EP1187861A1 - Procede de production de matieres moulables thermoplastiques a l'aide de solutions a base de caoutchouc - Google Patents

Procede de production de matieres moulables thermoplastiques a l'aide de solutions a base de caoutchouc

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Publication number
EP1187861A1
EP1187861A1 EP00925264A EP00925264A EP1187861A1 EP 1187861 A1 EP1187861 A1 EP 1187861A1 EP 00925264 A EP00925264 A EP 00925264A EP 00925264 A EP00925264 A EP 00925264A EP 1187861 A1 EP1187861 A1 EP 1187861A1
Authority
EP
European Patent Office
Prior art keywords
molding compositions
abs molding
compositions according
preparation
iii
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Withdrawn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
EP00925264A
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German (de)
English (en)
Inventor
Gisbert Michels
Heike Windisch
Norbert Steinhauser
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.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1187861A1 publication Critical patent/EP1187861A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof

Definitions

  • the present invention relates to thermoplastic ABS molding compositions, processes for their preparation by polymerization in rubber-containing solution and their
  • These methods include dissolving rubbers in vinyl aromatic monomers (e.g. styrene) and ethylenically unsaturated nitrile monomers (e.g. acrylonitrile) and optionally solvents and polymerizing the monomers.
  • a phase separation occurs between the rubber-containing polymer solution and the non-rubber-containing polymer solution during the polymerization.
  • the non-rubber containing polymer solution initially forms a discrete, discontinuous phase. With increasing monomer conversion, phase inversion takes place, i.e. the phase of the non-rubber-containing polymer solution becomes larger and the rubber solution becomes the discontinuous phase, while the non-rubber-containing polymer solution forms the homogeneous phase.
  • the rubber solutions prepared by dissolving the rubber in solid form are polymerized in the presence of further monomers and, if appropriate, solvents by known bulk, solution or suspension polymerization processes in a continuous, semi-continuous or batch procedure and by known evaporation methods isolated.
  • a disadvantage of the known processes for the production of ABS by the bulk, solution or suspension process is that soluble rubbers are used in solid form by being in styrene and / or other monomers and optionally dissolved solvents and then fed to the further polymerization process as a rubber solution. To dissolve the solid rubbers, they have to be cut into small pieces and dissolved in a dissolving container in styrene and / or other monomers and, if appropriate, solvents.
  • the use of rubbers in solid form is disadvantageous because the production of these is soluble
  • Rubbers are preferably carried out by solution polymerization, the solvents used being aliphatic and / or aromatic solvents which are inert during the polymerization and which themselves are not active in polymerization, and where the solvents may have to be separated off by distillation after the polymerization in order to separate the rubbers formed isolate solid form.
  • Another disadvantage is that rubbers with high cold flow or high stickiness are difficult to process and store.
  • anionic initiators such as e.g. Butyllithium, used for the polymerization of butadiene in styrene.
  • an SBR rubber suitable for HIPS production could be obtained by terminating the polymerization with a monomer conversion of butadiene of about 25% or about 36%. It is disadvantageous here that the main part of the butadiene used has to be separated off by distillation before the styrenic rubber solution is used further for impact modification.
  • SBR styrene-butadiene copolymers
  • anionic initiators because styrene-butadiene copolymers (SBR) are formed which, based on the butadiene units, allow only a slight control of the microstructure. By adding modifiers, only the proportion of 1,2- or 1,4-trans units can be increased, which leads to an increase in the glass transition temperature of the polymer. It is not possible to produce a highly cis-containing SBR with anionic initiators, in which the 1, 4- cis content based on the butadiene content of over 40%, preferably over 50%, particularly preferably over 60%.
  • Another disadvantage is the fact that SBR is formed in this process, which results in a further increase in the glass temperature with increasing styrene content compared to homopolymeric polybutadiene (BR).
  • BR homopolymeric polybutadiene
  • a high glass transition temperature of the rubber has a disadvantageous effect on the low temperature properties of the material, so that rubbers with low glass transition temperatures are preferred.
  • HIPS polystyrene
  • a catalyst system consisting of halogenated rare earth acetates, such as Nd (OCOCCl 3 ) 3 or Gd (OCOCF,) 3 - with tri (iosbutyl) aluminum and diethylaluminum chloride, which is described in the inert solvent Hexane enables the copolymerization of butadiene and styrene.
  • halogenated rare earth acetates such as Nd (OCOCCl 3 ) 3 or Gd (OCOCF,) 3 - with tri (iosbutyl) aluminum and diethylaluminum chloride
