EP1056791A1 - Procede de fabrication de polydienes a viscosite mooney reglee - Google Patents

Procede de fabrication de polydienes a viscosite mooney reglee

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Publication number
EP1056791A1
EP1056791A1 EP99908857A EP99908857A EP1056791A1 EP 1056791 A1 EP1056791 A1 EP 1056791A1 EP 99908857 A EP99908857 A EP 99908857A EP 99908857 A EP99908857 A EP 99908857A EP 1056791 A1 EP1056791 A1 EP 1056791A1
Authority
EP
European Patent Office
Prior art keywords
iii
neodymium
chloride
lanthanum
praseodymium
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Withdrawn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
EP99908857A
Other languages
German (de)
English (en)
Inventor
Gerd Sylvester
Günter MARWEDE
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
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 Bayer AG filed Critical Bayer AG
Publication of EP1056791A1 publication Critical patent/EP1056791A1/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Withdrawn legal-status Critical Current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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/903—Monomer polymerized in presence of transition metal containing catalyst and hydrocarbon additive affecting polymer properties of catalyst activity

Definitions

  • the invention relates to a process for the preparation of polydienes with a controlled Mooney viscosity in the presence of rare earth metal catalysts and in the presence of special molecular weight regulators.
  • the polydienes produced in this way are used in particular in the manufacture of car tires.
  • Catalyst based on rare earth compounds are polymerized.
  • EP 0 736 549 discloses a process for the preparation of diene rubbers in the gas phase, in which the dienes or
  • the present invention therefore relates to a method for producing
  • Polydienes with controlled Mooney viscosity by means of catalysts based on rare earth compounds which is characterized in that the conjugated dienes used in the presence of 0.005 to 80 wt .-% of 1,2-dienes, based on the sum of conjugated dienes used and 1, 2-dienes used, polymerized.
  • conjugated dienes which can be used in the gas phase process according to the invention are 1,3 butadiene, isoprene, pentadiene and / or dimethyl butadiene, especially 1,3-butadiene and isoprene.
  • other monomers such as e.g. Ethylene, propylene, butene, isobutylene, methylpentene, norbornene, cyclopentadiene, cyclohexene, styrene or chloroprene.
  • the amount of these monomers used can vary within wide limits. In general, the amount of additional monomers used is 0.01 to 200% by weight, based on the conjugated diene used, preferably 0.1 to 20% by weight.
  • the 1, 2-dienes used to control the Mooney viscosities are used in amounts of 0.005 to 80, preferably 0.01 to 30, and very particularly preferably 0.05 to 10% by weight, based on the total of the conjugates used Diene and the 1, 2-diene used.
  • the amount of use of the regulator according to the invention depends on various factors, for example on the amount of catalysts used, the type of monomers used, the proportion of monomers in the reaction mixture, the reaction temperature and the pressure. Appropriate preliminary tests make it easy to determine the most suitable amount of regulator for the desired Mooney viscosity of the polymer.
  • Suitable dienes are, in particular, those with boiling points below 140 ° C., preferably below 80 ° C., such as allen, 1, 2-butadiene, 1, 2-pentadiene, 1-vinylcyclopentene, 1-vinylcyclohexene and Vinyl acetylene, or mixtures containing such 1,2-dienes.
  • the amounts of 1,2-dienes to be used previously are mean values, i.e. Quantities that apply to the entire course of the reaction. This means, for example, that the regulator according to the invention can be metered in completely, continuously during the entire course of the polymerization or intermittently at the beginning of the polymerization reaction.
  • the process according to the invention is usually carried out at temperatures from -20 ° C. to 250 ° C., preferably 20 to 160 ° C., particularly preferably 50 to 120 ° C., and at pressures from 1 mbar to 50 bar, preferably at 0.5 to 30 bar , particularly preferably carried out at 1 to 20 bar.
  • the rare earth metal catalysts to be used for the process according to the invention consist, for example, of: A) an alcoholate of the rare earths (I), a carboxylate of the rare earths (II), a complex compound of the rare earths with diketones (III) and / or an addition compound of the halides of the rare earths with an oxygen or nitrogen donor compound (IV ) of the following formulas:
  • M is a trivalent element of the rare earths with the atomic numbers
  • R is identical or different and denotes alkyl radicals with 1 to 10 carbon atoms
  • X represents chlorine, bromine or iodine
  • y 1 to 6
  • n 1 to 50, C) a further Lewis acid and
