WO2004055064A2 - Verfahren zur herstellung von co- und terpolymeren aus olefinen - Google Patents
Verfahren zur herstellung von co- und terpolymeren aus olefinen Download PDFInfo
- Publication number
- WO2004055064A2 WO2004055064A2 PCT/EP2003/013423 EP0313423W WO2004055064A2 WO 2004055064 A2 WO2004055064 A2 WO 2004055064A2 EP 0313423 W EP0313423 W EP 0313423W WO 2004055064 A2 WO2004055064 A2 WO 2004055064A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aluminum
- phen
- dimethylamino
- propyl
- propene
- Prior art date
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Definitions
- the present invention relates to a process for the preparation of copolymers and terpolymers from olefins with improved properties.
- the invention relates to the production of ethylene / propene copolymers (EPR), ethylene / propylene / diene terpolymers (EPDM) and further copolymers of ethylene / propene, 1-olefins and dienes with their elastomeric properties caused by their structural structure , It is in particular a process for the production of EPR and EPDM rubbers by polymerizing ethylene and propene, optionally ethylidene norbornene as diene at temperatures between -20 to 150 ° C. using a titanium-containing mixed catalyst and donor-stabilized aluminum compounds.
- supported catalysts based on titanium compounds or soluble systems based on vanadium or metallocene catalysts have been used for the production of EPR and EPDM (Seppälä et al. [EU1994], Eur. Polym. J. 30,1111 ).
- the rubbers produced in this way are used, for example, in tires, hoses, roof foils, cable sheathing, seals and are also provided with fillers, stabilizers, antioxidants, oils, lubricants, vulcanization aids or sulfur.
- the supported catalysts are produced either by mixing magnesium halide, one or more electron donors (internal or external) and titanium trichloride or from finely crystalline titanium trichloride, with aluminum alkyls serving as the activator.
- Such catalysts are described, for example, by Govoni and Galli (1997), US Pat. 5698642 and by Kashiwa et al. (2984), Polym. Bull. 12, 362.
- a disadvantage of these catalyst systems is that crystalline ethylene sequences can be formed which reduce the elasticity of the material (Kakugo et al. (1989) Makromol. Ch. 190, 849).
- the proportion of diene required for EPDM elastomers is difficult and expensive to install. Therefore, in the process for producing this post Polymeric vanadium complexes which are technically soluble as catalyst systems are preferred. However, this is very complex since, after the polymerization, solvents and toxic catalyst residues have to be removed.
- Aids and silicon dioxide carriers obtained.
- the particle morphology is better than that of the titanium systems; for this there are blocks of isotactically linked propene units. This leads to an undesirable high temperature crystallinity.
- the present invention is therefore based on the object of providing a process for the preparation of copolymers and terpolymers by which the desired polymers are obtained, but which do not have the disadvantages listed.
- Another object is to provide catalyst systems which can be used in this process and which have high temperature stability combined with high activity in the copolymerization and terpolymerization of olefins, can be prepared in a simple and inexpensive manner, and copolymers and terpolymers with deliver technically interesting properties.
- the catalyst systems of the invention are said to be usable in large-scale plants under simple conditions.
- the object is achieved by a process as characterized by claims 1 to 14 and by copolymers and terpolymers which can be obtained by the process according to the invention.
- R 1 linear or branched alkylene, cycloalkylidene, alkenylene, ArNlene, silylene, which may contain heteroatoms such as ⁇ , P, O, S, F or X 1 or X 2 , optionally complex-bound to aluminum
- R 2 , R 3 independently of one another are linear or branched alkyl, cycloalkyl, alkenyl, aryl, alkynyl, silyl, H, F, Cl, Br, I or X 2 , which in turn can be partially fluorinated or perfluorinated
- R, R 'independently of one another are linear or branched alkyl, cycloalkyl, alkenyl, aryl, alkynyl, silyl or H, which in turn can be partially fluorinated or perfluorinated
- R 1 can independently have different meanings
- the coordination catalyst itself consists of
- (C) optionally also from a carrier based on MgCl 2 , SiO or SiO 2 in combination with MgCl 2 .
