, maleic anhydride and / or maleimide.
  • aliphatic vinyl compounds such as acrylonitrile, (meth) acrylates, maleic anhydride and / or maleimide.
  • Diacyl, dialkyl, diaryl peroxides, azo compounds, as well as peroxiesters, peroxidicarbonates and peroxiketals are suitable as initiators which act through radical decomposition.
  • Dibenzoyl peroxide, 1, l-di-t-butylperoxy-3, 3, 5-trimethylcyclohexane, 1, 1-di-t-butyl-peroxycyclohexane, dicumyl peroxide and dilauryl peroxide are preferred.
  • Molecular weight regulators such as, for example, dimeric ⁇ -methylstyrene, n- or t-dodecyl mercaptan, furthermore chain branching agents such as divinylbenzene, butanediol diacrylate, lubricants, stabilizers, mold release agents can be added as auxiliaries Polymer remain, otherwise must be removed.
  • the reaction zone 2 consisted of a stirred tank R with a volume of 5 l and two subsequent stirred tower reactors Ti and T 2, each with a content of 10 liters. All individual devices can be tempered.
  • Distilled styrene, stabilized acrylonitrile and methyl methacrylate were used to produce the thermoplastic molding composition.
  • the rubber solution obtained was fed continuously to the Ruhrkessel R together with 2.72 kg / h of styrene and polymerized at 130 ° C. to a solids content of 23%, the phase inversion taking place, ie a coherent rubber solution resulting in a coherent polystyrene solution.
  • the contents of the stirred tank R were fed continuously to the first reaction tower Ti and from there to the second reaction tower T 2 .
  • a solids content 5 of 73% was implemented, which corresponds to a styrene conversion of approx. 95%.
  • Example 1 was repeated with the difference that 2 times the amount of sec-butyllithium was used and the living polymer solution in tube section D was coupled with an epoxidized linseed oil (Edenol 318 B from Henkel). This resulted in a mixture of star block copolymers with predominantly 3, 4 and 5 star branches. This solution was further polymerized as described in Example 1 with 5 2.72 kg / h styrene.
  • Example 1 was repeated with the difference that 0.8 times the amount of butyllithium was used and no styrene was metered into reaction zone 1.
  • the butadiene content after the first reaction zone was 268 ppm.
  • reaction zone 2 45 27% by weight was fed continuously to reaction zone 2 and polymerized with the addition of 3.0 kg / h of styrene.
  • the solids content at the end of pipe section D was 27% and the monobutadiene content 124 ppm.
  • the solids content after reaction zone 2 is approximately 75% by weight, ie the styrene conversion is approximately 97%.
  • a transparent, tough polystyrene is obtained.
  • Pipe section A 0.51 kg / h butadiene; Pipe section C 0.17 kg / h styrene; Pipe section D 25.0 g / h C0 2 saturated water.
  • the polymer solution from tower 2 was continuously discharged and degassed in an extruder.
  • Pipe section D 15.0 g / h C0 2 saturated water.
  • the butadiene content after the first reaction zone was 32 ppm.
  • the temperatures in mixers A to C were 60 ° C, 85 ° C and 45 87 ° C.
  • the solution was further polymerized together with 2.72 kg / h of styrene.
  • the procedure for the production of a rubber-modified styrene-MMA copolymer was as follows: The rubber solution was prepared in reaction zone 1 as in Example 6, fed to the stirred tank of reaction zone 2 and there with 1.23 kg / h of styrene, 0 , 82 kg / h MMA and 100 g / h of a 0.5% solution of 1, l-di-t-butylperoxy-3,3,5-trimethylcyclohexane (TMCH) mixed in ethyl benzene.
  • TMCH 1, l-di-t-butylperoxy-3,3,5-trimethylcyclohexane
  • the temperature in the boiler was 122 ° C.
  • the mass was polymerized at 142 ° C or 151 ° C.
  • the solids content at the outlet from the last tower was 70%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention a pour objet un procédé de fabrication en deux étapes, en particulier de produits moulables, en solution, de polymères styrène et styrène-acrylonitrile modifiés de manière à améliorer la résistance au choc. Dans une première zone de réaction constituée, au moins dans sa dernière section dans le sens de progression du processus, d'un réacteur sans remélangeage, en particulier un réacteur tubulaire, on produit, par polymérisation anionique, un copolymère séquencé styrène-butadiène dont les extrémités de chaînes actives sont éventuellement couplées et/ou rompues; ce copolymère est immédiatement introduit dans une deuxième zone de réaction, dans laquelle on produit, par polymérisation ou copolymérisation radicaliare, un homopolymère ou un copolymère de styrène.
PCT/EP1997/001669 1996-04-11 1997-04-03 Procede en continu pour la fabrication de produits moulables thermoplastiques WO1997038031A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP97920616A EP0832141A1 (fr) 1996-04-11 1997-04-03 Procede en continu pour la fabrication de produits moulables thermoplastiques
JP9535823A JPH11507984A (ja) 1996-04-11 1997-04-03 熱可塑性成形材料を製造するための連続的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19614293.8 1996-04-11
DE1996114293 DE19614293A1 (de) 1996-04-11 1996-04-11 Kontinuierliches Verfahren zur Herstellung thermoplastischer Formmassen

