EP1114073A1 - Reduction de la teneur en gel dans un procede de production de cis-1,4-polybutadiene eleve - Google Patents

Reduction de la teneur en gel dans un procede de production de cis-1,4-polybutadiene eleve

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Publication number
EP1114073A1
EP1114073A1 EP99941342A EP99941342A EP1114073A1 EP 1114073 A1 EP1114073 A1 EP 1114073A1 EP 99941342 A EP99941342 A EP 99941342A EP 99941342 A EP99941342 A EP 99941342A EP 1114073 A1 EP1114073 A1 EP 1114073A1
Authority
EP
European Patent Office
Prior art keywords
process defined
aluminum
compound
mixtures
group
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Withdrawn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
EP99941342A
Other languages
German (de)
English (en)
Inventor
Akhtar Osman
Florin Barsan
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 Inc
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 Inc, Bayer AG filed Critical Bayer Inc
Publication of EP1114073A1 publication Critical patent/EP1114073A1/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Withdrawn legal-status Critical Current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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers 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
    • C08F136/04—Homopolymers 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
    • C08F136/06—Butadiene
    • 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
    • C08F4/60—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 refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7095—Cobalt, nickel or compounds thereof
    • C08F4/7096—Cobalt or compounds thereof

Definitions

  • the present invention relates to an improved process for the production of poly butadiene having a high cis-1,4 content and a reduced gel content.
  • Processes for the production of polybutadiene having a high cis-1,4 content are well known.
  • Such processes include the polymerization of 1 ,3-butadiene in an inert polymerization diluent using as catalyst a mixture of a transition metal salt, such as a cobalt salt, an aluminum alkyl halide or a mixture aluminum alkyl halides and water.
  • a transition metal salt such as a cobalt salt
  • aluminum alkyl halide such as a cobalt salt
  • aluminum alkyl halide aluminum alkyl halides
  • water aluminum alkyl halides
  • same gel is produced, such gel being essentially insoluble particles containing cross-linked polybutadiene.
  • the gel is not a desirable component due to the problems it can cause to equipment used for the production of the polymer and due to the problems it can cause relating to the quality of the cis-l,4-polybutadiene.
  • United States patent 3,094,514 teaches a process for the production of a cis-l,4-polybutadiene, having a cis-l,4-content greater than 90 per cent.
  • the process comprises polymerization of 1,3 -butadiene in a hydrocarbon diluent in the presence as catalyst of an anhydrous dihalide diluent cobalt salt, a monoalkyl aluminum, and dialkyl aluminum monohalide.
  • anhydrous dihalide diluent cobalt salt a monoalkyl aluminum, and dialkyl aluminum monohalide.
  • United States patent 3,646,001 teaches that cis-1-4- polybutadiene may be produced by polymerizing 1,3-butadiene in the presence of cobalt octoate and diethyl aluminum chloride which have been reacted with benzene containing water.
  • United States patent 4,224,426 teaches the polymerization of 1,3-butadiene to produce cis-l,4-polybutadiene in the presence of a cobalt compound, at least one organo-aluminum chloride and water, the polymerization diluent being a mixture of C 5 -C 8 cycloalkane, a saturated aliphatic hydrocarbon or an -monoolefin, and an alkyl substituted benzene having 1 to 4 alkyl substituents.
  • United States patent 5,397,851 teaches a process for the production of a cis-l,4-poly butadiene by the polymerization of 1,3-butadiene in an inert hydrocarbon diluent in the presence as catalyst of a diluent cobalt salt, an alkyl aluminum chloride, a tri-alkyl aluminum compound and water.
  • An objective of this invention is a process for the production of a high cis-l,4-poly butadiene having a very low level of gel content.
  • the present invention provides a process for the production of cis-1 ,4-polybutadiene having a low level of gel content, the process comprising the step of polymerizing 1,3 butadiene in the presence of a catalyst and a polymerization diluent, the polymerization diluent comprising an organic solvent and water particles having a median particle size less than or equal to about 10 ⁇ m.
  • the present invention provides a process for the preparation of an essentially linear cis-1, 4-polybutadiene having a very low level of gel content, the process comprising polymerizing 1,3-butadiene in the presence of a cobalt salt-organo aluminum halide- water catalyst system, the improvement being that the polymerization is carried out in the presence as polymerization diluent of a mixture of a C 5 -C 6 cycloalkane and butene-1, a cobalt salt of an organic acid having 6 to 12 carbon atoms in the organic acid, an organo aluminum halide selected from (I) a mixture of (a) an alkyl aluminum chloride selected from diethyl aluminum chloride and ethyl aluminum sesqui chloride and (b) an organo aluminum or formula R 3 Al wherein R is an alkyl group having 8 to 12 carbon atoms and (II) an alkyl aluminum chloride wherein the alkyl group has 8 to 12 carbon atoms
  • the present inventor has discovered that controlling the median particle size of the water used in the diluent surprisingly and unexpectedly results in the production of high cis-1, 4-polybutadiene having a relatively low level of gel content.
  • the median diameter of the water particles used in the polymerization diluent is less than or equal to about 10 ⁇ m.
  • the water is present in said polymerization diluent as particles having a median particle size in the range of from about 0.5 ⁇ m to about 8 ⁇ m, more preferably from about 0.5 ⁇ m to about 6 ⁇ m, most preferably from about 1 ⁇ m to about 5 ⁇ m.