  • a disadvantage of these catalysts in addition to the presence of inert solvents, is that the catalyst activity drops from less than 5 mol% to less than 10 g of polymer / mmol of catalyst / h, even with a small amount of styrene, and that the 1,4-cis content of the polymer based on the polymeric butadiene units decreases significantly with increasing styrene content.
  • the rubber is used in a matrix of acrylonitrile-styrene copolymers (SAN).
  • SAN acrylonitrile-styrene copolymers
  • the SAN matrix in ABS is incompatible with polystyrene. If, in addition to the rubber, homopolymers of the solvent, such as polystyrene, are formed during the polymerization of the diolefins in vinylaromatic solvents, the incompatibility of the SAN matrix with the homopolymerized vinylaromatics leads to a significant deterioration in the properties of the material.
  • WO 97/38031 and WO 98/07766 describe that styrene-butadiene copolymers or polybutadiene homopolymers are prepared anionically in solution and are used to produce toughened, thermoplastic polystyrene molding compositions and polystyrene-acrylonitrile molding compositions.
  • the disadvantage is that inert solvents are added in the butadiene polymerization, so that the vapors obtained after the degassing, which contain unreacted monomers and solvents, have to be separated and dried in a complex manner in order to reuse them in an anionic polymerization.
  • the invention is based on the object of developing a process for the production of ABS molding compositions by polymerization in a rubber-containing solution which, when using suitable catalysts, does not have the disadvantages mentioned above.
  • the solution to this problem is that to prepare the rubber-containing solution, diolefins are polymerized in a solution of vinylaromatic monomers.
  • the invention further provides that a catalyst is used for the polymerization containing
  • the rubber solutions to be used are obtained in a continuous or discontinuous procedure.
  • polymers are formed in which the content of cis-permanent double bonds based on the butadiene content is greater
  • the rubber solutions to be used are obtained by:
  • conjugated diolefins e.g. 1,3-butadiene, isoprene, 2,3-dimethyl-butadiene, 2,4-hexadiene, 1,3-pentadiene and / or 2-methyl-1,3-pentadiene, particularly preferably 1,3-butadiene, are used come.
  • the molar ratio in which the catalyst components A to C are used can be varied within wide limits.
  • the molar ratio of component A to component B can be 1: 1 to 1: 1000, preferably 1: 3 to 1: 200, particularly preferably 1: 3 to 1: 100.
  • the molar ratio of component A to component C can be 1 : 0.02 to 1:15, preferably 1: 0.4 to 1: 5.
  • component C can be dispensed with in whole or in part.
  • Suitable compounds of the rare earth metals are, in particular, those which are selected from
  • an alcoholate of the rare earth metals a phosphonate, phosphinates and / or phosphates of the rare earth metals, a carboxylate of the rare earth metals, - a complex compound of the rare earth metals with diketones and / or an addition compound of the halides of the rare earth metals with an oxygen or nitrogen donor compound .
  • the aforementioned compounds of rare earth metals are described in more detail, for example, in EP 1 1 184.
  • the compounds of the rare earth metals are based in particular on the elements with atomic numbers 21, 39 and 57 to 71.
  • Lanthanum, praseodymium or neodymium or a mixture of elements of the rare earth metals, which contains at least one of the elements lanthanum, praseodymium or, are preferably used as rare earth metals Contains neodymium to at least 10 wt .-%.
  • Lanthanum or neodymium are very particularly preferably used as rare earth metals, which in turn can be mixed with other rare earth metals.
  • the proportion of lanthanum and / or neodymium in such a mixture is particularly preferably at least 30% by weight.
  • Suitable alcoholates, phosphonates, phosphinates, phosphates and carboxylates of the rare earth metals or as complex compounds of the rare earth metals with diketones are, in particular, those in which the organic group contained in the compounds in particular straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as methyl,
  • Rare earth alcoholates e.g. called:
  • rare earth phosphonates, phosphinates and phosphates are: Neodymium (III) -dibutylphosphonate, neodymium (III) -dipentylphosphonate, neodymium (III) -dihexylphosphonate, neodymium (III) -diheptylphosphonate, neodymium (III) -dioctylphosphonate, neodymium (III) -dinonylymodonosphonate-neodymium , Neodymium (III) - dibutylphosphinate, neodymium (III) -dipentylphosphinate, neodymium (III) -dihexylphosphinate, neodymium (III) -diheptylphosphinate, neodymium (III) -dioctylphosphinate,
  • Suitable carboxylates of rare earth metals are:
  • Examples of addition compounds of the halides of rare earth metals with an oxygen or nitrogen donor compound are: Lanthanum (III) chloride with tributyl phosphate, lanthanum (HI) chloride with tetrahydrofuran, lanthanum (III) chloride with isopropanol, lanthanum (III) chloride with pyridine, lanthanum (III) chloride with 2-ethylhexanol, lanthanum (III) chloride with ethanol, praseodymium (III) chloride with tributyl phosphate, praseodymium (III) chloride with tetrahydrofuran, praseodymium (III) chloride with isopropanol, praseodymium (III) chloride with pyridine, praseodymium (III) -chloride with 2-ethylhexanol, praseodymium (III) chloride with ethanol, neodymium (III) chloride