Publications (1)

Publication Number Publication Date
WO1997038031A1 true WO1997038031A1 (fr) 1997-10-16

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PCT/EP1997/001669 WO1997038031A1 (fr) 1996-04-11 1997-04-03 Procede en continu pour la fabrication de produits moulables thermoplastiques

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EP (1) EP0832141A1 (fr)
JP (1) JPH11507984A (fr)
DE (1) DE19614293A1 (fr)
TW (1) TW339349B (fr)
WO (1) WO1997038031A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998052984A1 (fr) * 1997-05-22 1998-11-26 Basf Aktiengesellschaft Procede de preparation de solutions de polymerisats dieniques dans des monomeres vinylaromatiques

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2613352A1 (de) * 1976-03-29 1977-10-06 Basf Ag Verfahren zur herstellung von schlagfest modifizierten styrolpolymerisaten
DE2620853B2 (de) * 1975-05-12 1979-10-11 Asahi Kasei Kogyo K.K., Osaka (Japan) Hochschlagfestes Polystyrol
US4482677A (en) * 1980-08-25 1984-11-13 Japan Elastomer Co., Ltd. Process for producing high impact polystyrene
DE3506939A1 (de) * 1984-02-28 1985-09-12 Sumitomo Chemical Co., Ltd., Osaka Verfahren zur herstellung von polystyrol
DE2717587C2 (de) * 1976-06-22 1986-10-30 Valentin Pavlovič Šatalov Verfahren zur Herstellung von schlagfestem Polystyrol

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2620853B2 (de) * 1975-05-12 1979-10-11 Asahi Kasei Kogyo K.K., Osaka (Japan) Hochschlagfestes Polystyrol
DE2613352A1 (de) * 1976-03-29 1977-10-06 Basf Ag Verfahren zur herstellung von schlagfest modifizierten styrolpolymerisaten
DE2717587C2 (de) * 1976-06-22 1986-10-30 Valentin Pavlovič Šatalov Verfahren zur Herstellung von schlagfestem Polystyrol
US4482677A (en) * 1980-08-25 1984-11-13 Japan Elastomer Co., Ltd. Process for producing high impact polystyrene
DE3506939A1 (de) * 1984-02-28 1985-09-12 Sumitomo Chemical Co., Ltd., Osaka Verfahren zur herstellung von polystyrol

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998052984A1 (fr) * 1997-05-22 1998-11-26 Basf Aktiengesellschaft Procede de preparation de solutions de polymerisats dieniques dans des monomeres vinylaromatiques

Also Published As

Publication number Publication date
MX9710011A (es) 1998-07-31
EP0832141A1 (fr) 1998-04-01
DE19614293A1 (de) 1997-10-16
JPH11507984A (ja) 1999-07-13
TW339349B (en) 1998-09-01

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