- the compounds of the general formula (I) have the function of the cocatalyst in the coordination catalyst system, i.e. they convert the catalyst into the catalytically active species and thus have a major influence on the activity and productivity of the catalyst system.
- these compounds can also have stereoselectivity-imparting properties in addition to the cocatalytic properties.
- Compounds of the general formula (I) can be prepared by methods known to those skilled in the art for the preparation of organometallic compounds. Methods for the preparation of such compounds are described, for example, in G. Bahr, P. Burba, Methods of Organic Chemistry, Vol. XIII / 4. Georg Thieme Verlag, Stuttgart (1970), Z. Anorg. Allg.Chem. 2000, 626, 2081, DE10128299 or in DE10149785. The mentioned documents are therefore part of the disclosure of the present invention.
- the compounds of the general formula (I) are quite stable with respect to oxygen, in particular the oxygen in the air, and with respect to the influence of moisture. They have an extremely high temperature stability. This also applies to the coordination catalysts produced with the aid of these compounds. Corresponding coordination catalyst systems also have a particularly high resistance under the reaction conditions. They tend to be less susceptible to deactivation compared to compounds with free electron pairs, in particular those compounds which contain heteroatoms such as sulfur, oxygen, nitrogen or phosphorus. They also have a higher tolerance towards polyunsaturated compounds / comonomers such as dienes.
- the catalyst systems according to the invention have very particularly advantageous properties in co- and terpolymerization reactions of olefins.
- linear or branched alkyl is understood to mean linear or branched carbon chains with 1 to 20 C atoms.
- Such are e.g. B. methyl, ethyl, i- and n-propyl groups and further groups include the branched and unbranched isomers of butyl, pentyl, hexyl, heptyl, octyl, etc. to C 20 .
- Cycloalkyl groups are understood to mean, for example, cyclopentyl, cyclohexyl or cycloheptyl groups.
- Alkenyl groups in turn are linear or branched carbon chains with 2 to 10 carbon atoms such as B. vinyl, allyl or the isomeric butenyl groups. This includes not only the monounsaturated but also polyunsaturated groups such as B. Pentadienyl.
- Aryl groups can be, for example, phenyl or naphthyl, indenyl, and other fused aromatic groups.
- Alkyne groups are linear or branched carbon chains with 2 to 10 carbon atoms such as ethynyl, propynyl, butynyl etc. to C 10 or the corresponding isomeric representatives.
- Silyl groups can be, for example, (CH 3 ) 3 Si, (C 2 H 5 ) 3 Si, (C 3 H 7 ) 3 Si or (C 6 H 5 ) 3 Si.
- linear or branched carbon chains with 1 to 20 are linear or branched alkylene Understand C atoms.
- Such are e.g. B. methylene, ethylene groups and further groups to understand the branched and unbranched isomers of propylene, butylene, pentylene, hexylene, heptylene, octylene, etc. to C 20 .
- Cycloalkylidene groups are, for example, cyclopentylidene, cyclohexylidene or cycloheptylidene groups.
- Alkenylene groups in turn are linear or branched carbon chains with 2 to 10 carbon atoms such as. B. vinylene, allylene or the isomeric butenylene groups. This includes not only the monounsaturated but also polyunsaturated groups such as B. pentadienylene.
- Arylene groups can be, for example, phenylene or naphthylene, inddenylene, and other condensed aromatic groups.
- Silylene groups can be, for example, (CH 3 ) 2 Si, (C 2 H 5 ) 2 Si, (C 3 H 7 ) 2 Si or (C 6 H 5 ) 2 Si.
- X 2 stands for NRR 'or OR, complex-bound to aluminum
- R 1 is linear or branched C 2 -C ⁇ 0 alkylene, C 2 -C 10 alkenylene, C 6 -C 10 arylene or silylene,
- R 2 , R 3 represents linear or branched Ci-C-io-alkyl
- R, R ' represents linear or branched CC 10 alkyl, C 6 -C 10 aryl or silyl, mo,
- R 1 represents linear or branched C 3 -C 5 alkylene, C 3 -C 5 alkenylene or C 6 -C 10 arylene,
- R 2 , R 3 represents linear or branched CC 4 alkyl
- n 1, 2, 3, 4,
- [3- (Dimethylamino) propyl] dimethylaluminium are suitable for the copolymerization of ethene with hexene.