  • the median particle size of the water particles may be determined in a conventional manner, for example, using a Master sizerTM particle size measuring system commercially available from Malvern Instruments Inc.
  • the present process relates to the use of a polymerization diluent comprising an organic solvent and water particles.
  • the organic solvent is selected from the group comprising an aliphatic compound, an aromatic compound and mixtures thereof.
  • the aliphatic compound may be selected from a saturated hydrocarbon, an unsaturated hydrocarbon and mixtures thereof.
  • Preferred saturated hydrocarbons may be selected from the group comprising C 4 -C 10 aliphatic hydrocarbon, a C 5 -C 10 cyclic aliphatic hydrocarbon, a C 6 -C 9 aromatic hydrocarbon, a C 2 -C 10 monoolefinic hydrocarbon and mixtures thereof.
  • Non-limiting examples of a suitable C 4 -C, 0 aliphatic hydrocarbon may be selected from the group comprising butane, pentane, hexane, heptane, octane and mixtures thereof.
  • Non-limiting examples of a suitable C 2 -C 10 monoolefinic hydrocarbon may selected from the group comprising butene-1, pentene-1, hexene-1 and mixtures thereof.
  • Non-limiting examples of a suitable C 5 -C ]0 cyclic aliphatic hydrocarbon may be selected from the group comprising unsubstituted cycloalkanes, methyl substituted cycloalkanes, ethyl substituted cycloalkanes and mixtures thereof.
  • Non-limiting examples of a suitable C 5 -C 10 cyclic aliphatic hydrocarbon is selected from the group comprising cylcopentane, cyclohexane, cyclooctane and mixtures thereof.
  • Non-limiting examples of a suitable a C 6 -C 9 aromatic hydrocarbon may be selected from the group comprising benzene, toluene, xylene and mixtures thereof.
  • the most preferred organic solvent for use in the present process comprises a mixtures of cyclohexane and butene-1.
  • the polymerization diluent further comprises a polymerization modifier.
  • a polymerization modifier allows for controlling the molecular weight of the polymer product.
  • Illustrative examples of useful polymerization modifiers for use in the present process may selected from the group comprising C 2 -C lg non-conjugated dienes, C 6 -C 12 cyclic dienes and mixtures thereof.
  • Non-limiting examples of suitable polymerization modifiers may be selected from the group comprising 1,2-butadiene, 1 ,3- cyclooctadiene, 1,5-cyclooctadiene and mixtures thereof.
  • the amount of polymerization modifier may be from about 1.6 to about 3.5, preferably from about 1.95 to about 3.0, millimols per mole of 1,3-butadiene in the polymerization mixture.
  • the choice catalyst that is employed in butadiene polymerization art are well known.
  • the catalyst comprises a substantially anhydrous cobalt salt and an organo-aluminum halide compound.
  • the substantially anhydrous cobalt salt may comprise a compound having the formula CoA m , wherein A is selected from a monovalent anion and a divalent anion, and m is 1 or 2.
  • the anion is derived from a C 6 -C 12 organic acid.
  • non-limiting examples of usefully such anions may be selected from the group comprising an acetylacetonate, an acetate, a hexanoate, an octoate, an oxalate, a tartrate, a stearate, a sorbate, an adipate and a naphthenate.
  • the most preferred substantially anhydrous cobalt salt for use in the present process is cobalt octoate.
  • the organo-aluminum halide compound comprises a compound having the formula:
  • R is a C 2 -C 12 alkyl group
  • X is a halogen and p+q is 3.
  • the organo-aluminum halide compound is selected from the group comprising a dialkyl aluminum chloride compound, an alkyl aluminum sesquichoride compound and mixtures thereof.
  • the organo-aluminum halide compound is selected from:
  • Embodiment (I) is more preferred.
  • it is especially preferred to use the organo aluminum compound of formula R 3 A1 is present in an amount of 0 to 1 percent by weight of the mixture of (I) and (II).
  • the preferred organo aluminum compound of formula R 3 A1 comprises tri-octyl aluminum.
  • the preferred catalyst system for use in the present process comprises a cobalt salt selected from cobalt octoate and cobalt naphthenate, and an organo aluminum halide compound selected from: (i) a mixture of diethyl aluminum chloride and one or more of trioctyl aluminum, tridecyl aluminum and tridodecyl aluminum, and (ii) one or more of dioctyl aluminum chloride, didecyl aluminum chloride and didodecyl aluminum chloride.
  • a cobalt salt selected from cobalt octoate and cobalt naphthenate
  • an organo aluminum halide compound selected from: (i) a mixture of diethyl aluminum chloride and one or more of trioctyl aluminum, tridecyl aluminum and tridodecyl aluminum, and (ii) one or more of dioctyl aluminum chloride, didecyl aluminum chloride and didodecyl aluminum chloride.
  • the weight ratio of butene-1 in the cyclohexane-butene-1 mixture may be from about 24 to about 40, preferably from about 24 to about 38 and most preferably from about 34 to about 36, weight percent.
  • a preferred catalyst cobalt octoate which is used with a preferred organo aluminum halide compound which is a mixture of diethyl aluminum chloride and trioctyl aluminum, wherein the molar ratio of cobalt octoate to the total of the diethyl aluminum chloride plus trioctyl aluminum is from about 1: 15 to about 1:30, preferably from about 1: 15 to about 1 :20 and wherein the molar ratio of chlorine in the diethyl aluminum chloride to the total aluminum in the diethyl aluminum chloride plus trioctyl aluminum is from about 0.7: 1 to about 0.95: 1, preferably from about 0.8: 1 to about 0.9: 1.
  • the amount of 1,3-butadiene in the 1.3-butadiene plus diluent mixture may be from about 15 to about 35, preferably from about 25 to about 35, weight percent.
  • the polymerization mixture also contains water.
