GB2247024A - Polymerisation catalyst and process - Google Patents

Polymerisation catalyst and process Download PDF

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Publication number
GB2247024A
GB2247024A GB9117493A GB9117493A GB2247024A GB 2247024 A GB2247024 A GB 2247024A GB 9117493 A GB9117493 A GB 9117493A GB 9117493 A GB9117493 A GB 9117493A GB 2247024 A GB2247024 A GB 2247024A
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United Kingdom
Prior art keywords
catalyst
component
alkylene oxide
aluminoxane
rare earth
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GB9117493A
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GB2247024B (en
GB9117493D0 (en
Inventor
Derek Keith Jenkins
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Enichem Elastomers Ltd
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Enichem Elastomers Ltd
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Publication of GB9117493D0 publication Critical patent/GB9117493D0/en
Publication of GB2247024A publication Critical patent/GB2247024A/en
Application granted granted Critical
Publication of GB2247024B publication Critical patent/GB2247024B/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerization Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

A catalyst for the homopolymerisation of an alkylene oxide or copolymerisation of two or more alkylene oxides comprises a) a rare earth salt or complex and b) an aluminoxane in hydrocarbon solvent or diluent. The invention includes a process for the polymerisation of alkylene oxide(s) by contacting with said catalyst, or the components thereof, in hydrocarbon solvent or diluent. Component (a) is preferably neodymium naphthenate or neodecanoate. Component (b) is preferably a C2-6 alkyl aluminoxane, e.g. butyl aluminoxane. The alkylene oxide exemplified is propylene oxide.

Description

Polymerisation Catalyst and Process This invention relates to the homopolymerisation of an alkylene oxide and the copolymerisation of two or mote alkylene oxides.
Polymers and copolymers of alkylene oxides have been known for many years and are now manufactured in very large tonnages We have now found a new catalyst for the homopolymerisation and copolymerisation of alkylene oxides based on a rare earth metal salt or complex. In this context a rare earth metal is defined as any element having an atomic number of 57 to 71. Rare earth based catalysts have been the subject of much research in recent years mainly in the area of diene polymerisations and have reached the stage where rare earth based catalysts are now used in the commercial production of polydienes. Such catalysts for the polymerisation of dienes generally comprise three components a) a neodymium salt or complex; b) an aluminium alkyl or alkyl hydride and c) a source of halogen. Examples of such catalyst systems are disclosed in U.S.
Patents Nos. 4,429,089; 4,444,903; 4,525,549, and 4,436,884.
In our research work in this area we have examined aluminoxanes as a cocatalyst in the polymerisation of dienes and other monomers.
According to the present invention a catalyst for the homopolymerisation of an alkylene oxide or copolymerisation of two or more alkylene oxides comprises: a) a rare earth salt or complex and b) an aluminoxane in hydrocarbon solvent or diluent.
The invention also includes a process for the homopolymerisation of an alkylene oxide or copolymerisation of two or more alkylene oxides comprising contacting the alkylene oxide(s) in hydrocarbon solvent or diluent, with said catalyst or the components thereof.
The rare earth salt or complex is preferably soluble in hydrocarbons. Neodymium salts are particularly preferred especially neodymium naphthenate and neodymium versatate (neodymium neo decanoate).
Aluminoxanes have been the subject of papers and patents in the field of polymerisation of olefins (see, for example, Polymer 1989, 30 (7) 1350-6) but do not appear to be active as a component of a rare earth based diene polymerisation catalyst. However, we have found that, in combination with a rare earth salt or complex, an aluminoxane forms a catalyst which will polymerise alkylene oxides.
The alkyl groups in the aluminoxane preferably have 2 to 6 carbon atoms, for example butyl aluminoxane. This may be prepared by a method similar to that disclosed in Polymer Communications 1988 Vol.
29, June p180 or by the method of Chien (J.C.W. Chien, B-P. Wang.
J.Poly.Sci. Poly Chem. 26 3089 (1988)).
The molar ratio of component (b) to component (a) in the catalyst is preferably 5:1 to 100:1, more preferably 15:1 to 50:1. Preferably component (a) is used in an amount such that the molar concentration of rare earth e.g. [Nd] is 1 to 10 m.mole per lOOg. of alkylene oxide.
Typically the polymerisation reaction is carriedlin hydrocarbon solvent or diluent, toluene being preferred. One suitable procedure is to add the monomer(s) to the hydrocarbon followed by the aluminoxane and finally the rare earth component, (a). However other orders of addition may be used. For example a premix of the catalyst components may be prepared in hydrocarbon and added to the monomer(s) in hydrocarbon solvent/diluent. The polymerisation may be carried out at e.g. 0 C to 150 C, but moderately elevated temperatures, e.g. 60"C are convenient.
The following Examples illustrate the invention.
Examples 1 to 3 Propylene oxide, neodymium versatate (neodecanoate) and butyl aluminoxane were contacted in toluene at 600C at the mole ratios shown below, in the order toluene, propylene oxide, butyl aluminoxane, neodymium versatate. The neodymium concentration was 5mM/100g. propylene oxide. Polymerisation began upon addition of the last component and was continued for 24 hrs. The polymers were isolated by removing the solvent under vacuum. The conversion and intrinsic viscosity of the polymers obtained was as shown: Ex. Aluminoxane:Nd Conversion No. molar ratio 1 15:1 23.6 2.05 2 20:1 47.8 2.11 3 30:1 68.7 1.81 *I.V. = Intrinsic viscosity measured in toluene at 30"C.
Examples 4 - 6 The polymerisation, as above, was repeated in hexane solvent, although 15-20% by volume of toluene was added with the aluminoxane components.
The results were: Ex. Aluminoxane:Nd Conversion I.V.
No. molar ratio 4 15:1 45.9 1.47 5 20:1 61.3 1.65 6 30:1 84.2 2.21 Example 7 Example 2 was repeated except that the neodymium complex was added before the aluminoxane. The results were: Nd:Aluminoxane molar ratio 7 1:20 50.4 2.22