- Suitable olefinically unsaturated hydrocarbons are, for example, ethylene, C 3 -C 1 -alk-1-enes such as propene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1 Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, furthermore styrene, ⁇ -methylstyrene, cycloolefins such as cyclopentene, norbomen or dienes such as 1, 3-
- Ethylene, propylene, 1-butene, 1-hexene, 1-octene, norbornene, butadiene or ethylidene norbomene are preferably used.
- the compounds of the general formula (I) are very stable compounds, with the aid of which very stable coordination catalyst systems are also advantageously obtained, as a result of which their production, storage and use are much less problematic than in the past known systems.
- the catalysts are produced and used in a manner known per se, as is customary for the particular system and the particular application.
- the catalyst is supported or unsupported in a solvent, for. B dissolved or suspended in a hydrocarbon such as pentane, hexane, heptane, octane or toluene.
- a hydrocarbon such as pentane, hexane, heptane, octane or toluene.
- Ethene / propene / copolymer is 50% and AIEt 3 is 37%.
- the molecular weights of the copolymers achieved are in the range from 110,000 to 1,200,000 g / mol. In comparison, molar masses between 50,000 and 1,100,000 g / mol were found with AIEt 3 as cocatalyst.
- ethylene / propene copolymers with molecular weights in the range from 50,000 to 1,500,000 g / mol, the molar ethylene / propene ratio being in the range from 1:99 to 99: 1.
- the compounds of the general formula (I) have a great tolerance towards dienes compared to AIEt 3 .
- ENB ethylidene norbomene
- the presence of ethylidene norbomene (ENB) in the starting olefin monomer solution (ethylene, propylene, ENB) not only leads to a drop in activity and non-incorporation of ENB when using AIEt 3 , but also to the fact that propene is almost not incorporated into the polymer chain, although in ethene-propene copolymerization, propene is definitely incorporated into the polymer chain.
- XEthyler . 0.5 - 0.9
- X Pra p y ia 0.05 - 0.3
- XEthylidennorbomervO-05 - g / mol to produce 0.2 ITIOl a molecular weight in the range from 50,000 to 1,000,000.
- the polymerization processes in the presence of the cocatalysts according to the invention for the preparation of the copolymers are not restricted to a specified method. Conditions such as when using a Ziegler-Natta catalyst system or a Kaminsky catalyst system can advantageously be selected.
- bulk or bulk polymerizations in which monomers are used as solvents, solution polymerizations in a suitable solvent, suspension polymerizations in a suitable inactive solvent and gas-phase polymerizations under the influence of a suitable pressure can advantageously be used as components in the presence of the compounds of the general formula (I) according to the invention a catalyst system are carried out as long as the copolymers or terpolymers produced have the desired properties.
- the polymers can be produced batchwise or continuously. Although this does not completely change the constitution of the polymers, it is necessary to control certain parameters in a suitable manner in each polymerization process and to optimize them by choosing a suitable cocatalyst system according to the invention.
- the choice of the concentrations of the monomers to be polymerized, the mixing by suitable measures, the set reaction temperatures, separation methods and the like also play a role and can be optimized.
- the individual components (A), (B) and (C) can be assembled in advance to form a directly usable catalyst system.
- the components can be mixed with one another beforehand in a suitable manner and then used for the polymerization. However, they can also be mixed together only in the polymerization mixture.
- the catalyst components can be applied on a support based on MgCl 2 , SiO 2 or SiO 2 in combination with MgCl 2 .
- inert hydrocarbons such as propane, butane, pentane, hexane, octane, decane
- cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane
- aromatic hydrocarbons such as benzene, toluene and xylene
- halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane
- Temperature, pressure, gas atmosphere and duration are selected in a known manner during the manufacturing process. It goes without saying that low temperatures require a longer reaction time. However, a he temperature reduce the achievable activity of the catalyst system.
- the catalyst system is preferably prepared at a temperature at which the polymerization reaction also takes place.