  • the amount of water is from about 0.3 to about 0.8, preferably from about 0.5 to about 0.65, millimols per millimol of the alkyl aluminum chloride used.
  • the water is mixed with at least a portion of the polymerization diluent. Accordingly, in the preferred diluent comprising cycloalkane and butene-1, the water may be mixed with cycloalkane alone, or, preferably with cycloalkane and butene-1 mixture.
  • the mixing of the water with the polymerization diluent is such that the water as present in the polymerization diluent as particles having a median particle size equal to or less than 10 ⁇ m. Because of the very low solubility of water in hydrocarbons, including the polymerization diluents, and because of the long time to achieve a solution of water in such hydrocarbons, it is desirable for the present polymerization system to disperse the water in the polymerization diluent as very small particles to provide as high as possible a surface area to weight ratio for the particles so that interaction with the aluminum compound(s) is as efficiently as possible - this is believed to be important in reducing the amount of gel in the polybutadiene produced.
  • the dispersion of water in the polymerization diluent may be achieved by various means such as, but not limited to, mechanical methods and sonic treatment.
  • the improvement of the present invention is not dependent on the method used to obtain the dispersion of water in the polymerization diluent and is only dependent on the median diameter of the water particles used in the polymerization diluent being less than or equal to about 10 ⁇ m.
  • the water is present in said polymerization diluent as particles having a median particle size in the range of from about 0.5 ⁇ m to about 8 ⁇ m, more preferably from about 0.5 ⁇ m to about 6 ⁇ m, most preferably from about 1 ⁇ m to about 5 ⁇ m.
  • the polymerization may be undertaken at a temperature of from about -10°C to abut 50°C, preferably from about 5°C to about 40°C and most preferably from about 15 °C to about 35 °C.
  • the polymerization process may be carried out in a batch process or in a continuous process, the continuous process being preferred.
  • the reaction time for the polymer ization may be from about 20 to about 90 minutes, preferably from about 25 to about 60 minutes. However, the reaction time is not a critical aspect of the process and may be affected by the desired conversion of the 1,3-butadiene to polymer which may range from about 40 to about 90 percent.
  • the gel content of the polymer may be determined by a method in which the gel is separated from a solution of the polymer in styrene and weighed. In detail, approximately 50 g of polymer, accurately weighed, is dissolved in pure, filtered styrene to produce an approximately 4 weight percent by volume solution. The polymer-styrene mixture is shaken for 4 to 5 hours, then allowed to stand for 10 minutes and then filtered through a previously weighed filtration screen of 400 mesh. The filtration screen is then weighed again and the amount of wet gel is calculated as parts per million by weight based on the original weight of polymer used. Gel contents of less than about 250 ppm are desirable and less than about 150 ppm are more desirable and less than about 100 ppm are most desirable. In order to provide the greatest accuracy to the gel content of the polymer, normally at least three and up to 5 samples of the polymer are used to provide the corresponding number of gel content measurements. In the following examples, the 1,3-butadiene was obtained from
  • Cobalt octoate was obtained from Mooney Chemical Inc. and used as a 6% cobalt solution in cyclohexane. Diethyl aluminum chloride was mixed with trioctyl aluminum in sealed bottles under an inert gas in such ratios as to provide a solution having an average composition of Et, 8 Oct 03 Al j Cl 09 in cyclohexane which was used in all examples and is referred to as M-DEAC. Polymerization was undertaken in sealed 1 litre polymerization bottles at a temperature of 27 °C for 40 minutes at the end of which time the polymerization was stopped by the injection of 5 ml of ethanol containing required amount of stabilizer and the polymer was recovered by steam coagulation.
  • Example 2 Using the procedure and components described in Example 1 , polymerizations were undertaken in which the cyclohexane, 1,3-butadiene, butene-1, water and M-DEAC were mixed by shaking for a period ranging from 0 to 30 minutes. The other components were added on completion of the shaking.
  • the gel results shown in Table 2 show that when the median particle size is reduced less than 10 ⁇ m, the gel content of the polymer is significantly reduced.
  • Example 2 Using the procedure described in Example 1 , the following experiments were undertaken. 110 g of cyclohexane and 0.011 mL of water was subjected to sonification for 5 minutes producing a mixture containing particles of water having a median particle size of less than 10 ⁇ m.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur un procédé de production de cis-1,4-polybutadiène ayant une faible teneur en gel. Ce procédé consiste à polymériser 1,3 butadiène en présence d'un catalyseur et d'un diluant de polymérisation. Le diluant de polymérisation comprend un solvant organique et des particules d'eau dont la taille moyenne est inférieure ou égale à environ 10νm. En régulant la taille moyenne des particules de l'eau présente dans le diluant, la teneur en gel du produit polymère peut être réduite.
EP99941342A 1998-09-04 1999-09-03 Reduction de la teneur en gel dans un procede de production de cis-1,4-polybutadiene eleve Withdrawn EP1114073A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CA002246608A CA2246608A1 (fr) 1998-09-04 1998-09-04 Reduction du contenu en gel dans le procede de production de cis-1,4 polybutadiene de haute masse moleculaire
CA2246608 1998-09-04
PCT/CA1999/000804 WO2000014130A1 (fr) 1998-09-04 1999-09-03 Reduction de la teneur en gel dans un procede de production de cis-1,4-polybutadiene eleve

