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Rare earth catalyst system for preparing high trans-diolefin homopolymer and copolymer and method for catalyzing polymerization of diolefin

A technology of diene polymer and rare earth catalysis, which is applied in the field of rare earth catalyst system and catalytic diene polymerization, to achieve good catalytic activity and facilitate application

Active Publication Date: 2015-05-20
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, there are few reports on the preparation of high-trans polydienes using rare-earth catalyst systems

Method used

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  • Rare earth catalyst system for preparing high trans-diolefin homopolymer and copolymer and method for catalyzing polymerization of diolefin
  • Rare earth catalyst system for preparing high trans-diolefin homopolymer and copolymer and method for catalyzing polymerization of diolefin
  • Rare earth catalyst system for preparing high trans-diolefin homopolymer and copolymer and method for catalyzing polymerization of diolefin

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preparation example Construction

[0076] The present invention has no special limitation on the preparation method of the rare earth catalytic composition, the rare earth compound, the conjugated diene, the first auxiliary component and the second auxiliary component can be added to an organic solvent such as a hydrocarbon solvent, or first Mix and add organic solvent. For the order of addition, the rare earth compound, the conjugated diene and the second auxiliary component can be mixed in sequence to obtain a rare earth mixture, the first auxiliary component is added to the polymerization liquid, and then the prepared rare earth mixture is added to obtain a rare earth catalytic composition It is also possible to mix the rare earth compound, the conjugated diene, the second auxiliary component and the first auxiliary component successively to obtain a rare earth mixture, and the first auxiliary component is added to the polymerization liquid, and then the prepared rare earth mixture is added to obtain Rare ea...

Embodiment 1

[0103] 1.1 In the reactor, according to the molar ratio of neodymium oxide and trifluoromethanesulfonic acid as 10:1, add neodymium oxide into trifluoromethanesulfonic acid solution, heat to 70°C under stirring conditions, and react for 8 hours. Remove unreacted neodymium oxide by filtration, and concentrate to obtain an aqueous solution of neodymium trifluoromethanesulfonate compound, and then place the concentrated solution at room temperature to naturally precipitate crystals, which are neodymium trifluoromethanesulfonate with crystal water compound.

[0104] 1.2 According to the molar ratio of rare earth: electron donor L being 1:3, add the neodymium trifluoromethanesulfonate compound crystal and electron donor L into the reactor respectively, then add 40mL tetrahydrofuran as a solvent, and boil the solution Condensed under reflux for 16 hours, evaporated the solvent, and dried to constant weight to obtain the rare earth compound represented by formula I. For the structur...

Embodiment 2

[0108] 2.1 Add lanthanum oxide to the benzenesulfonic acid solution in the reactor according to the molar ratio of lanthanum oxide to benzenesulfonic acid is 10:1, heat to 80°C under stirring condition, react for 5 hours, filter the untreated The reacted lanthanum oxide is removed and concentrated to obtain an aqueous solution of lanthanum benzenesulfonate compound, and then the concentrated solution is placed at room temperature to naturally precipitate crystals, which are lanthanum benzenesulfonate compounds with crystal water.

[0109] 2.2 According to the ratio of rare earth: electron donor L molar ratio of 1:3, respectively add the lanthanum benzenesulfonate compound crystal and electron donor L into the reactor, then add 40mL tetrahydrofuran as a solvent, in the solution boiling state Condensate and reflux for 16 hours, evaporate the solvent, and dry to constant weight to obtain the rare earth compound shown in formula I. For the structure of the rare earth compound, see ...

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Abstract

The application provides a rare earth catalyst system for preparing a high trans-diolefin copolymer. The rare earth catalyst system comprises a rare earth compound shown in a formula I Ln(RSO3)3.xH2O.yL, conjugated diene and a first auxiliary component shown in a formula II R1MR2; in the formula I, Ln is rare earth; R is alkyl, substituted alkyl, aryl or substituted aryl; L is alcohol, sulfoxide, amine or ester ligand; x is equal to or greater than 0 and less than or equal to 8, y is equal to or greater than 1 and less than or equal to 4; in the formula II, M is magnesium or zinc; R1 and R2 are independently alkyl, aryl, substituted aryl or benzyl; and the molar ratio of the first auxiliary component to rare earth compound is (5-30): 1. The rare earth catalyst system preferably further comprises an alkyl-containing aluminum compound and is used for further improving the catalytic activity of the rare earth catalyst system. The application provides a method for catalyzing the polymerization of diolefin. The rare earth catalyst system provided by the application has better catalytic activity and the high trans-diolefin copolymer can be prepared under the catalysis action of the rare earth catalyst system.

Description

technical field [0001] The invention relates to the technical field of catalysts, in particular to a rare earth catalyst system for preparing high trans diene polymers and a method for catalyzing diene polymerization. Background technique [0002] In recent years, with the advancement of science and technology and the development of social economy, the requirements for the variety and performance of rubber materials have been continuously improved. Among them, high-trans polybutadiene (TPBD) and high-trans polyisoprene (TPI) rubbers polymerized from butadiene and isoprene monomers, as well as high-trans butadiene and isoprene Diene copolymer rubber (TBIR) has unique properties, so it has attracted widespread attention. [0003] High-trans polymers refer to polymers with a trans-structure molar content greater than 65%, and high-trans-structure diene polymers have good dynamic properties, such as low rolling resistance and compression heat generation, and excellent Flex res...

Claims

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Application Information

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IPC IPC(8): C08F136/06C08F136/08C08F236/06C08F236/08C08F4/54
Inventor 代全权张学全白晨曦胡雁鸣张春雨毕吉福于琦周
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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