EP1032603A1 - Composants de catalyseur destines a la polymerisation de dienes, catalyseur ainsi obtenu, et procede de preparation de polydienes a l'aide de celui-ci - Google Patents

Composants de catalyseur destines a la polymerisation de dienes, catalyseur ainsi obtenu, et procede de preparation de polydienes a l'aide de celui-ci

Info

Publication number
EP1032603A1
EP1032603A1 EP99948809A EP99948809A EP1032603A1 EP 1032603 A1 EP1032603 A1 EP 1032603A1 EP 99948809 A EP99948809 A EP 99948809A EP 99948809 A EP99948809 A EP 99948809A EP 1032603 A1 EP1032603 A1 EP 1032603A1
Authority
EP
European Patent Office
Prior art keywords
iii
catalyst component
solid catalyst
component according
compound
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Withdrawn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
EP99948809A
Other languages
German (de)
English (en)
Inventor
Maurizio Galimberti
Ofelia Fusco
Giuseppe Gioia
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.)
Basell Polyolefine GmbH
Original Assignee
Montell Technology Co BV
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 Montell Technology Co BV filed Critical Montell Technology Co BV
Priority to EP99948809A priority Critical patent/EP1032603A1/fr
Publication of EP1032603A1 publication Critical patent/EP1032603A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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