  • Neodymium versatate, neodymium octanoate and / or neodymium naphthenate are very particularly preferably used as compounds of the rare earth metals.
  • the above-mentioned compounds of rare earth metals can be used both individually and in a mixture with one another.
  • Compounds selected from an aluminum trialkyl, a dialkylaluminium hydride and / or an alumoxane of the formulas (I) - (IV) are used as organoaluminum component B.
  • R can be the same or different and straight-chain and branched alkyl radicals having 1 to 10 carbon atoms, preferably 1 to
  • alumoxanes (III) and (IV) are: methylalumoxane, ethylalumoxane and isobutylalumoxane, preferably methylalumoxane and isobutylalumoxane.
  • the aluminum alkyls can be used individually or as a mixture with one another.
  • Lewis acids are used as component C.
  • Ethylaluminum dichloride ethylaluminum butylaluminum dibromide, butylaluminum dichloride, di methylaluminiumbromid, dimethylaluminum chloride, diethylaluminum bromide, di-, thylaluminiumsesquibromid Dibutylaluminiumbromid, dibutylaluminum chloride, methyl, methylaluminum sesquichloride, ethylaluminum sesquibromid, ethylaluminum sesquichloride, aluminum tribromide, Antimontri- chloride, antimony pentachloride, silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, Trimethylchlorosilane, ethyltrichlorosilane, diethyldichlorosilane, triethylchlorosilane, vinyltrichlorosilane, divinyld
  • Diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide and / or ethyl aluminum dibromide are preferably used.
  • reaction products of aluminum compounds as described as component B with halogens or halogen compounds for example triethyl aluminum with bromine or triethyl aluminum with butyl chloride, can also be used as component C.
  • the reaction can be carried out separately, or the amount of the alkyl aluminum compound required for the reaction is added to the amount required as component B.
  • Ethyl aluminum sesquichloride, butyl chloride and butyl bromide are preferred.
  • component C can be dispensed with in whole or in part.
  • This component D can be a conjugated diene, which can be the same diene that is later to be polymerized with the catalyst. Butadiene and / or isoprene are preferably used.
  • the amount of D is preferably 1 to 1000 mol, based on 1 mol of component A, particularly preferably 1 to 100 mol. 1 to 50 mol of D, based on 1 mol of component A, are very particularly preferably used.
  • the catalysts are used in amounts of 1 ⁇ mol to 10 mmol, preferably 10 ⁇ mol to 5 mmol, of the compound of the rare earth metals based on 100 g of the monomers.
  • the rubber solution is prepared in the presence of vinylaromatic monomers, in particular in the presence of styrene, ⁇ -methylstyrene, ⁇ -methylstyrene dimer, p-methylstyrene, divinylbenzene and / or other alkylstyrenes, preferably with 2 to 6 carbon atoms in the alkyl radical carried out.
  • styrene particularly preferred.
  • the solvents can be used individually or in a mixture.
  • the amount of vinyl aromatic monomers used as solvent is usually 10 g to 2,000 g, preferably 100 to 1,000 g, very particularly preferably
  • the rubber solutions are preferably produced at temperatures from -20 to 100.degree. C., very particularly preferably at temperatures from 20 to 90.degree.
  • the production can be carried out without pressure or at elevated pressure (0.1 to 12 bar).
  • the production can be carried out continuously or discontinuously, preferably in a continuous manner.
  • the rubber-modified then.ioplastischen molding compositions according to the invention can preferably by radical polymerization of a vinyl aromatic
  • Monomers and an ethylenically unsaturated nitrile monomer can be produced.
  • the reaction takes place in the presence of one of the rubber solutions described above with the addition of ethylenically unsaturated nitrile monomer and, if appropriate, with the addition of further vinylaromatic monomer and, if appropriate, in the presence of solvents by known methods of
  • Vinylaromatic monomers which are radically polymerized together with ethylenically unsaturated nitrile monomers and thereby the homogeneous phase
  • Ethylenically unsaturated nitrile monomers are preferably acrylonitrile and methacrylonitrile, particularly preferably acrylonitrile.
  • the ratio of vinyl aromatic monomers to ethylenically unsaturated nitrile monomers in the ABS molding compositions according to the invention is 60-90% by weight to 40-10% by weight, based on the matrix phase.
  • the rubber content in the ABS molding compositions according to the invention is 5-35% by weight, preferably 8-25% by weight, based on the ABS molding composition.
  • aromatic hydrocarbons such as toluene, ethylbenzene, xylenes and ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone and mixtures of these solvents are suitable as solvents.
  • aromatic hydrocarbons such as toluene, ethylbenzene, xylenes and ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone and mixtures of these solvents are suitable as solvents.
