EP1448639A2 - Procede de polymerisation anionique continue de polystyrol resilient - Google Patents

Procede de polymerisation anionique continue de polystyrol resilient

Info

Publication number
EP1448639A2
EP1448639A2 EP02779496A EP02779496A EP1448639A2 EP 1448639 A2 EP1448639 A2 EP 1448639A2 EP 02779496 A EP02779496 A EP 02779496A EP 02779496 A EP02779496 A EP 02779496A EP 1448639 A2 EP1448639 A2 EP 1448639A2
Authority
EP
European Patent Office
Prior art keywords
rubber
styrene
weight
polymerization
reactor cascade
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP02779496A
Other languages
German (de)
English (en)
Inventor
Hermann Gausepohl
Jürgen DEMETER
Philippe Desbois
Christian Schade
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 SE filed Critical BASF SE
Publication of EP1448639A2 publication Critical patent/EP1448639A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • 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

Definitions

  • the invention relates to a process for the preparation of impact-resistant molding compositions by anionic polymerization of vinyl-aromatic monomers in the presence of a rubber in a continuously flowed reactor cascade comprising at least two reactors.
  • EP-A 595121 describes the transfer to a continuous process in a boiler-boiler-tower-tower cascade, as was known for the radical polymerization of impact-resistant polystyrene.
  • the monomer stream is here to split a 'zel- nen reactors.
  • larger tower reactors it has been shown that the metered-in monomeric styrene cannot be homogenized quickly enough with the highly viscous polymer solution and therefore uncontrolled reactions can occur.
  • WO 96/18666 describes a process in which impact-modified polystyrene is polymerized continuously in a single reactor above the phase inversion point.
  • a process for the preparation of impact-resistant molding compositions by anionic polymerization of vinyl aromatic monomers in the presence of a rubber in a continuously flowed reactor cascade from at least two reactors, the vinyl aromatic monomers in partial streams to the reactors of the reactor cascade and an anionic initiator and a rubber to at least the first reactor are supplied, found, the reactor cascade consisting of back-mixing reactors.
  • Continuously flowed stirred tanks are suitable as reactors. They ensure a sufficiently rapid mixing of the feeds with the polymerization mixture and an effective removal of the heat of reaction by evaporative cooling. The vapors formed in this way usually run back into the reactor. Some of the solvent-containing condensate can also be removed using the heat of reaction.
  • polymerization is preferably carried out in a reactor cascade consisting of two stirred tanks connected in series, the solids content in the first stirred tank being above the phase inversion point.
  • the solids content in the first stirred tank is preferably at least twice the weight fraction of the rubber therein and in the second stirred tank in the range of 50-85% by weight.
  • the solids content in the first stirred kettle is particularly preferably 5 to 30% by weight above twice the value by weight of the rubber, with a rubber content of 5 to 15% by weight, that is to say in the range from 15 to 60% by weight.
  • the solids content in the first stirred tank is below the phase inversion point, in the second stirred tank at least twice the weight fraction of the rubber and in the third stirred tank in the range from 50 to 85% by weight.
  • Isomerism in the individual reactors of the reactor cascade is preferably polymerized at temperatures in the range from 50 to 170 ° C., particularly preferably in the range from 70 to 130 ° C. Here will preferably set a higher temperature within the reactor cascade from reactor to reactor.
  • the polymerization can be carried out via a degasser at temperatures in the range from 200 to 280 ° C.
  • Styrene and styrene derivatives in particular styrene and .alpha.-methylstyrene or mixtures of different styrene derivatives, can be used as vinyl aromatic monomers.
  • the vinyl aromatic monomers are fed to the reactors of the reactor cascade in partial flows.
  • the monomer conversion in each reactor should be above 95%, preferably above 99%. Since the monomer conversion determines the heat of reaction released, the maximum possible monomer feed to the individual reactors results from their boiling cooling capacities.
  • the ratio of the individual sub-streams to one another depends on the desired solids content which one would like to achieve in the individual reactors of the reactor cascade.
  • the vinylaromatic partial monomer streams are generally divided in the ratio R2 / R1 of 0.1-15, preferably 1-7, in particular 3-4.