  • M is a trivalent element of the rare earths with the atomic numbers 21, 39 or 57 to 71 identified in the periodic table.
  • Preferred compounds are those in which M is lanthanum, cerium, praseodymium or neodymium or a mixture of rare earth elements, which contains at least one of the elements lanthanum, cerium, praseodymium or neodymium to at least 10% by weight
  • % contains means.
  • Compounds in which M is lanthanum or neodymium or a mixture of rare earths which contain at least 30% by weight of lanthanum or neodymium are very particularly preferred.
  • radicals R in the formulas (I) - (IV) are in particular straight-chain or branched
  • component A e.g. called: neodymium (III) -n-propanolate
  • Suitable carboxylates of component A are: lanthanum (III) propionate, lanthanum
  • lanthanum (III) acetyl acetonate lanthanum (III) acetyl acetonate, praseodymium (III) acetylacetonate, neodymium (III) acetylacetonate, are preferred
  • Neodymium (III) acetylacetonate Neodymium (III) acetylacetonate.
  • Examples of addition compounds of component A with donors are: lanthanum (III) chloride with tributyl phosphate, lanthanum (III) chloride with tetrahydrofuran, lanthanum (HI) chloride with isopropanol, lanthanum (III) chloride with
  • the rare earth compounds can be used individually or as a mixture with one another.
  • Neodymium versatate, neodymium octanoate, the addition compound of neodymium chloride with tributyl phosphate and / or neodymnaphthenate are very particularly preferably used as component A.
  • R denotes a straight-chain or branched alkyl radical having 1 to 10 C atoms, preferably 1 to 4 C atoms.
  • suitable aluminum alkyls of the formulas (V) and (VI) are:
  • alumoxanes are: methylalumoxane, ethylalumoxane and isobutylalumoxane, preferably methylalumoxane and isobutylalumoxane.
  • Lewis acids are used as component C.
  • 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 e.g. Triethyl aluminum with bromine or triethyl aluminum with butyl chloride can be used.
  • 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 omitted if component B contains a compound of formula VII or if component A is used of compound IV. - 9 -
  • the specific surface area (BET) is determined in the usual way according to S.
  • the pore volume is determined by the centrifugation method according to M. McDaniel, J. Colloid Interface Sei. 78: 31 (1980).
  • Particularly suitable inert solids are silica gels, precipitated silicas, clays,
  • inert is understood to mean that the solids neither have a reactive surface nor contain adsorbed material which prevent the formation of an active catalyst or react with the monomers.
  • inert inorganic solids mentioned which meet the above-mentioned specification and are therefore suitable for use, are described in more detail, for example, in Ullmanns, Enzyclopadie der Technische Chemie, volume 21, page 439 ff. (Silica gel), volume 23, page 311 ff. (Tone), volume 14, p. 633 ff. (soot), volume 24, p. 575 ff. and volume 17, p. 9 ff. (zeolites).
  • the inorganic solids can be used individually or in a mixture with one another.
  • the molar ratio in which the catalyst components A to D are used can be varied within wide limits. - 10 -
  • the molar ratio of component A to component B is usually 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 is 1: 0.4 to 1:15, preferably 1: 0.5 to 1: 8.
  • component D 0.1 mmol to 1 mol of component A, preferably 1 to 50 mmol of component A, are used per 100 g of component D.
  • Component E is a conjugated diene, which can be the same diene that will later be polymerized with the catalyst. Butadiene and isoprene are preferably used.
  • the amount of E is preferably 1-1000 mol, based on 1 mol of component A, particularly preferably 1-
  • the amount of the catalyst to be used is usually 0.01 to 10, in particular 0.1 to 5,% by weight, based on the monomers used.
  • the cheapest amount can be easily determined by means of appropriate preliminary tests.
  • the process according to the invention can be carried out either continuously or batchwise in the customary reactors suitable for this. - 11 -
  • the process according to the invention is preferably carried out in the gas phase.
  • the regulator according to the invention can be added continuously or intermittently, for example at the start of the reaction or during the reaction.
  • Suitable reactors are e.g. Stirred reactors, rotating reactors, stirred / rotating reactors, mixing nozzle reactors, fluidized bed or fluidized bed reactors.
  • the regulators according to the invention can optionally be used together with inert diluents, such as alkanes, e.g. Methane, ethane, propane, butane and / or pentane, or with nitrogen or argon. They can also be absorbed into solids in solid form and fed into the reaction space. As solids e.g. the same substances are suitable that can be used as catalyst supports. The amount of inert diluent or diluent mixture can also be easily determined by appropriate preliminary tests.
