DMAP-thiourea catalyst and preparation method thereof, and high-molecular-weight biodegradable polyester and preparation method thereof

A technology for biodegrading polyester and thiourea catalysts, applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problems of low molecular weight of polyesters, and achieve The effect of high molecular weight, optimized polymerization temperature, and narrow distribution

Active Publication Date: 2021-07-09
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the molecular weight of polyesters obtained by ring-opening polymerization of OCAs monomers is

Method used

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  • DMAP-thiourea catalyst and preparation method thereof, and high-molecular-weight biodegradable polyester and preparation method thereof
  • DMAP-thiourea catalyst and preparation method thereof, and high-molecular-weight biodegradable polyester and preparation method thereof
  • DMAP-thiourea catalyst and preparation method thereof, and high-molecular-weight biodegradable polyester and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0079] The preparation method of acid anhydride in O-carboxyl ring:

[0080]

[0081] Dissolve α-hydroxy acid (10mmol) in 30mL of anhydrous tetrahydrofuran, add 200mg of activated carbon, 6.7mmol of triphosgene, stir at room temperature for 20 hours, filter with suction, and recrystallize from diethyl ether three times to obtain O-carboxyl ring anhydride. Spectra and carbon spectrum characterization, as follows.

[0082] (1) L-EthylOCA: 1 H NMR (300MHz, CDCl 3 ):δ5.06-5.10(t,1H),1.90-2.14(m,2H),1.07-1.12(t,3H). 13 C NMR (300MHz, CDCl 3 ): δ167.02, 148.50, 79.92, 21.45, 10.21.

[0083] (2) L-tBuOCA: 1 H NMR (300MHz, CDCl 3 ): δ4.71(s,1H),1.12(s,9H). 13 C NMR (300MHz, CDCl 3 ): δ165.76, 148.77, 86.80, 35.33, 25.03.

[0084] (3)L-LacOCA: 1 H NMR (300MHz, CDCl 3 ):δ5.13(q,1H),1.68(d,3H). 13 C NMR (300MHz, CDCl 3 ): δ167.96, 148.39, 76.41, 16.34.

[0085] (4) L-Ser(Bn)OCA: 1 H NMR (300MHz, CDCl 3 ):δ7.26-7.40(m,5H),5.10(m,1H),4.60(m,2H,),3.91(m,2H,). 13 C NMR (C...

preparation Embodiment 1

[0095] Preparation Example 1 Preparation of Catalyst 1

[0096]

[0097] Specific steps are as follows:

[0098] (1) Add 1.43g (10mmol) of 4-chloro-2-pyridinemethanol, 3.15g (12mmol) of triphenylphosphine, 1.77g (12mmol) of phthalimide and 15mL of anhydrous tetrahydrofuran into a round bottom flask . Stir at 0°C for 15 minutes. Azodiisopropyl ester 2.4mL (15mmol) was slowly added dropwise into the solution. After the dropwise addition, slowly return to room temperature and stir for 12h. A white solid was obtained by suction filtration with a yield of 60%. With deuterated chloroform (CDCl 3 ) as a reagent with a 300 MHz nuclear magnetic resonance instrument (hydrogen spectrum, 1 H NMR) to characterize its structure. 1 H NMR (300MHz, CDCl 3 ): δ8.43(d,1H),7.89-7.91(m,2H),7.74-7.77(m,2H),7.29(s,1H),7.20(d,1H),4.99(s,2H).

[0099] (2) Dissolve 1.36g (5mmol) of the product from the previous step in 15mL of ethanol, add 2.4mL of hydrazine hydrate and reflux for 3h. Extr...

preparation Embodiment 2

[0102] Preparation Example 2 Preparation of Catalyst 5

[0103]

[0104] Specific steps are as follows:

[0105] Steps (1) and (2) follow steps (1) and (2) of Catalyst 1 synthesis.

[0106] (3) Put 0.50g (3.5mmol) of 4-chloro-2-pyridinemethylamine, 10mL of water, 2.49g (35mmol) of pyrrolidine and 1.4g (35mmol) of sodium hydroxide in a sealed tank, and stir at 100°C for 24 hours , to obtain 4-pyrrolidinyl-2-pyridinemethanamine with a yield of 60%. deuterated dimethyl sulfoxide (DMSO-d 6 ) as a reagent with a 300 MHz nuclear magnetic resonance instrument (hydrogen spectrum, 1 H NMR) characterized the structure of 4-pyrrolidinyl-2-pyridinemethylamine. 1 H NMR (300 MHz, DMSO-d 6 ):δ8.00(d,1H),6.48(s,1H),6.30(d,1H),3.61(s,2H),3.24(m,4H),1.94(m,4H).

[0107] (4) Add 0.354g (2mmol) of 4-pyrrolidinyl-2-pyridinemethanamine, 0.540g (2mmol) of 3,5-bis(trifluoromethyl)phenylisothiocyanate and 3 mL of dichloromethane. Stir at room temperature for 12 hours. Catalyst 5 was obtain...

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Abstract

The invention relates to a DMAP-thiourea catalyst and a preparation method thereof as well as high-molecular-weight biodegradable polyester and a preparation method thereof. The DMAP-thiourea catalyst disclosed by the invention has the characteristic of living polymerization when being used for catalyzing ring opening polymerization of O-carboxyl anhydride monomers (OCAs). According to the DMAP-thiourea catalyst disclosed by the invention, a thiourea group is used as Lewis acid, a monomer is activated through a hydrogen bond, DMAP is used as Lewis alkali and a nucleophilic addition monomer, and ring opening polymerization of an OCAs monomer is commonly catalyzed by utilizing an adjacent synergistic effect. Especially, the increased active species are zwitterions, and no alcohol is needed as an initiator. The polymerization speed is high, the reaction temperature is low, and the obtained polyester is high in molecular weight and narrow in distribution. By adjusting the structure of the catalyst, changing the acidity and alkalinity of the catalyst and the steric hindrance of the catalyst and optimizing parameters such as polymerization temperature, concentration and the like, controllable polymerization of the OCAs monomer is realized, and finally, biodegradable polyester with molecular weight as high as 130,000 is obtained.

Description

technical field [0001] The invention relates to the technical field of polymer material preparation, in particular to a DMAP-thiourea catalyst and a preparation method thereof, and a high molecular weight biodegradable polyester and a preparation method thereof. Background technique [0002] With the development and progress of human society, the demand for polymer materials such as plastics, fibers, and rubbers is increasing year by year. However, with the continuous consumption of petroleum resources, the utilization of renewable resources has been put on the agenda. The significance of using renewable resources to synthesize polymer materials is self-evident. In addition, traditional polymer materials are poor in biodegradability and biocompatibility. Therefore, it is important to synthesize polymer materials with good degradability and biocompatibility. [0003] Polyα-hydroxy acid is an attractive biodegradable and biocompatible polymer widely used in biomedicine, agr...

Claims

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Application Information

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IPC IPC(8): C07D213/74B01J31/02C08G63/87C08G63/00
CPCC07D213/74B01J31/0271B01J31/0244C08G63/87C08G63/00
Inventor 陶友华李茂盛张帅
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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