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Method for simply, conveniently and controllably synthesizing alpha-sulfydryl-omega-hydroxyl polyether by taking thiocarboxylic acid as initiator

A technology of thiocarboxylic acid and hydroxyl polyether, which is applied in the field of polyether synthesis, can solve the problems of slow development of synthetic methods, and achieve the effect of strong nucleophilicity

Active Publication Date: 2020-12-04
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Disulfide bonds and tert-butyl sulfide are currently reported in the literature for the protection of thiol groups in initiators, but they are only suitable for anionic ring-opening polymerization under strong alkaline conditions
The thiol-based diheterofunctional PEG is widely used, but the development of synthetic methods is relatively slow, which arouses our thinking, how to obtain a high degree of thiol functionalization and controllable structure and molecular weight through a simpler and more practical method. α-Mercapto-ω-hydroxyl polyether

Method used

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  • Method for simply, conveniently and controllably synthesizing alpha-sulfydryl-omega-hydroxyl polyether by taking thiocarboxylic acid as initiator
  • Method for simply, conveniently and controllably synthesizing alpha-sulfydryl-omega-hydroxyl polyether by taking thiocarboxylic acid as initiator
  • Method for simply, conveniently and controllably synthesizing alpha-sulfydryl-omega-hydroxyl polyether by taking thiocarboxylic acid as initiator

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] One-pot two-step synthesis of α-mercapto-ω-hydroxypolyethylene oxide. (1) Ring-opening polymerization of ethylene oxide (EO) was carried out using thioacetic acid as an initiator and a metal-free Lewis acid-base pair as a catalyst; (2) In situ aminolysis deacetylation. The specific operation is as follows:

[0053] Both tetrahydrofuran (THF) and EO are used after purification and dehydration treatment, and thioacetic acid can be used directly. Under an inert atmosphere, mix 1 part of thioacetic acid (0.5 mmol), 0.1 part of phosphazene base t BuP 1 , 0.5 parts of tri-sec-butylborane and THF (1ml) were successively added into a dry glass reactor and stirred and mixed evenly. In this example, the molar ratio of thioacetic acid, organic base and alkylboron was 1:0.1:0.5 . Connect the glass reactor to a vacuum line, remove part of the gas in the bottle, and cool down with an ice-water bath. Distilled 90 parts of dry EO (where [EO] 0 =15mol / L), and react in a sealed gla...

Embodiment 2

[0056]Two-pot synthesis of α-mercapto-ω-hydroxypolyethylene oxide. (1) With thioacetic acid as initiator, metal-free Lewis acid-base pair is the ring-opening polymerization of ethylene oxide (EO) implemented as a catalyst; (2) the α-thioacetate-ω that the first step obtains After the -hydroxypolyethylene oxide precipitate is dried, the acetyl group is deacetylated by ammonia cleavage. The specific operation is as follows:

[0057] The first step epoxy polymerization is with embodiment 1. After the end of the polymerization reaction, the product was collected, diluted with THF (2mL) and added with neutral Al 2 o 3 Stir, filter twice, and vacuum dry to obtain α-thioacetate-ω-hydroxypolyethylene oxide. Under an inert atmosphere, weigh the initial product in a clean glass reactor, add 7.0 mol / L ammonia in methanol solution (the amount of ammonia used is 10 parts) and methanol (1 mL), and react at room temperature for 8 h. After the reaction was completed, the vacuum line was ...

Embodiment 3

[0059] Change the amount of Lewis acid-base pair, add 0.01 part of phosphazene base t BuP 1 And 0.01 part of tri-sec-butylborane, the rest are consistent with Example 1, and the EO polymerization time is extended to 6h. In this example, the molar ratio of thioacetic acid, organic base and alkyl boron is 1:0.01:0.01. After the first polymerization reaction is completed, 1 The conversion rate of EO monomer was 100% as measured by H NMR, the molecular weight of the crude product as measured by SEC was 4.3 kg / mol, and the degree of dispersion was 1.10. 1 H NMR (600MHz, Chloroform-d), δ3.92 (ddd, J=9.1, 6.3, 2.8Hz, 2H), 3.65 (m, 366H), 3.02 (dq, J=5.1, 1.8Hz, 2H), 2.34 (d,J=1.3Hz,3H).

[0060] After the second step ammonolysis reaction finishes, 1 The degree of thiol functionalization as measured by H NMR is 100%, the molecular weight of the product as measured by SEC is 4.2 kg / mol, and the degree of dispersion is 1.09. 1 H NMR (600MHz, Chloroform-d), δ3.93 (d, J=6.4Hz, 2H), ...

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Abstract

The invention discloses a method for simply, conveniently and controllably synthesizing alpha-sulfydryl-omega-hydroxyl polyether by taking thiocarboxylic acid as an initiator. The method comprises thesteps: in an inert atmosphere, adding an epoxy monomer into a catalytic initiation system containing thiocarboxylic acid, organic alkali and alkyl boron, and reacting to obtain alpha-thiocarboxylate-omega-hydroxy polyether; and carrying out ammonolysis on thioester to obtain alpha-sulfydryl-omega-hydroxyl polyether. A traditional hydroxyl initiator is replaced with thiocarboxylic acid, thioesteris quantitatively introduced to the tail end of polyether in a fixed-point mode, and sulfydryl is quantitatively introduced to the tail end of polyether in a fixed-point mode according to the characteristic that thioester is prone to ammonolysis. The synergistic catalysis effect of metal Lewis acid-base pairs is avoided, so that the reaction of thiocarboxylic acid and an epoxy monomer and the reaction of hydroxyl and the epoxy monomer can be efficiently carried out at room temperature; the selectivity of the catalytic system enables ester exchange, chain transfer to monomers and other side reactions to be completely inhibited, so that the double-end heterofunctionalized polyether with controllable molecular weight and a clear end group structure is synthesized.

Description

technical field [0001] The invention belongs to the field of polyether synthesis, and in particular relates to a simple and controllable method for synthesizing α-mercapto-ω-hydroxy polyether by using thiocarboxylic acid as an initiator. Background technique [0002] Using ethylene oxide, propylene oxide, etc. as raw materials, the aliphatic polyether synthesized by ring-opening homopolymerization or copolymerization under the action of a catalyst is a kind of important polymer with relatively mature development. The polyether main chain is composed of ether bonds (-C-O-C-), which is an important supplement to polyolefin polymers in terms of performance. Among them, polyethylene oxide (PEO; also known as polyethylene glycol, PEG) has excellent water solubility and biocompatibility, and is regarded as the "gold standard" in the fields of pharmaceuticals, cosmetics, and medical treatment. In addition to the main chain structure and side groups, the functional groups at the ch...

Claims

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Application Information

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IPC IPC(8): C08G65/26C08G65/325
CPCC08G65/2636C08G65/2672C08G65/2675C08G65/2687C08G65/3255
Inventor 赵俊鹏刘利君刘珊张广照
Owner SOUTH CHINA UNIV OF TECH
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