  • inert diluents such as alkanes, e.g. Methane, ethane, propane, butane and / or pentane, or with nitrogen or argon. They can also be absorbed into solids in solid form and fed into the reaction space. As solids e.g. the same substances are suitable that can be used as catalyst supports. The amount of inert diluent or diluent mixture can also be easily determined by appropriate
  • flow agents or powdering agents can be introduced into the reaction space.
  • the polydienes obtained by the process according to the invention have a high 1,4-cis content (approx. 60 to 99.9%) and are predominantly in free-flowing, non-bonded form.
  • the average particle diameter of the polymers can be up to several centimeters.
  • the average particle diameter is preferably 0.05 to 1.5 cm.
  • the polydienes obtained have average Mooney values (ML 1 + 4 ', 100 ° C.) of 30 to 180 ME, preferably 50 to 70 ME. - 12 -
  • the polymers obtained according to the invention can be stabilized, compounded and vulcanized in a known manner. They are mainly used to build car tires.
  • Zeosil 1165 MP was used as the carrier.
  • Zeosil 1165 MP is a precipitated silica from Rhone Poulenc with an average particle size of 252 ⁇ m and a BET surface area of 139 m 2 / g. The pore volume is 1.97 ml / g.
  • the Zeosil 1165 MP was dried at 900 ° C in a nitrogen countercurrent and filled with the exclusion of air and moisture.
  • a catalyst was prepared by using 120 ml of dry n-hexane in a 1 liter flask equipped with a ⁇ feed and a magnetic stirrer.
  • DIB AH diisobutyl aluminum hydride
  • EASC ethyl aluminum sesquichloride
  • the polymerization was carried out in a rotary evaporator equipped with a magnetic stir bar, a mercury pressure relief valve and connections to a vacuum pump and to the supply with gaseous nitrogen and
  • Butadiene and a thermocouple reaching almost to the bottom of the 1 1 flask was carried out.
  • the inclination of the rotary evaporator was adjusted so that the axis of rotation formed an angle of 45 ° with that of the bar magnet.
  • the total volume of the apparatus was 2 liters.
  • the apparatus was via an adjustable valve with one on one
  • the apparatus was heated with a hot air blower, the temperature of which was adjustable, so that a temperature of 60 ° C. was maintained in the bed.
  • the reaction was terminated after 6 hours.
  • the yield was 154.1 g.
  • the polymer was stopped and stabilized with 1g Vulkanox BKF from Bayer AG, dissolved in 200ml acetone. The excess acetone was removed in vacuo.
  • the Mooney viscosity was 50 ME. Content of cis-l, 4 double bonds: 96.5% - 15 -
  • the polymerization was carried out in the same manner as in Example 1. 9.3 g of the catalyst described under lb) and 14.9 g of the eluent described under lc) were used. The polymerization was carried out at 60 ° C. with a mixture which had been prepared from 3 g of 1,2-butadiene and 298 g of 1,3-butadiene. The polymerization was terminated after 4 hours. The yield was 138.9 g. The polymer was stabilized with 0.6 g Vulkanox BKF. The Mooney viscosity was 19 ME.
  • the polymerization was carried out in the same manner as in Example 1. 10.6 g of the catalyst described under lb) and 10.6 g of the eluent described under lc) were used. The polymerization was carried out at 90 ° C. using a mixture which had been prepared from 0.75 g of 1,2-butadiene and 299 g of 1,3-butadiene. The polymerization was stopped after 3.5 hours. The yield was 185 g. The polymer was stabilized with 0.9 g Vulkanox BKF. The Mooney viscosity was 21 ME.
  • the polymerization was carried out in the same manner as in Example 1. 9.5 g of the catalyst described under lb) and 8.7 g of the eluent described under lc) were used. The polymerization was carried out without the addition of 1,2-butadiene only with 1,3-butadiene at 60 ° C. The polymerization was terminated after 4 hours. The yield was 380 g. The polymer was stabilized with 2 g Vulkanox BKF. The Mooney viscosity was 1 1 1 ME.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerization Catalysts (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de fabrication de polydiènes à viscosité Mooney réglée, avec utilisation de catalyseurs à base de composés des terres rares, caractérisé en ce qu'on polymérise les diènes conjugués introduits en présence de 0,005 à 80 % en poids de 1,2-diènes, par rapport à la somme des diènes conjugués introduits et des 1,2-diènes introduits. Les polydiènes ainsi obtenus sont utilisés notamment pour la fabrication de pneumatiques.
EP99908857A 1998-02-19 1999-02-06 Procede de fabrication de polydienes a viscosite mooney reglee Withdrawn EP1056791A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19806931A DE19806931A1 (de) 1998-02-19 1998-02-19 Verfahren zur Herstellung von Polydienen mit geregelter Mooney-Viskosität
DE19806931 1998-02-19
PCT/EP1999/000803 WO1999042503A1 (fr) 1998-02-19 1999-02-06 Procede de fabrication de polydienes a viscosite mooney reglee