- copolymers and terpolymerizations according to the invention are preferably carried out at temperatures in a range from -20 to 120 ° C., preferably in a range from 0 to 100 ° C.
- Suitable solvents are, for example, aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene, or cyclic hydrocarbons such as cyclopentane, methylcyclohexane or aliphatic hydrocarbons such as pentane, hexane, heptane, octane, or halogenated hydrocarbons such as chloroform, dichloromethane, or mixtures thereof. It is also possible to use a monomer as a solvent and in excess, so that it serves as a solvent, provided that this does not adversely affect the composition of the desired copolymer.
- the setting of the polymerization temperature during the reaction is very important. According to the present invention, it is possible for the person skilled in the art to determine the optimum by various methods known to him To determine the temperature range for the production of a co- or terpolymer with the desired properties. In particular, this is possible for him by creating a parameter matrix in which all reaction parameters are incorporated, with the help of which an experimental plan is processed.
- the polymerization temperatures are generally in a range from -20 to 120 ° C., preferably in a range from 0 to 100 ° C.
- Copolymers and terpolymers with particularly good properties shafts are obtained by solution polymerization, in particular at temperatures from 20 to 100 ° C. Particularly good results are achieved at temperatures of 30 - 100 ° C.
- the catalyst activity drops, so that the polymerization reaction is stopped. Conversely, if the temperature is set too high, the catalyst activity may decrease, which may be due to decomposition. On the other hand, undesirable side reactions can also occur in this case, or the interruption can also be terminated
- the polymerization temperature is to be selected by the person skilled in the art in such a way that a high catalyst activity is ensured, as a result of which the highest possible reaction rate is ensured during the entire reaction time and a copolymer or terpolymer is obtained with the desired properties, ie. H. with the corresponding comonomer incorporation rates, a sufficiently high molecular weight with low crystallinity and with improved processing properties.
- the reaction product can be separated off by methods known to the person skilled in the art. These methods include simple distillation of the solvent as well as steam distillation to remove solvent or the addition of methanol to precipitate; but other methods are also suitable.
- the product can be separated, collected and dried. It has been found that 30-90% by weight of ethylene have been incorporated into ethylene copolymers which have been prepared by the process according to the invention. These polymers have a glass transition temperature of less than -30 ° C, preferably lower than -40 ° C.
- the polymers produced by the tests and according to the invention also have densities of less than 0.89 g / cm 3 .
- control of the molecular weight of the polymer product produced is one of the important characteristics. This can be decisively influenced by the choice of the catalyst system, by the molar ratio of the monomers used to one another, the polymerization temperature, but also by the pressure during the polymerization reaction, so that polymers with very different average molecular weights can be produced by the process according to the invention.
- component (A) has a decisive influence both on the molecular weight and on the composition of the polymer obtained.
- connections have been selected from the group
- [2- (methoxy) benzyl] dibutyl aluminum, [3- (dimethylamino) propyl] dimethyl aluminum, [3- (dimethylamino) propyl] diethyl aluminum and [2- (diethylaminomethyl) phen-1-yl] diethyl aluminum are particularly suitable as components in coordination catalysts proven for the copolymerization of olefins.
- [2- (methoxy) benzyl] dibutylaluminum, [3 - (dimethylamino) propyl] dimethylaluminium and [2- (diethylaminomethyl) phen-1-yldiethylaluminum lead to an increased incorporation of propene in the polymer molecule in polymerization reactions.
- a corresponding effect is brought about in the copolymerization of ethene and hexene by [2- (diethylaminomethyl) phen-1-yljdiethylaluminium.
- the figures also show the thermal properties of the polymers in the form of melting or glass transition temperatures.
- the molar mass is also given in order to clarify that the polymer characteristics correspond to the technical requirements.
- the polymerizations were carried out semi-continuously in a 1-1-
- the reaction solution was then saturated first with propene and then with ethene.
- the polymerization was started by injecting the aluminum alkyl solution using a Hamilton syringe.