Definitions

  • the cobalt compound can be any organic compound such as the cobalt salts of organic acids, cobalt complexes and the like.
  • the cobalt compound is selected from the group consisting of cobalt ⁇ -ketone complexes, for example, cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; cobalt ⁇ -ketoacid ester complexes, for example, cobalt acetylacetonate ethylester complexes; cobalt salts of organic carboxylic acids having 6 or more carbon atoms, for example, cobalt octoate, cobalt naphthenate, and cobalt benzoate; and cobalt halide complexes, for example, cobalt chloride-pyridine complexes; cobalt chloride-ethyl alcohol complexes and cobalt complexes coordinated with butadiene, for example, (1,3 -butadiene) [1- (2-
  • cobalt sorbate cobalt adipate, cobalt 2-ethylhexoate, cobalt stearate, and the like compounds wherein the organic portion of the molecule contains about 5 to 20, preferably 8 to 18 carbon atoms and one or two carboxylic functions, as well as acetylacetonate.
  • the rare earth metal compounds can be selected from the group consisting of : an alcholate of formula (RO) 3 M (I); a carboxylate of formula (RCO 2 ) 3 M (II); a complex compound of the rare earth with diketones and/or an addition compound of the halides of the rare earth with an oxygen or nitrogen donor compound corresponding to the following formulae:
  • M is a trivalent element of the rare earth with atomic numbers of 57 to 71; R groups may be the same or different and represent hydrocarbon radicals containing 1 to 20 carbon atoms; L is chlorine, bromine or iodine; and y is from 1 to 6.
  • Preferred compounds are those in which M is lanthanum, cerium, praseodymium, gadolinium or neodymium or a mixture of elements of the rare earth which contains at least 10% by weight of at least one of the elements lanthanum, cerium, praseodymium or neodymium.
  • Compounds in which M is lanthanum or neodymium or a mixture of rare earth containing at least 30% by weight of lanthanum or neodymium are most preferred.
  • porous polymer can also be in a prepolymerized form that is as a polymer obtained by low conversion polymerization using the catalysts disclosed above.
  • the prepolymer is generally produced in a quantity ranging from 0.5 g per g of solid catalyst component to 2000 g/g. Preferably, however, the amount is between 5 and 500 g per g of solid component and more preferably between 10 and 100 g per g of solid component.
  • the porosity (measured by the mercury method) is higher than 0.02 cmVg and preferably in the range of from 0.04 to 1.4 cm 3 /g, more preferably of from 0.04 to 1.2 cmVg measured by the mercury method described below.
  • a porous prepolymer when a porous prepolymer is used its porosity is preferably from 0.3 to 1.2 cmVg, while when a porous polymer is used its porosity is preferably from 0.04 to 0.3.
  • the porous polymer used in the present invention is further characterized by a porosity, expressed as void percentage, of higher than 10% preferably higher than 15%.
  • the porous polymer is also preferably endowed with a spherical form that is obtainable for example by using the catalyst components mentioned above.
  • the metal compound is first converted into a final active catalyst by suitable reaction with the co-catalyst and then the whole system is supported on the porous polymer. Therefore, this process of supportation specifically comprises:
  • the supportation process can be carried out conveniently in a gas-phase loop reactor in which a stream of inert gas keeps the porous polymer moving.
  • the metal compound optionally dissolved in hydrocarbon solvent, is fed successively, for example using a sprayer, to the gas-phase loop reactor and a smooth-flowing product is obtained at the end of the treatment.
  • the active catalysts usable in the polymerization of dienes are formed upon reaction of the metal components with the suitable cocatalyst compounds.
  • R 7 substituents are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C,-C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl and C 7 -C 20 arylalkyl radicals, optionally containing Si or Ge atoms, or R 7 is a group -O-Al(R 7 ) 2 .
  • linear alumoxanes have formula:
  • n is an integer ranging from 0 to 40 and R 7 has the meaning reported above; and cyclic alumoxanes have formula:
  • m is an integer ranging from 2 to 40 and R 7 has the meaning reported above.
  • R 7 is preferably methyl, ethyl, isobutyl or 2,4,4-trimethyl-pentyl.
  • Suitable activating cocatalysts in the catalyst systems of the invention are also the products of the reaction between water and an organometallic aluminum compound, preferably of formula A1R 7 3 or Al 2 R 7 6 , wherein R 7 has the meaning reported above.
  • organometallic aluminum compounds described in EP 0 575 875 (formula (II)) and those described in WO 96/02580 (formula (II)).
  • Suitable activating cocatalysts can also be the compounds of formula Y + Z " , wherein Y + is a Br ⁇ nsted acid, able to donate a proton and to react irreversibly with a substituent X of the metal compound, and Z " is a compatible non- coordinating anion, able to stabilize the active catalytic species which results from the reaction of the two compounds and which is sufficiently labile to be displaceable by an olefin substrate.
  • the anion Z " consists of one or more boron atoms.
  • the cocatalyst is preferably selected from triethylaluminum (TEAL), tris(isobutyl)aluminum (TIBAL) diethylaluminum chloride (DEAC), MAO and mixtures thereof. Furthermore, also promoters, including hydrogen fluoride, boron trifluoride and their etherate derivatives, are preferably used.
  • Both the Al/Nd and the Cl/Nd molar ratios of the catalyst are somewhat critical for the polymerization activity.
  • the Al/Nd molar ratio is higher than 10 and more preferably is between 15 and 70.
  • the Cl/Nd molar ratio is preferably higher than 2 and in particular comprised between 2.5 and 5.
  • the catalyst is prepared by first adding the chlorinating agent to the hydrocarbon solution of the Nd carboxylate and then reacting the so obtained slurry mixture with the alkylating agent. In developing this procedure it has been found particularly advantageous, for the increase of the activity, contacting the first mixture with small amounts of the dieninc monomer before adding the alkylating agent.
