Initiator for synthesizing high cis-1, 4-hydroxyl-terminated polybutadiene and preparation method and application thereof

Abstract

The invention belongs to the technical field of initiators for synthesizing high cis-1, 4-hydroxyl-terminated polybutadiene, and discloses an initiator for synthesizing high cis-1, 4-hydroxyl-terminated polybutadiene, and a preparation method and application thereof. The initiator comprises: A neodymium carboxylate with the carbon atom number of 7-14; B, alkyl aluminum of general formula AlR<1>3; C, halide of general formulaAlR<2>2Cl; D, polymerization grade butadiene; E, alkyl lithium with hydroxyl protected by silane. The method comprises the steps of: under an inert atmosphere, adding the component E into the solution of the component D for reaction, and then adding the component A into the reaction solution for continuous reaction to obtain a first reaction solution; adding the component B into the solution of the component C, and reacting to obtain a second reaction solution; and adding the second reaction solution into the first reaction solution, and reacting to obtain the initiator for synthesizing the high cis-1, 4-hydroxyl-terminated polybutadiene. The initiator can realize the terminal functionalization of high cis-coordination polymerization, and the terminal hydroxylated polybutadiene rubber with high cis-content is synthesized.

Description

technical field [0001] The invention relates to an initiator for synthesizing high cis-1,4-terminated hydroxyl polybutadiene, in particular to an initiator for synthesizing high cis-1,4-terminated hydroxyl polybutadiene, a preparation method and application thereof. Background technique [0002] Hydroxyl-terminated polybutadiene (HTPB) is a functional polymer whose main chain is polybutadiene with hydroxyl groups at both ends. The spatial configuration of HTPB can be divided into cis 1,4 structure, trans 1,4 structure and 1,2 structure, among which, the 1,4 structure refers to the polymer chain link of butadiene monomer through 1-C and 4-C, and the glass transition temperature of the cis-1,4 structural segment is -106°C, which is all The glass transition temperature of the hydroxylated butadiene polymer is the highest. The glass transition temperature of the 1,2 structure is -15°C. The trans 1,4 structure is easy to crystallize due to the regular arrangement of the chain seg...

AI Technical Summary

Problems solved by technology

However, it is technically impossible to directly synthesize HTPB with a high cis-1,4 structure by rare earth coordination catalysis, because neodymium naphthenate, neodecanoate, and triisobutylaluminum in rare earth neodymium catalysts do not contain hydroxyl groups. functional groups, which makes the final polybutadiene without hydroxyl functional groups at both ends

[0005] Patent document 1CN101274972A discloses a method for preparing low-molecular-weight hydroxyl-terminated polybutadiene, which uses butadiene as a monomer, uses aliphatic alkyllithium containing silane-protected hydroxyl as an initiator, and uses organic non-polar compound As a solvent, epoxy compounds are used as end-capping reagents, fluorides are used as protective group removal reagents, anionic polymerization technology is used, and polymerization is carried out at 20-80°C in an inert gas environment, and the obtained prepolymer is subjected to acid solution, a series of narrow molecular weight distribution, molecular weight controllable hydroxyl-terminated polybutadiene liquid rubber, but the cis-1,4-butadiene structural unit content in the hydroxyl-terminated polybutadiene liquid rubber obtained in this document Low, poor low temperature performance