- Ethene was replenished during the reaction so that the total pressure remained constant during the reaction. Since the monomer composition of the batch changes continuously in the case of co- and terpolymerizations, the reactions were stopped so early that the conversion of the components not topped up did not exceed 5-10% in each case.
- the reaction was ended by destroying the catalyst by injecting 5 ml of ethanol, which was saturated with 2,6-di- tert- butyl-p-cresol to stabilize the double bonds in the polymer. The gaseous monomers were carefully released into the fume cupboard.
- the toluene-insoluble polymers were removed from the reactor and stirred overnight in about 300 ml of a washing solution consisting of demineralized water, ethanol and concentrated hydrochloric acid (7: 2: 1). It was then filtered and the polymers were washed neutral with a semi-saturated sodium hydrogen carbonate solution and then several times with demineralized water. The polymer was then dried to constant weight in an oil pump vacuum at 60 ° C.
- the toluene-soluble polymers were removed from the reactor and also stirred overnight with the wash solution mentioned above.
- the toluene phase was separated, neutralized with sodium hydrogen carbonate solution and washed three times with demineralized water.
- the toluene and any residues of liquid monomer were removed using a rotary evaporator. Finally, drying was also carried out here at 40-60 ° C in an oil pump vacuum.
- T p 60 ° C
- ethene / propene / ethylidene norbomen 0.3 / 0.6 / 0.1.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03785686A EP1572754A2 (de) | 2002-12-17 | 2003-11-28 | Verfahren zur herstellung von co- und terpolymeren aus olefinen |
JP2004559731A JP2006509866A (ja) | 2002-12-17 | 2003-11-28 | オレフィン類からのコポリマーおよびターポリマーの製造方法 |
US10/539,513 US20060149006A1 (en) | 2002-12-17 | 2003-11-28 | Method for producing copolymers and terpolymers from olefins |
AU2003294746A AU2003294746A1 (en) | 2002-12-17 | 2003-11-28 | Method for producing copolymers and terpolymers from olefins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10259243A DE10259243A1 (de) | 2002-12-17 | 2002-12-17 | Verfahren zur Herstellung von Co- und Terpolymeren aus Olefinen |
DE10259243.8 | 2002-12-17 |
Publications (2)
Publication Number | Publication Date |
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WO2004055064A2 true WO2004055064A2 (de) | 2004-07-01 |
WO2004055064A3 WO2004055064A3 (de) | 2004-11-25 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2003/013423 WO2004055064A2 (de) | 2002-12-17 | 2003-11-28 | Verfahren zur herstellung von co- und terpolymeren aus olefinen |
Country Status (6)
Country | Link |
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US (1) | US20060149006A1 (de) |
EP (1) | EP1572754A2 (de) |
JP (1) | JP2006509866A (de) |
AU (1) | AU2003294746A1 (de) |
DE (1) | DE10259243A1 (de) |
WO (1) | WO2004055064A2 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2946048A1 (fr) * | 2009-06-02 | 2010-12-03 | Michelin Soc Tech | Systeme catalytique pour la polymerisation de dienes conjugues,procede de polymerisation et polymere fonctionnel obtenu |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2946047B1 (fr) | 2009-06-02 | 2011-07-29 | Michelin Soc Tech | Nouveaux composes organometallique a base d'un metal appartenant a la 2eme colonne de la classification periodique et procede de preparation |
CN106883325B (zh) * | 2015-12-16 | 2019-05-07 | 中国石油天然气股份有限公司 | 乙丙橡胶聚合催化剂失活方法 |
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US4145313A (en) * | 1977-04-25 | 1979-03-20 | Exxon Research & Engineering Co. | Novel trialkyl aluminum cocatalyst |
