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Cyclic ester bulk ring-opening polymerization method by taking thiazole onium salt as catalyst and catalyst preparation method

A thiazolium salt and ring-opening polymerization technology, which is applied in the direction of carboxylate preparation, sulfonate preparation, chemical instruments and methods, etc., can solve the problem of harsh conditions for the preparation of nitrogen-heterocyclic carbene, low catalytic efficiency of thiazole-based carbene, and inability to Catalytic ring-opening polymerization and other problems, to achieve good catalytic ability, easy and stable storage and use, and good catalytic efficiency

Active Publication Date: 2019-02-15
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in catalyzing the ring-opening polymerization of cyclic esters, thiazole carbenes have low catalytic efficiency, and also have the common defect of nitrogen heterocyclic carbene-extremely sensitive to water and oxygen
The conditions for the preparation of nitrogen heterocyclic carbene are relatively harsh and the stability is insufficient; while the easier to prepare and more stable azoliums cannot catalyze ring-opening polymerization

Method used

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  • Cyclic ester bulk ring-opening polymerization method by taking thiazole onium salt as catalyst and catalyst preparation method
  • Cyclic ester bulk ring-opening polymerization method by taking thiazole onium salt as catalyst and catalyst preparation method
  • Cyclic ester bulk ring-opening polymerization method by taking thiazole onium salt as catalyst and catalyst preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Dissolve 3.37g of thiamine hydrochloride in 5ml of water to make solution A, dissolve 0.40g of sodium hydroxide in 2ml of water to make solution B, dissolve 2.87g of lithium bistrifluoromethanesulfonylimide in 2ml of water, and make It is solution C; mix A and B solutions, and after fully stirring, the hydrochloric acid in thiamine hydrochloride is basically neutralized; then add solution C to the mixed solution of A and B, fully stir and let it stand until the precipitation is complete; filter, Dry to obtain white powdery solid i.

[0036] Using i as a catalyst, the molar ratio of caprolactone to catalyst is 100 / 1 (caprolactone 2.85g, catalyst 0.137g) After feeding, close the reaction system, stir fully in an oil bath at 150°C for 12h, then stop heating; dissolve the product in 20ml of dichloromethane, after filtering, add the filtrate dropwise to 80ml of ethanol, stir fully after the dropwise addition, let it stand until the precipitation is complete, filter out the p...

Embodiment 2

[0038] Dissolve 3.37g of thiamine hydrochloride in 5ml and water to make solution A, dissolve 0.40g of sodium hydroxide in 2ml and water to make solution B, dissolve 1.68g of sodium hexafluorophosphate in 2ml and water to make solution C; mix A and B solutions, after fully stirring, the hydrochloric acid in thiamine hydrochloride is basically neutralized; then add solution C to the mixed solution of A and B, stir fully and let stand until the precipitation is complete; filter and dry to obtain white Powdered solid ii.

[0039] Use ii as the catalyst, the molar ratio of caprolactone to catalyst is 100 / 1 (caprolactone 2.85g, catalyst 0.103g) After feeding, close the reaction system, stir fully in an oil bath at 150°C for 12h, then stop heating; dissolve the product in 20ml of dichloromethane, after filtering, add the filtrate dropwise to 80ml of ethanol, stir fully after the dropwise addition, let it stand until the precipitation is complete, filter out the precipitation, and dr...

Embodiment 3

[0041] Dissolve 3.37g of thiamine hydrochloride in 5ml and water to make solution A, dissolve 0.40g of sodium hydroxide in 2ml and water to make solution B, dissolve 1.10g of sodium tetrafluoroborate in 2ml and water to make solution C; mix A and B solutions, after fully stirring, the hydrochloric acid in thiamine hydrochloride is basically neutralized; then add solution C to the mixed solution of A and B, stir fully and let stand until the precipitation is complete; filter and dry to obtain white Powdered solid iii.

[0042] Use iii as the catalyst, the molar ratio of caprolactone to catalyst is 100 / 1 (caprolactone 2.85g, catalyst 0.088g) After feeding, close the reaction system, stir fully in an oil bath at 150°C for 12h, then stop heating; dissolve the product in 20ml of dichloromethane, after filtering, add the filtrate dropwise to 80ml of ethanol, stir fully after the dropwise addition, let it stand until the precipitation is complete, filter out the precipitation, and dr...

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Abstract

The invention provides a cyclic ester bulk ring-opening polymerization method by taking a thiazole onium salt as a catalyst, and further provides a preparation method of the thiazole onium salt catalyst. Negative ions of the thiazole onium are regulated by virtue of ion exchange, so that the thiazole onium salt catalyst can be dissolved into a cyclic ester monomer, and an excellent catalytic effect on cyclic ester bulk ring-opening polymerization is achieved. According to the method provided by the invention, the thiazole onium is directly used for catalyzing ring-opening polymerization, and is then prepared into N-heterocyclic carbenes without hydrogen removal. Therefore, compared with an another type of catalyst, namely thiazole carbene, prepared by removing hydrogen from thiazole oniumin the prior art, the thiazole onium catalyst provided by the invention has excellent stability on water and oxygen, and is simpler to prepare, green, environmentally-friendly and easy to store and use stably. Moreover, the catalytic bulk ring-opening polymerization provided by the invention is applicable to multiple monomers, the catalytic efficiency is moderate, the catalytic temperature windowis wide, and the industrial application degree of the cyclic ester ring-opening polymerization and polyester preparation can be obviously improved.

Description

technical field [0001] The invention belongs to the technical field of catalytic ring-opening polymerization, and in particular relates to a method for using a metal-free catalyst as a catalyst for ring-opening polymerization of cyclic esters. Background technique [0002] Catalyzed ring-opening polymerization of cyclic esters is a typical method for preparing polyesters such as polylactic acid, polycaprolactone, polydioxanone, polyvalerolactone, and polycarbonate. This kind of polyester is widely used in biomedicine due to its excellent biocompatibility and degradability. Therefore, there are strict restrictions on the residue and toxicity of ring-opening polymerization catalysts. Traditional ring-opening polymerization catalysts are mostly metal complexes, and their metal ions are often toxic and difficult to remove, which limits their use in biomedical applications. Among many metal complex catalysts (organotin, organoaluminum, organozinc, rare earth complexes), only st...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G63/87C08G63/84C08G63/82C08G63/08C07D417/06C07C303/40C07C311/48C07C303/32C07C309/30C07C51/41C07C59/01C07D277/24C07D277/22C07F9/6558C07D277/62
CPCC07D277/22C07D277/24C07D277/62C07D417/06C07F9/65583C08G63/08C08G63/823C08G63/84C08G63/87
Inventor 陈思翀田国强陈力王玉忠谢思宇
Owner SICHUAN UNIV
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