  • the alkylating agent is firstly added to the hydrocarbon solution of the Nd carboxylate.
  • the so obtained mixture is then aged for a time longer than 4 hours thereby obtaining a homogeneous mixture which is then added with the halogenating agent.
  • This technique allows to obtain a final catalyst system which is completely soluble in the hydrocarbon medium and that is particularly suitable for the supportation on the porous polymer.
  • the time span of the aging of the first mixture is preferably about 1 day in particular when carboxylates with at least 10 carbon atoms are used.
  • longer aging times in particular from about 2 to 10 days are preferred.
  • the use of longer aging times of the first mixture generates a final catalyst system solution capable to remain clear for times longer than 5 days.
  • the aging of the final catalyst solution is beneficial for the activity.
  • aging times form about 2 to 4 days are especially preferred.
  • the hydrocarbon medium used for the preparation of the catalyst system is generally selected form the group consisting of saturated hydrocarbons like propane, butane, pentane, hexane, heptane or aromatic hydrocarbons such as toluene and benzene.
  • this catalyst system is particularly suited for the preparation of polydienes by polymerization processes carried out in gas-phase.
  • the gas-phase process can be carried out in a fluidized bed reactor or under conditions in which the polymer is mechanically stirred, and operating in one or more reactors.
  • the polymerization temperature is generally comprised between -10 and 250°C, preferably between 10 and 160°C.
  • the pressure is generally comprised between 0.1 and 50 bar and preferably between 1 and 20 bar.
  • the molecular weight of the resulting polymers can be regulated by using molecular weight regulator agents, or by using the polymerization conditions.
  • the molecular weight can be adjusted through the composition of the catalyst and by varying the polymerization conditions. Typical molecular weights are in the range from 10 3 to 10 6 , as measured by GPC (gel permeation chromatography).
  • the Mooney viscosity, ML (1+4', 100°C), is typically in the range from 30 to 180 MU. It is also possible by the gas-phase polymerization to produce polymers of very high molecular weight that would be extremely difficult to obtain by solution polymerization because of the high viscosity and the possibility of transfer reactions through the solvent used.
  • the polymer obtained may be compounded and vulcanized in the usual way.
  • the porosity is determined by absorption of mercury under pressure. For this determination use is made of a calibrated dilatometer (diameter 3 mm) CD 3 (Carlo Erba) connected to a reservoir of mercury and to a high-vacuum pump (1#10 "2 mba). A weighed amount of sample is placed in the dilatometer. The apparatus is then placed under high vacuum ( ⁇ 0.1 mm Hg) and is maintained in these conditions for 10 minutes. The dilatometer is then connected to the mercury reservoir and the mercury is allowed to flow slowly into it until it reaches the level marked on the dilatometer at a height of 10 cm.
  • the valve that connects the dilatometer to the vacuum pump is closed and then the mercury pressure is gradually increased with nitrogen up to 140 kg/cm 2 . Under the effect of the pressure, the mercury enters the pores and the level goes down according to the porosity of the material.
  • the porosity (cm 3 /g), and the distribution of pores is directly calculated from the integral pore distribution curve which is function of the volume reduction of the mercury and applied pressure values (all these data are provided and elaborated by the porosimeter associated computer which is equipped with a "MILESTONE 200/2.04" program by C. Erba.
  • the porosity expressed as percentage of voids is calculated from the following formula:
  • V is the volume of the pores and V, is the apparent volume of the sample.
  • V is the volume of the pores and V, is the apparent volume of the sample.
  • the value of V is directly provided by the instrument that calculates it on the basis of the difference between the initial and final level of the mercury in the.
  • the apparent volume of the sample is given by:
  • Neodimium versatate (1.65 ml of a 0.317 M solution in hexane)
  • isoprene 15 mmoles of DIBAH (10 mL of a 1.5 M solution in toluene)
  • EASC 2.5 ml of a 0.121 M solution in hexane
  • the solution was stirred for 5 minutes and was then cannulated under nitrogen into the flask and homogeneously distributed on the solid support.
  • the solid was dried at reduced pressure for 30 minutes by gently shaking the flask.
  • the flask was then weighted and the weight of the supported catalyst was calculated to be 12. 4 grams.
  • the flask containing the supported catalyst prepared as described in the previous paragraph, was connected to the rotavapor and it was allowed to rotate, at 80-100 rpm, plunged in a water bath thermostatted at 40°C. 1,3 -butadiene, previously flashed twice and passed on a column of molecular sieves, was fed into the rotavapor and continuously discharged at a pressure of 0.26 barg.
  • Example 2 The same procedure disclosed in Example 1 was followed, except that silica was used instead of the polyethylene pre-polymer as the support for the neodimium based catalytic system.
  • the polymerization was carried out according to the procedure disclosed in Example 1 with the only difference that the polymerization time lasted 1 hour. At the end of the polymerization 40 grams of solid were recovered corresponding to 18.96 of grams of polybutadiene (activity 30gpol/mmolNd/h/bar).
  • TIBAL containing 10 mmol of Al.
  • the so obtained solution was left to stand for about one day after which a hexane solution containing 1.08 mmol of DEAC were added.
  • the resulting clear mixture having a 0.02 molar concentration, was then used in the next step.
  • the flask containing 7.85 g of the supported catalyst prepared as described in the previous paragraph, was connected to the rotavapor and it was allowed to rotate, at 80-100 rpm, plunged in a water bath at room temperature. 1,3-butadiene, previously flashed twice and passed on a column of molecular sieves, was fed into the rotavapor until a pressure of about 1.2 atmosphere was reached.