Claims (7)

  1. Claims 1. A catalyst for the homopolymerisation of an alkylene oxide or copolymerisation of two or more alkylene oxides comprising a) a rare earth salt or complex and b) an aluminoxane in hydrocarbon solvent or diluent.
  2. 2. A catalyst according to claim 1 in which the mole ratio of component (b) to component (a) is 5:1 to 100:1.
  3. 3. A catalyst according to claim 2 in which the mole ratio of component (b) to component (a) is 15:1 to 50:1.
  4. 4. A process for the homopolymerisation of an alkylene oxide or copolymerisation of two or more alkylene oxide comprising contacting the alkylene oxide(s) in hydrocarbon solvent or diluent with a catalyst, or the components thereof, according to any one of claims 1 to 3.
  5. 5. A process according to claim 4 in which component (a) is used in an amount such that the molar concentration of rare earth is 1 to 10 m.mole per lOOg. of alkylene oxide.
  6. 6. A process according to claim 4 or claim 5 in which propylene oxide is homopolymerised.
  7. 7. A process according to any one of claims 4 to 6 substantially as herein described with reference to the Examples.
GB9117493A 1990-08-15 1991-08-13 Polymerisation catalyst and process Expired - Lifetime GB2247024B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB909017875A GB9017875D0 (en) 1990-08-15 1990-08-15 Polymerisation catalyst and process

Publications (3)

Publication Number Publication Date
GB9117493D0 GB9117493D0 (en) 1991-09-25
GB2247024A true GB2247024A (en) 1992-02-19
GB2247024B GB2247024B (en) 1993-10-27

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GB9117493A Expired - Lifetime GB2247024B (en) 1990-08-15 1991-08-13 Polymerisation catalyst and process

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Also Published As

Publication number Publication date
GB2247024B (en) 1993-10-27
GB9017875D0 (en) 1990-09-26
GB9117493D0 (en) 1991-09-25

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Expiry date: 20110812