EP0919557A1 (de) * | 1997-11-29 | 1999-06-02 | MERCK PATENT GmbH | Aluminiumalkylkomplexe als Cokatalysatoren |
EP1132409A1 (de) * | 2000-03-08 | 2001-09-12 | MERCK PATENT GmbH | Katalysatorsysteme für die Ziegler-Natta-Olefin-Polymerisation |
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NL294793A (de) * | 1962-07-05 | |||
US4224181A (en) * | 1979-03-07 | 1980-09-23 | Exxon Research & Engineering Co. | Ziegler type catalyst system |
JPH0618826B2 (ja) * | 1983-11-25 | 1994-03-16 | 宇部興産株式会社 | エチレンの重合法 |
JPH06104685B2 (ja) * | 1985-05-02 | 1994-12-21 | 株式会社トクヤマ | ポリオレフインの製造方法 |
FR2649708B1 (fr) * | 1989-07-17 | 1991-10-25 | Bp Chem Int Ltd | Procede de fabrication en phase gazeuse de copolymeres du propylene a l'aide d'un systeme catalytique de haute activite |
US4994534A (en) * | 1989-09-28 | 1991-02-19 | Union Carbide Chemicals And Plastics Company Inc. | Process for producing sticky polymers |
US5646098A (en) * | 1990-07-23 | 1997-07-08 | Exxon Chemical Patents Inc | Carbonyl containing compounds and their derivatives as multi-functional fuel and lube additives |
JP3198663B2 (ja) * | 1992-10-16 | 2001-08-13 | 宇部興産株式会社 | 超高分子量エラストマー状オレフィン系共重合体の製造方法 |
US5569516A (en) * | 1995-03-03 | 1996-10-29 | Union Carbide Chem Plastic | Membrane and mixture comprising a thermoplastic elastomer |
US6225426B1 (en) * | 1996-04-10 | 2001-05-01 | Uniroyal Chemical Company, Inc. | Process for producing polyolefin elastomer employing a metallocene catalyst |
-
2002
- 2002-12-17 DE DE10259243A patent/DE10259243A1/de not_active Withdrawn
-
2003
- 2003-11-28 US US10/539,513 patent/US20060149006A1/en not_active Abandoned
- 2003-11-28 JP JP2004559731A patent/JP2006509866A/ja active Pending
- 2003-11-28 AU AU2003294746A patent/AU2003294746A1/en not_active Abandoned
- 2003-11-28 WO PCT/EP2003/013423 patent/WO2004055064A2/de active Application Filing
- 2003-11-28 EP EP03785686A patent/EP1572754A2/de not_active Withdrawn
Patent Citations (3)
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US4145313A (en) * | 1977-04-25 | 1979-03-20 | Exxon Research & Engineering Co. | Novel trialkyl aluminum cocatalyst |
EP0919557A1 (de) * | 1997-11-29 | 1999-06-02 | MERCK PATENT GmbH | Aluminiumalkylkomplexe als Cokatalysatoren |
EP1132409A1 (de) * | 2000-03-08 | 2001-09-12 | MERCK PATENT GmbH | Katalysatorsysteme für die Ziegler-Natta-Olefin-Polymerisation |
Non-Patent Citations (1)
Title |
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DATABASE CHEMABS [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; "Polymerization of ethylene Polymerization of ethylene" XP002276321 gefunden im STN Database accession no. 1985:560996 & JP 60 112803 A (UBE INDUSTRIES, LTD., JAPAN UBE INDUSTRIES, LTD., JAPAN) 19. Juni 1985 (1985-06-19) * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2946048A1 (fr) * | 2009-06-02 | 2010-12-03 | Michelin Soc Tech | Systeme catalytique pour la polymerisation de dienes conjugues,procede de polymerisation et polymere fonctionnel obtenu |
WO2010139449A1 (fr) * | 2009-06-02 | 2010-12-09 | Societe De Technologie Michelin | Systeme catalytique pour la polymerisation de dienes conjugues, procede de polymerisation et polymere fonctionnel obtenu |
US9315590B2 (en) | 2009-06-02 | 2016-04-19 | Compagnie Generale Des Etablissements Michelin | Catalytic system for conjugated diene polymerisation, polymerisation method and functional polymer obtained |
Also Published As
Publication number | Publication date |
---|---|
DE10259243A1 (de) | 2004-07-01 |
US20060149006A1 (en) | 2006-07-06 |
JP2006509866A (ja) | 2006-03-23 |
AU2003294746A1 (en) | 2004-07-09 |
WO2004055064A3 (de) | 2004-11-25 |
EP1572754A2 (de) | 2005-09-14 |
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