  • the distribution is generally in the ratio R3 / R1 and R2 / R1 of 0.1-15, preferably 2-10, in particular 2-3.
  • the process according to the invention can be carried out in inert solvents, for example aliphatic, cycloaliphatic or aromatic hydrocarbons or mixtures thereof.
  • Preferred hydrocarbons are those with 3 to 12 carbon atoms.
  • Preferred solvents are toluene, cyclohexane or methylcyclohexane.
  • the usual mono-, bi- or multifunctional alkali metal alkyls, aryls or aralkyls can be used as anionic polymerization initiators.
  • Organolithium compounds such as ethyl, propyl, isopropyl, N-butyl, sec-butyl-, tert-butyl-, phenyl-, diphenylhexyl-, hexamethyl-, butadienyl-, isoprenyl or polystyryllithium as well as 1, 4-dilithium-butane, 1, 4-dilithium-2-butene or 1, 4- Dilithium benzene used.
  • the required amount depends on the desired molecular weight. As a rule, it is in the range from 0.001 to 5 mol%, based on the total monomer.
  • sub-stoichiometric amounts may also be sufficient in view of a particular molecular weight to be achieved due to transfer reactions to the solvent.
  • the savings can be up to 50%, based on the stoichiometric amount.
  • the anionic initiator is fed to at least the first reactor. However, it can also be divided into partial streams in any ratio among the various reactors in the reactor cascade. This enables bimodal or multimodal molecular weight distributions of the vinylaromatic hard matrix to be achieved.
  • Lewis bases such as tetrahydrofuran, tertiary amines or soluble potassium salts, can be added to accelerate the reaction.
  • the rubber is also fed to at least the first reactor.
  • the rubber used should be compatible with the vinylaromatic matrix.
  • Suitable rubbers are styrene block copolymers with at least one block of dienes, such as butadiene, methylbutadiene or isoprene, and copolymer blocks of diene and styrene with a statistical structure.
  • Styrene-butadiene block copolymers or a mixture of a styrene-butadiene block copolymer with a polybutadiene are preferably used as the rubber.
  • the rubber preferably has a solution viscosity of 120 ml / g or less, preferably less than 40 85 ml / g, measured as a 5% strength by weight solution in styrene.
  • the diene content of the rubbers is generally in the range from 10 to 90% by weight, preferably in the range from 65 to 75% by weight.
  • the rubber is preferably used in an amount which leads to a diene content in the range from 6 to 12% by weight, based on the impact-resistant molding composition.
  • a styrene-butadiene two-block or styrene-butadiene-styrene three-block copolymer with at least one styrene block with a number-average molecular weight M n of at least 35,000, preferably at least 70,000 g / mol is particularly preferably used as the rubber.
  • the rubbers used can be produced batchwise using the known methods of sequential anionic polymerization.
  • the solvent which is also used for the polymerization of the vinylaromatic hard matrix is preferably used as the solvent.
  • the rubber is preferred without isolation, if necessary after chain termination with a proton-active substance or Lewis acid, such as water, alcohols, aliphatic or aromatic carboxylic acids and inorganic acids or carbon dioxide, or by reaction with bi- or polyfunctional coupling agents, such as polyfunctional aldehydes, ketones, Esters, anhydrides or epoxides are fed directly to the reactor cascade.
  • a proton-active substance or Lewis acid such as water, alcohols, aliphatic or aromatic carboxylic acids and inorganic acids or carbon dioxide
  • bi- or polyfunctional coupling agents such as polyfunctional aldehydes, ketones, Esters, anhydrides or epoxides are fed directly to the reactor cascade.
  • Styrene / butadiene / styrene / three-block copolymers were obtained by sequential anionic polymerization in toluene and initiation with sec. -Butyllithium (s-BuLi) manufactured. After the polymerization, the mixture was terminated with isopropanol. The rubber solution was then diluted with styrene.
  • the solution contained 130 kg of an SBS three-block copolymer with the block lengths 11,000 / 145,000 / 40,000 g / mol in 390 kg of toluene and 130 kg of styrene.
  • the solution contained 80 kg of an SBS three-block copolymer with the block lengths 12,000 / 168,000 / 57,000 g / mol in 240 kg of toluene and 116 kg of styrene. Production of impact-resistant polystyrenes
  • a reactor cascade consisting of two stirred tanks Rl and R2 equipped with an anchor stirrer and having a volume of 1 or 1.9 liters was used.
  • the styrenic rubber solution and the initiator were fed to the stirred tank R1 via separate feed lines ZI and Z2. Additional monomeric styrene was metered into the second stirred tank R2 via Z3.
  • the throughput was about 800 g / h, based on the impact-resistant polystyrene.

