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Method of homopolymerization of conjugated dienes or copolymerization of conjugated dienes and monovinyl aromatics

A conjugated diene and monomer technology, applied in the field of conjugated diene polymerization, can solve the problems of product structure and performance influence, coupling efficiency, reactive species, etc.

Inactive Publication Date: 2009-02-04
CHINA PETROLEUM & CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Most of the traditional anionic structure regulators have poor regulation ability at higher polymerization temperature conditions, and high temperature can ensure a faster reaction rate, which is the premise of industrial production; if the amount of structure regulator added is large, it will Affect the reactive species, and then affect the structure and performance of the product; there are also some symmetrical ethers that can be used as structure regulators, such as 2G, etc., but they will kill the reactive species and affect the coupling efficiency

Method used

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  • Method of homopolymerization of conjugated dienes or copolymerization of conjugated dienes and monovinyl aromatics
  • Method of homopolymerization of conjugated dienes or copolymerization of conjugated dienes and monovinyl aromatics
  • Method of homopolymerization of conjugated dienes or copolymerization of conjugated dienes and monovinyl aromatics

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Experimental program
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Effect test

Embodiment 1

[0038] Under the protection of high-purity nitrogen, mixed solvent (mixture of cyclohexane and n-hexane: 82 / 18, mass ratio), 1,3-butadiene (Bd), and styrene (St) were added to the mixture according to the batching ratio. 5 liters of stainless steel polymerization reactor with stirring. The reactor was heated to 50° C. by heating the jacket with hot water, and n-butyllithium (Li) in the amount shown below and sodium morpholine ethoxide (Na) in the molar ratio to n-butyllithium in the molar ratio shown below were sequentially added. Polymerization was carried out at 50-120° C. for one hour, followed by the addition of tin tetrachloride (Sn) with n-butyllithium in the molar ratio shown below for coupling for 30 minutes. Then add isopropanol in an amount 1.2 times (molar ratio) of n-butyllithium to terminate the reaction, and condense with water vapor to obtain a random styrene-butadiene copolymer product. The microstructure of the product is shown in Table 1 below. The microstr...

Embodiment 2-4

[0050] According to the procedure described in Example 1, the difference is that the structural regulators added to the polymerization system become sodium morpholine propoxide, sodium morpholine butoxide and sodium morpholine pentoxide respectively, that is, R in the formula I is respectively -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -and-CH 2 CH 2 CH 2 CH 2 CH 2 -. The results are shown in Table 2.

[0051] Table 2

[0052] serial number

Embodiment 5-7

[0054] Carry out according to the procedure described in Example 1, the difference is to adjust the dosage of the structure regulator added to the polymerization system, so that the ratio of it and organolithium becomes 1.0, 2.0 and 5.0 in turn. The results are shown in Table 3.

[0055] table 3

[0056] serial number

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Abstract

The invention provides a method for homopolymerizing conjugated dialkene or co-polymerizing conjugated dialkene and monovinyl aromatic hydrocarbon. The method comprises the following steps: the conjugated dialkene is homopolymerized or the conjugated dialkene and the monvinyl aromatic hydrocarbon are co-polymerized randomly. The method is characterized in that at least one alkali metal alkoxide compound expressed by the formula (I) is used as a structure regulator; in the formula, R is linear chain or branched chain alkylidene radical having 1 to 10 carbon atoms; M is alkali metal selected from Li, Na, K, Rb and Cs. In addition, the invention further relates to a catalyzer combination used for polymerizing a conjugated dialkene monomer and the anions of an optional mono-vinyl aromatic hydrocarbon into a polydiene polymer having high and medium vinyl content. The catalyzer combination comprises (a) an organolithium compound used as an anionic polymerization initiator, (b) at least an alkali metal alkoxide compound expressed by the formula (I) as a structure regulator. By adopting the compound expressed by the formula (I) as the structure regulator for polymerization of the conjugated dialkene, the dialkene polymer having high and medium vinyl content can be got.

Description

technical field [0001] The invention relates to a method for polymerizing conjugated diene, in particular to a method for homopolymerization of conjugated diene or copolymerization of conjugated diene and monovinylarene using morpholine alkoxide as a structural regulator. Furthermore, the present invention also relates to a catalyst composition comprising an organolithium compound as an anionic polymerization initiator and at least one morpholino alkoxide as a structure regulator. Background technique [0002] Polybutadiene rubber and solution-polymerized styrene-butadiene rubber with high vinyl content have good wet skid resistance and low rolling resistance, and are suitable for rubber products such as automobile tread rubber, so they have broad development prospects. In the conjugated diene polymerization product initiated by organolithium in an inert solvent, the vinyl content is relatively low, generally only about 10%. In order to increase the vinyl content in the pro...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F297/04C08F2/38C08F4/48
Inventor 梁爱民刘炼李伟于国柱李传清王世朝王雪闫冰张杰
Owner CHINA PETROLEUM & CHEM CORP
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