Publications (1)

Publication Number Publication Date
EP1056791A1 true EP1056791A1 (fr) 2000-12-06

Family

ID=7858273

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99908857A Withdrawn EP1056791A1 (fr) 1998-02-19 1999-02-06 Procede de fabrication de polydienes a viscosite mooney reglee

Country Status (7)

Country Link
US (1) US6344527B1 (fr)
EP (1) EP1056791A1 (fr)
JP (1) JP2002504574A (fr)
AU (1) AU2832199A (fr)
CA (1) CA2320886A1 (fr)
DE (1) DE19806931A1 (fr)
WO (1) WO1999042503A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA02009287A (es) * 2000-03-24 2003-05-23 Bayer Ag Procedimiento para la polimerizacion de diolefinas conjugadas (dienos) con catalizadores de tierras raras en presencia de disolvente vinilaromatico.
US8816032B1 (en) * 2013-05-24 2014-08-26 The Goodyear Tire & Rubber Company Copolymer of conjugated diene and 1-vinylcycloalkene

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU37959A1 (fr) * 1958-11-26
US3297667A (en) * 1963-02-28 1967-01-10 Union Carbide Corp Production of cis-1, 4-polydienes by polymerization of 1, 3-dienes
US4663405A (en) * 1986-04-16 1987-05-05 The Goodyear Tire & Rubber Company Molecular weight modifier for use with lanthanide and actinide catalysts
DE4334045A1 (de) 1993-10-06 1995-04-13 Bayer Ag Katalysator, dessen Herstellung und Verwendung zur Gasphasenpolymerisation von konjugierten Dienen
US5428119A (en) * 1993-11-09 1995-06-27 Polysar Rubber Corporation Process for polybutadiene production using catalyst with high activity
US5914377A (en) 1995-04-04 1999-06-22 Bayer Ag Method for the production of diene rubbers in the gas phase
US6001478A (en) * 1997-08-08 1999-12-14 Union Carbide Chemicals & Plastics Technology Corporation Resin particle produced by diene polymerization with rare earth and transition metal catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9942503A1 *

Also Published As

Publication number Publication date
US6344527B1 (en) 2002-02-05
WO1999042503A1 (fr) 1999-08-26
JP2002504574A (ja) 2002-02-12
CA2320886A1 (fr) 1999-08-26
AU2832199A (en) 1999-09-06
DE19806931A1 (de) 1999-08-26

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