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Preparation method of terminal alkenyl end-capped unsaturated polyether

A technology of alkenyl end capping and alkenyl end capping, which is applied in the field of unsaturated polyether preparation, can solve the problems of low reaction conversion rate, strong reversibility, double bond destruction, etc., and achieve high production efficiency and wide application range

Active Publication Date: 2019-07-05
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, during the alkoxide reaction, the alkali metallization reagent used will destroy the double bond of the raw material polyether at high temperature.
In the preparation of high-quality polyether-modified silicone, it involves the hydrosilylation reaction of capped unsaturated polyether and hydrogen-containing silicone oil. The higher the double bond content of polyether, the faster the reaction speed, and the prepared silicone The better the performance; on the contrary, when the blocked unsaturated polyether with low double bond content is used for hydrosilylation reaction, it not only introduces the blocked polyether impurities whose double bonds are destroyed, but also affects the reaction speed and product performance.
[0015] The common point of the above two types of methods is that they both adopt the method of equilibrium reaction to introduce other groups to the other end of the polyether with a certain group. The disadvantage of the method of equilibrium reaction is that it is highly reversible, and most polyether reactions are still formula reaction, under back-mixing conditions, the reaction conversion rate is low, and the actual end-capping rate of the obtained product is low (directly leading to the decline and instability of product quality) or requires more energy consumption to reach the required end-capping rate, thereby improving synthetic cost

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] The concrete reaction process that present embodiment prepares polyether is as follows:

[0043] step 1):

[0044] 1.1) With water and ethylene glycol mixture as initiator (wherein the mass fraction of water is 50wt%), the amount of initiator is 0.2wt% of the final polyether product quality, add 0.6wt% (based on polyether product quality) The catalyst is sodium hydroxide, replaced by nitrogen, the temperature is raised to 120°C, and the pressure is reduced to -0.095MPa for dehydration reaction for 2 hours, and the water generated by the reaction is removed;

[0045] 1.2) Add uniformly mixed EO / PO (the mass fraction of EO is 50wt%, and the amount of EO and PO are both 1.6% of the mass of the polyether product) raw material into the system of step 1.1), the reaction temperature is 100°C, and the reaction pressure is 0.05MPa After reacting for 1 hour, neutralize and refine to obtain the raw material for bimetallic catalytic polymerization (the neutralization and refining ...

Embodiment 2

[0052] The concrete reaction process that present embodiment prepares polyether is as follows:

[0053] step 1):

[0054] 1.1) With the mixture of glycerin and pentaerythritol as initiator (wherein the mass fraction of glycerin is 50%wt), the amount of initiator is 1.07wt% of polyether product quality, add 1wt% (based on polyether product quality) catalyst hydrogen Potassium oxide, replaced by nitrogen, heated to 100°C, depressurized to -0.097MPa for dehydration reaction for 1 hour, and removed the water generated by the reaction;

[0055] 1.2) Add EO raw material (being 63wt% of polyether product quality) to step 1.1) system, reaction temperature 150 ℃, reaction pressure 0.5MPa, after reacting for 10h, obtain bimetallic catalytic polymerization raw material (neutralization and Refined specific operation with reference to embodiment 1, repeats no more). Add a bimetallic catalyst (DMC catalyst, produced by Huai'an Bard Company, the amount used accounts for 0.01wt% of the poly...

Embodiment 3

[0062] The concrete reaction process that present embodiment prepares polyether is as follows:

[0063] step 1):

[0064] 1.1) Using neopentyl glycol as the initiator, the amount of the initiator is 54.2wt% of the mass of the polyether product, additionally adding 0.6wt% (based on the mass of the polyether product) catalyst potassium methoxide, replacing with nitrogen, and raising the temperature to 120°C, Reduce the pressure to -0.095MPa to carry out the desolvation reaction for 2 hours, and remove the methanol generated by the reaction;

[0065] 1.2) Add EO raw material (45.8wt% of the mass of the polyether product) to the system in step 1.1), react at a reaction temperature of 100° C. and a reaction pressure of 0.05 MPa for 3 hours.

[0066] Step 2): Add the calculated isobutylene oxide to the system (the molar ratio of isobutylene oxide to the initiator for capping is 1.2×n:1, n=2, that is, 2.4:1, mature After 3h, add phosphoric acid to neutralize to PH<7, at this time t...

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Abstract

The invention provides a preparation method of terminal alkenyl end-capped unsaturated polyether. The method includes the steps of: 1) taking one of or a mixture of polyol and water as the starting agent for polymerization with ethylene oxide and / or propylene oxide to prepare uncapped polyether; 2) contacting the uncapped polyether with isobutane oxide for curing reaction so as to obtain tertiaryalcohol end-capped polyether; and 3) subjecting the tertiary alcohol end-capped polyether to intramolecular dehydration under the action of a dehydration catalyst to eliminate hydroxyl on tertiary carbon, thus obtaining terminal alkenyl end-capped unsaturated polyether. The preparation method of terminal alkenyl end-capped unsaturated polyether provided by the invention has the characteristics ofsimple synthesis route and strong operability, is easy for preparation of polyether products with required double-bond end-capping rates, and can be flexibly applied to the requirements of polyether products with different double-bond end-capping rates.

Description

technical field [0001] The invention relates to the technical field of unsaturated polyether preparation, in particular to a preparation method of an alkenyl-terminated unsaturated polyether. Background technique [0002] The alkenyl-terminated unsaturated polyether plays a very important role in polymer synthesis technology, benefiting from the high flexibility of the polyether main chain, and the polyether structure can be hydrophilically modified by adjusting the PO / EO ratio. [0003] Modified products of alkenyl-terminated unsaturated polyether can be widely used in various industries: [0004] 1. CN201210526464.7 introduces an alkyl-terminated alkenyl-terminated polyether, which undergoes a copolymerization reaction with hydrogen-containing silicone oil, and the prepared polyether-modified silicone belongs to Si-C type, which has strong wetting force and excellent surface Active, the product can be used in textile auxiliaries, high-grade shampoo, sterilization and othe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G65/28C08G65/331C08G65/32
CPCC08G65/26C08G65/2609C08G65/32
Inventor 叶天陈海波信勇刘运海鞠昌迅王竞辉张琴花刘斌黎源
Owner WANHUA CHEM GRP CO LTD