  • Ethylbenzene is preferred,
  • the polymerization is advantageously triggered by radical initiators, but can also be carried out thermally; the molecular weight of the polymer formed can be adjusted by molecular weight regulators.
  • Suitable initiators for radical polymerization are graft-active peroxides which break down into free radicals, such as peroxycarbonates, peroxydicarbonates, diacyl peroxides, perketals, or dialkyl peroxides and / or azo compounds or mixtures thereof.
  • examples are azodiisobutyronitrile, azoisobutter acid, alkyl ester, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl perneodecanoate, tert-butyl per- (2-ethylhexyl) carbonate.
  • These initiators are used in amounts of 0.005 to 1% by weight, based on the monomers.
  • molecular weight regulators such as mercaptans, olefins, e.g. tert-Dodecyl mercaptan, n-dodecyl mercaptan, cyclohexene, terpinolene, ⁇ -methylstyrene dimer in amounts of 0.05 to 2% by weight, based on the monomers, are used.
  • the process according to the invention can be carried out batchwise, semi-continuously and continuously.
  • the rubber solution, monomers and, if appropriate, solvents can advantageously be polymerized in a continuously charged, mixed and stirred tank reactor with a stationary monomer conversion after the phase inversion in the first stage of more than 10% and the free-radical-initiated polymerization in at least a further stage up to a monomer conversion of 30 to
  • Residual monomers and solvents can be prepared using conventional techniques (for example in heat exchanger evaporators. Flash evaporators, strand evaporators. Thin film or thin film evaporators, screw evaporators, stirred multiphase evaporators with kneading and Stripping devices) are removed, the use of propellants and entraining agents, for example water vapor, is also possible, and are returned to the process. Additives, stabilizers, anti-aging agents, fillers and lubricants can be added during the polymerization and during the polymer isolation.
  • the discontinuous and semi-continuous polymerization can be carried out in one or more filled or partially filled stirred tanks connected in series with the rubber solution, monomers and, if appropriate, solvents and polymerization, up to the stated monomer conversion of 30 to 90%.
  • the syrup can be pumped in a circle over both mixing and shearing organs with continuous and discontinuous operation.
  • Loop reactors are state of the art and can be helpful in adjusting the particle size of the rubber.
  • the arrangement of shear members between two separate reactors is more advantageous in order to avoid back-mixing, which leads to a broadening of the particle size distribution.
  • the average residence time is 1 to 10 hours, preferably 2 to 6 hours.
  • the polymerization temperature is 50 to 180 ° C, preferably 70 to 170 ° C.
  • the rubber-modified thermoplastic molding compositions according to the invention have rubber particle sizes with a diameter (weight average, d w ) of 0.1 to 10 ⁇ m, preferably of 0.1 to 2 ⁇ m.
  • the molding compositions according to the invention can be processed into molded parts by extrusion, injection molding, calendering, blow molding, pressing and sintering. Examples
  • the solution viscosity of the rubber solutions is measured on a 5% strength by weight solution using a Brookfield viscometer at 25 ° C. (Brookfield RV, Syncro-Lectric, model LVT, spindle 2, speed can be set permanently, depending on viscosity: 6.12 , 30, 60 rpm).
  • the sales are determined by determining the solids by evaporation
  • the polymerizations were carried out in the absence of air and moisture
  • the polymerization was carried out in a 40-1 steel reactor with anchor stirrer (100 rpm).
  • the catalyst components were added to a solution of butadiene in styrene in the following order: 1) di-iso-butylaluminium hydride (DIBAH, as a 3.2 molar solution in hexane), 2) neodymium versatate (NDV, as a 0.24 molar solution in Cyclohexane), 3) ethyl aluminum sesquichloride (EASC, as 0.1 molar solution in hexane).
  • DIBAH di-iso-butylaluminium hydride
  • NDV neodymium versatate
  • EASC ethyl aluminum sesquichloride
  • Example C and D only part (40%) of the amount of butadiene was introduced and the remainder was metered in during the polymerization after heating to 65 ° C. within 1 h.
  • the polymer solution was transferred to a second reactor (80-1 reactor, anchor stirrer, 100 rpm) and the polymerization was carried out by adding 500 g of methyl ethyl ketone with 18 g of p-2,5-di-tert-butylphenol-propionic acid octyl ester (Irganox 1076, Ciba-Geigy) and 18 g of tris (nonylphenyl) phosphite (Irgafos TNPP, Ciba-Geigy).
  • the internal reactor pressure at 50 ° C was within
  • the solution is in a 5 1 flat ground vessel with anchor stirrer and reflux condenser
  • metering solution III consisting of methyl ethyl ketone and alpha-methylstyrene dimer, is added in 1-2 minutes, and the stirrer is then set to 100 rpm. After metering in of solution II, the mixture is stirred at 85 ° C. for a further 2 h, then up
  • compositions of the formulations results of the polymerization and characterization of the ABS molding compositions are summarized in the tables below.
  • Composition of the recipes (all data in g)

