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A kind of synthetic method of high molecular weight polycaprolactone

A synthesis method and polycaprolactone technology are applied in the field of catalytic synthesis of high molecular weight polycaprolactone, which can solve problems such as difficult commercial production and achieve the effect of stable and reliable operation.

Active Publication Date: 2021-12-03
安徽红太阳新材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Although there are also some catalysts that can meet the requirements of polycaprolactone with high synthetic molecular weight and controllability, they have already had intellectual property rights (Macromolecules, 2008, 41, 3782; Macromolecules, 2011, 44, 1999; Macromolecules, 1996, 29, 1399, etc.), it is difficult to apply to commercial production

Method used

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  • A kind of synthetic method of high molecular weight polycaprolactone

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Embodiment 1

[0028] t-BuP 2 (25 μmol, 1 equiv.) and phenylpropanol (25 μmol, 1 equiv.) were mixed into a polymerization tube with 5 mL of dichloromethane, and stirred evenly. Then ε-caprolactone (2.5mmol, 100equiv.), ZnCl 3 (37.5 μmol, 1.5 equiv) was added and mixed into the reaction system to start the polymerization reaction, the polymerization reaction was carried out at room temperature, and the whole system was under the protection of argon. used during the reaction 1 H NMR was used to detect the monomer content. When the monomer in the system was completely consumed, an excess of benzoic acid was added, and then triethylamine was added to terminate the reaction. The dichloromethane was spun off with a rotary evaporator to obtain the crude product. Use toluene to separate out the complexes and metal salts in the crude product, filter off the solid impurities, and then spin off the toluene. Finally, the product was redissolved in a small amount of CH 2 Cl 2 Then, the mixed liquid...

Embodiment 2

[0030] t-BuP 2 (25 μmol, 1 equiv.) and butanol (25 μmol, 1 equiv.) were mixed into a polymerization tube with 4 mL of dichloromethane, and stirred evenly. Then ε-caprolactone (1.75mmol, 70equiv.), AlCl 3 (30 μmol, 1.2 equiv.) was added and mixed into the reaction system to start the polymerization reaction, the polymerization reaction was carried out at room temperature, and the whole system was under the protection of argon. used during the reaction 1 H NMR was used to detect the monomer content. When the monomer in the system was completely consumed, an excess of benzoic acid was added, and then triethylamine was added to terminate the reaction. The dichloromethane was spun off with a rotary evaporator to obtain the crude product. Use toluene to separate out the complexes and metal salts in the crude product, filter off the solid impurities, and then spin off the toluene. Finally, the product was dissolved in a small amount of CH 2 Cl 2 Then, the mixed liquid was added...

Embodiment 3

[0032] t-BuP 2 (25 μmol, 1 equiv.) and phenylpropanol (25 μmol, 1 equiv.) were mixed into a polymerization tube with 3 mL of dichloromethane, and stirred evenly. Then ε-caprolactone (3.75mmol, 150equiv.), FeCl 3 (42.5 μmol, 1.7 equiv.) was added and mixed into the reaction system to start the polymerization reaction, the polymerization reaction was carried out at room temperature, and the whole system was under the protection of argon. used during the reaction 1 H NMR was used to detect the monomer content. When the monomer in the system was completely consumed, an excess of benzoic acid was added, and then triethylamine was added to terminate the reaction. The dichloromethane was spun off with a rotary evaporator to obtain the crude product. Use toluene to separate out the complexes and metal salts in the crude product, filter off the solid impurities, and then spin off the toluene. Finally, the product was dissolved in a small amount of CH 2 Cl 2 Then, the mixed liquid...

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Abstract

The invention discloses a catalytic synthesis method of high molecular weight polycaprolactone, which belongs to the technical field of polymer materials. In the present invention, hydroxyl alcohol is used as an initiator, Lewis base catalyzes the hydroxyl hydrogen of the initiator to form an oxyanion, and the oxyanion attacks the carbonyl carbon of the ε-caprolactone monomer, and at the same time, the Lewis acid activates the carbonyl oxygen and stabilizes the terminal oxyanion, realizing the development Ring polymerization, after the polymerization is complete, terminate the reaction, and finally synthesize polycaprolactone. The Lewis acid-base of the invention is easy to obtain; the reaction is carried out at room temperature without heating and energy consumption, and is gentle and efficient; the reaction process is simple and easy to operate: the molecular weight of the polycaprolactone product is high and controllable.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and in particular relates to a method for catalytically synthesizing high molecular weight polycaprolactone. Background technique [0002] As a biodegradable material, polycaprolactone is widely used in medical fields such as surgical sutures, tissue engineering, drug sustained release systems, orthopedic fixation materials, etc. [0003] Polycaprolactone is generally prepared by ring-opening polymerization of ε-caprolactone (ε-CL). In the ring-opening polymerization reaction, the catalyst plays a very critical role. Today, researchers have developed a wide variety of highly efficient catalysts ranging from metal catalysts to organic catalysts and organometallic composite catalysts. However, many catalysts have more or less limitations, some polymers have low molecular weight, and some have uncontrollable molecular weight. There are few synthetic methods of this polycaprolactone with...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G63/84C08G63/83C08G63/82C08G63/87C08G63/08
CPCC08G63/08C08G63/823C08G63/826C08G63/83C08G63/84C08G63/87
Inventor 谢珊陶峻郭畅唐定良陈永福诸江徽张开炳
Owner 安徽红太阳新材料有限公司
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