Landscapes

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

Abstract

L'invention concerne un procédé de fabrication de matières à mouler résilientes par polymérisation anionique de monomères vinylaromatiques en présence d'un caoutchouc, dans une cascade de réacteurs parcourue en continu, composée d'au moins deux réacteurs. Les monomères vinylaromatiques sont alimentés aux réacteurs de la cascade de réacteurs sous la forme de courants partiels, et un initiateur anionique et un caoutchouc sont au moins alimentés au premier réacteur, ladite cascade de réacteurs étant composée de réacteurs de remélange.
EP02779496A 2001-10-23 2002-10-18 Procede de polymerisation anionique continue de polystyrol resilient Withdrawn EP1448639A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10152116 2001-10-23
DE10152116A DE10152116A1 (de) 2001-10-23 2001-10-23 Verfahren zur kontinuierlichen anionischen Polymerisation von schlagzähem Polystyrol
PCT/EP2002/011668 WO2003035709A2 (fr) 2001-10-23 2002-10-18 Procede de polymerisation anionique continue de polystyrol resilient

Publications (1)

Publication Number Publication Date
EP1448639A2 true EP1448639A2 (fr) 2004-08-25

Family

ID=7703320

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02779496A Withdrawn EP1448639A2 (fr) 2001-10-23 2002-10-18 Procede de polymerisation anionique continue de polystyrol resilient

Country Status (9)

Country Link
US (1) US6951901B2 (fr)
EP (1) EP1448639A2 (fr)
JP (1) JP2005506415A (fr)
KR (1) KR20040047947A (fr)
CN (1) CN1575306A (fr)
AU (1) AU2002342837A1 (fr)
DE (1) DE10152116A1 (fr)
MX (1) MXPA04003318A (fr)
WO (1) WO2003035709A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10241850A1 (de) * 2002-09-09 2004-03-18 Basf Ag Anionisch polymerisiertes schlagzähes Polystyrol mit guter Fliessfähigkeit
KR101489954B1 (ko) 2011-12-23 2015-02-04 제일모직주식회사 공액 디엔으로부터 열가소성 수지를 연속적으로 제조하는 방법 및 그로부터 제조된 열가소성 수지
CN104558429B (zh) * 2013-10-18 2017-11-07 中国石油化工股份有限公司 聚苯乙烯组合物生产方法及由此得到的聚苯乙烯组合物
CN113698558B (zh) * 2020-05-20 2024-07-02 中国石油化工股份有限公司 丁苯共聚物及其制备方法与应用

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4153647A (en) * 1977-06-15 1979-05-08 Glukhovskoi Vladimir S Process for producing-impact polystyrene
DE4235977A1 (de) * 1992-10-24 1994-04-28 Basf Ag Verfahren zur Herstellung von schlagzähem Polystyrol
DE4235978A1 (de) * 1992-10-24 1994-04-28 Basf Ag Thermoplastische Formmasse
US5990236A (en) * 1993-10-18 1999-11-23 Basf Aktiengesellschaft Preparation of impact-resistant polystyrene
EP0918806B1 (fr) * 1996-08-19 2000-11-08 Basf Aktiengesellschaft Procede pour la preparation de solutions polymeres dieniques dans des monomeres aromatiques vinyliques
JP3838668B2 (ja) * 1996-08-19 2006-10-25 ビーエーエスエフ アクチェンゲゼルシャフト アニオン重合
DE19701865A1 (de) * 1997-01-21 1998-07-23 Basf Ag Kontinuierliches Verfahren zur Herstellung von thermoplastischen Formmassen
DE19804912A1 (de) * 1998-02-07 1999-08-12 Basf Ag Kontinuierliches Verfahren zur Herstellung thermoplastischer Formmassen
JP2002502899A (ja) * 1998-02-07 2002-01-29 ビーエーエスエフ アクチェンゲゼルシャフト 耐衝撃性の熱可塑性成形材料組成物を製造する方法
CN1092216C (zh) * 1998-11-26 2002-10-09 中国石油化工集团公司 一种聚乙烯与粘土的纳米级复合材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03035709A2 *