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de production de matières moulables ABS. Ce procédé consiste à produire une solution à base de caoutchouc puis à effectuer la polymérisation en présence de cette solution à base de caoutchouc pour obtenir les matières moulables ABS. Pour obtenir la solution à base de caoutchouc, on effectue la polymérisation de dioléfines dans une solution de monomères vinylaromatiques en présence d'un catalyseur, contenant A) au moins un composé des métaux terreux rares, B) au moins un composé aluminiumorganique et C) éventuellement un acide de Lewis.
EP00925264A 1999-05-18 2000-05-05 Procede de production de matieres moulables thermoplastiques a l'aide de solutions a base de caoutchouc Withdrawn EP1187861A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19922640A DE19922640A1 (de) 1999-05-18 1999-05-18 Verfahren zur Herstellung von thermoplastischen Formmassen unter Verwendung von Kautschuklösungen
DE19922640 1999-05-18
PCT/EP2000/004031 WO2000069939A1 (fr) 1999-05-18 2000-05-05 Procede de production de matieres moulables thermoplastiques a l'aide de solutions a base de caoutchouc

Publications (1)

Publication Number Publication Date
EP1187861A1 true EP1187861A1 (fr) 2002-03-20

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EP00925264A Withdrawn EP1187861A1 (fr) 1999-05-18 2000-05-05 Procede de production de matieres moulables thermoplastiques a l'aide de solutions a base de caoutchouc

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Country Link
EP (1) EP1187861A1 (fr)
JP (1) JP2002544349A (fr)
KR (1) KR20010113961A (fr)
CN (1) CN1351618A (fr)
AU (1) AU4404200A (fr)
BR (1) BR0010753A (fr)
CA (1) CA2372174A1 (fr)
DE (1) DE19922640A1 (fr)
HK (1) HK1046696A1 (fr)
MX (1) MXPA01011764A (fr)
WO (1) WO2000069939A1 (fr)

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Publication number Priority date Publication date Assignee Title
MXPA05008841A (es) 2003-02-21 2005-10-18 Dow Global Technologies Inc Proceso para homo- o copolimerizacion de olefinas conjugadas.
KR100922700B1 (ko) 2007-06-15 2009-10-20 금호석유화학 주식회사 저용융점도 말레이미드-α-알킬스티렌계 삼원 괴상공중합체 및 이를 만드는 연속괴상중합공정

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Publication number Priority date Publication date Assignee Title
DE2848964A1 (de) * 1978-11-11 1980-05-22 Bayer Ag Katalysator, dessen herstellung und verwendung zur loesungspolymerisation von butadien
JP3211274B2 (ja) * 1991-08-27 2001-09-25 旭化成株式会社 共役ジエン系重合体の製造方法
JPH05117341A (ja) * 1991-10-30 1993-05-14 Asahi Chem Ind Co Ltd 新規な共役ジエン系ブロツク共重合体及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0069939A1 *

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DE19922640A1 (de) 2000-11-23
CN1351618A (zh) 2002-05-29
WO2000069939A1 (fr) 2000-11-23
BR0010753A (pt) 2002-02-26
CA2372174A1 (fr) 2000-11-23
HK1046696A1 (zh) 2003-01-24
AU4404200A (en) 2000-12-05
KR20010113961A (ko) 2001-12-28
JP2002544349A (ja) 2002-12-24
MXPA01011764A (es) 2002-06-21

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