Publications (1)

Publication Number Publication Date
EP1114073A1 true EP1114073A1 (fr) 2001-07-11

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Application Number Title Priority Date Filing Date
EP99941342A Withdrawn EP1114073A1 (fr) 1998-09-04 1999-09-03 Reduction de la teneur en gel dans un procede de production de cis-1,4-polybutadiene eleve

Country Status (6)

Country Link
EP (1) EP1114073A1 (fr)
JP (1) JP2002524587A (fr)
KR (1) KR20010085758A (fr)
AU (1) AU5500199A (fr)
CA (1) CA2246608A1 (fr)
WO (1) WO2000014130A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0114663A (pt) 2000-10-12 2004-01-13 Dow Global Technologies Inc Sistema catalisador para polibutadieno de alto teor de cis
TW201129594A (en) 2009-12-02 2011-09-01 Styron Europe Gmbh Catalyst systems for rubber polymerizations
EP2523978A2 (fr) * 2010-01-15 2012-11-21 Reliance Industries Limited Caoutchouc de polybutadiène à teneur élevée en composés cis dans des solvants faibles et procédé pour le préparer
JP5873709B2 (ja) 2011-08-22 2016-03-01 株式会社日本自動車部品総合研究所 高周波プラズマ生成システム及びこれを用いた高周波プラズマ点火装置。
CN112844284B (zh) * 2020-12-29 2022-07-15 烟台联利化工有限公司 一种氯化二乙基铝矿物油的制备设备及生产工艺

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4730071A (en) * 1986-08-15 1988-03-08 Shell Oil Company Process for preparing aluminoxanes
JP3073509B2 (ja) * 1990-07-26 2000-08-07 日本ゼオン株式会社 シス１，４―ポリブタジエンの製造方法
US5397851A (en) * 1993-11-09 1995-03-14 Polysar Rubber Corporation Process for cis-1,4-polybutadiene production with reduced gel formation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0014130A1 *

Also Published As

Publication number Publication date
CA2246608A1 (fr) 2000-03-04
KR20010085758A (ko) 2001-09-07
JP2002524587A (ja) 2002-08-06
WO2000014130A1 (fr) 2000-03-16
AU5500199A (en) 2000-03-27

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