Also Published As

Publication number Publication date
WO2003035709A3 (fr) 2003-09-18
US20040266946A1 (en) 2004-12-30
MXPA04003318A (es) 2004-07-23
DE10152116A1 (de) 2003-04-30
KR20040047947A (ko) 2004-06-05
AU2002342837A1 (en) 2003-05-06
JP2005506415A (ja) 2005-03-03
US6951901B2 (en) 2005-10-04
CN1575306A (zh) 2005-02-02
WO2003035709A2 (fr) 2003-05-01

Similar Documents

Publication Publication Date Title
EP0918806B1 (fr) Procede pour la preparation de solutions polymeres dieniques dans des monomeres aromatiques vinyliques
DE69008971T2 (de) Verfahren zur Herstellung von Kautschukmodifiziertem-Vinylaromat-Polymeren.
DE2541511C2 (de) Verfahren zur Herstellung eines Blockcopolymerengemisches
DE69810484T2 (de) Hochglänzende und hochschlagfeste aromatische monovinylidenpolymere
DE69700829T2 (de) Verfahren zur Herstellung von mit Kautschuk verstärkten vinylaromatischen Polymeren
EP1560860A1 (fr) Procede pour la polymerisation anionique de polystyrene resilient
EP1053266B1 (fr) Procede de production de matieres de moulage thermoplastiques modifiees a resistance elevee aux chocs
DE69420777T2 (de) Kautschuk-verstärktes vinylaromatische (Co-)Polymer
EP1448639A2 (fr) Procede de polymerisation anionique continue de polystyrol resilient
DE19828104A1 (de) Verfahren zur Herstellung von schlagzäh modifizierten, thermoplastischen Formmassen
EP0595120B1 (fr) Masse à mouler thermoplastique
EP1017731B1 (fr) Styrene-polymere a distribution bimodale des poids moleculaires
EP1718686A1 (fr) Procede ameliore de production de polystyrene resistant aux chocs
WO2001010917A1 (fr) Procede pour preparer une solution de polymeres de dienes dans des composes aromatiques vinyliques et pour produire des polymeres aromatiques vinyliques resistants aux chocs par polymerisation de cette solution
EP1280839A1 (fr) Polystyrene a polymerisation anionique resistant aux chocs, dont les particules presentent une morphologie en forme de capsule
WO1998031721A1 (fr) Procede de production continue de matieres de moulage thermoplastiques
EP0049775A2 (fr) Procédé de préparation en continu de polymères vinylaromatiques modifiés par du caoutchouc
DE69419174T2 (de) Verfahren zur herstellung von monovinyliden aromatischen polymeren mit hohem molekulargewicht
EP1682592A1 (fr) Procede de polymerisation anionique de monomeres en alpha-methylstyrene
DE19715035A1 (de) Verfahren zur kontinuierlichen Herstellung von Blockcopolymeren
DE1720252B2 (de) Verfahren zur herstellung von schlagfesten monovinylaromatischen polymeren
DE4235977A1 (de) Verfahren zur Herstellung von schlagzähem Polystyrol
WO1998052984A1 (fr) Procede de preparation de solutions de polymerisats dieniques dans des monomeres vinylaromatiques
WO2005082958A1 (fr) Procede simplifie pour la production de polystyrene resilient
WO1998031746A1 (fr) Matiere de moulage thermoplastique resiliante

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040524

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SCHADE, CHRISTIAN

Inventor name: DESBOIS, PHILIPPE

Inventor name: DEMETER, JUERGEN

Inventor name: GAUSEPOHL, HERMANN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20060104