Abstract

L'invention concerne un composant de catalyseur comprenant un composé métallique choisi dans le groupe constitué par Co, Ni et des éléments de terre rare, et supporté sur un polymère dont la porosité (essai au mercure) est supérieure à 0,02 cm3/g. L'utilisation de ce composant de catalyseur permet de préparer des polymères diéniques, en phase gazeuse, et d'obtenir des rendements importants.
EP99948809A 1998-09-26 1999-09-21 Composants de catalyseur destines a la polymerisation de dienes, catalyseur ainsi obtenu, et procede de preparation de polydienes a l'aide de celui-ci Withdrawn EP1032603A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99948809A EP1032603A1 (fr) 1998-09-26 1999-09-21 Composants de catalyseur destines a la polymerisation de dienes, catalyseur ainsi obtenu, et procede de preparation de polydienes a l'aide de celui-ci

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98203313 1998-09-26
EP98203313 1998-09-26
PCT/EP1999/006979 WO2000018812A1 (fr) 1998-09-26 1999-09-21 Composants de catalyseur destines a la polymerisation de dienes, catalyseur ainsi obtenu, et procede de preparation de polydienes a l'aide de celui-ci
EP99948809A EP1032603A1 (fr) 1998-09-26 1999-09-21 Composants de catalyseur destines a la polymerisation de dienes, catalyseur ainsi obtenu, et procede de preparation de polydienes a l'aide de celui-ci

Publications (1)

Publication Number Publication Date
EP1032603A1 true EP1032603A1 (fr) 2000-09-06

Family

ID=8234176

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99948809A Withdrawn EP1032603A1 (fr) 1998-09-26 1999-09-21 Composants de catalyseur destines a la polymerisation de dienes, catalyseur ainsi obtenu, et procede de preparation de polydienes a l'aide de celui-ci

Country Status (12)

Country Link
EP (1) EP1032603A1 (fr)
JP (1) JP2002525402A (fr)
KR (1) KR20010032176A (fr)
CN (1) CN1286703A (fr)
AR (1) AR021825A1 (fr)
AU (1) AU6193799A (fr)
BR (1) BR9913013A (fr)
CA (1) CA2310647A1 (fr)
HU (1) HUP0004951A3 (fr)
IL (1) IL135868A0 (fr)
WO (1) WO2000018812A1 (fr)
ZA (1) ZA200002583B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101186663B (zh) * 2007-11-13 2010-05-26 中国科学院长春应用化学研究所 催化异戊二烯或丁二烯顺1,4-选择性聚合的稀土催化剂

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2939801B1 (fr) * 2008-12-15 2010-12-31 Michelin Soc Tech Procede de preparation d'un elastomere dienique fonctionnalise, tel qu'un polybutadiene.
KR101685744B1 (ko) * 2013-09-17 2016-12-12 주식회사 엘지화학 희토류 금속을 함유하는 이분자계 착화합물 및 이의 제조 방법
KR20170000756A (ko) 2015-06-24 2017-01-03 주식회사 엘지화학 공액 디엔계 중합체 제조용 촉매 조성물 및 이를 이용하여 제조된 공액 디엔계 중합체
KR101864015B1 (ko) * 2015-06-24 2018-06-04 주식회사 엘지화학 공액 디엔계 중합체 제조용 촉매 조성물 및 이를 이용하여 제조된 공액 디엔계 중합체
CN110256618A (zh) * 2019-05-31 2019-09-20 宁波金海晨光化学股份有限公司 一种顺式-1,4结构的聚间戊二烯及其制备方法和应用
CN111057170B (zh) * 2019-12-06 2022-06-03 中玺新材料（安徽）有限公司 一种负载铬钕钴三金属催化剂及其制备方法和应用

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US5466649A (en) * 1993-10-15 1995-11-14 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
US5453471B1 (en) * 1994-08-02 1999-02-09 Carbide Chemicals & Plastics T Gas phase polymerization process
EP0903355B1 (fr) * 1997-09-19 2003-04-09 Bayer Ag Catalyseur sur support à deux composants et son application à la polymérisation en phase gazeuse
DE19754789A1 (de) * 1997-12-10 1999-07-01 Bayer Ag Katalysator, dessen Herstellung und Verwendung zur Gasphasenpolymerisation von konjugierten Dienen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0018812A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101186663B (zh) * 2007-11-13 2010-05-26 中国科学院长春应用化学研究所 催化异戊二烯或丁二烯顺1,4-选择性聚合的稀土催化剂

Also Published As

Publication number Publication date
AU6193799A (en) 2000-04-17
JP2002525402A (ja) 2002-08-13
KR20010032176A (ko) 2001-04-16
BR9913013A (pt) 2001-05-02
WO2000018812A1 (fr) 2000-04-06
ZA200002583B (en) 2001-02-28
HUP0004951A2 (hu) 2001-05-28
IL135868A0 (en) 2001-05-20
HUP0004951A3 (en) 2002-02-28
AR021825A1 (es) 2002-08-07
CA2310647A1 (fr) 2000-04-06
CN1286703A (zh) 2001-03-07

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