A catalytic system for ring-opening polymerization of lactones with controllable activity

A ring-opening polymerization and catalytic system technology, applied in the field of active controllable polymerization catalytic system, can solve the problems of low polymer molecular weight, large amount of catalyst, wide molecular weight distribution, etc., and achieve wide substrate applicability, narrow molecular weight distribution, The effect of using less

Active Publication Date: 2019-04-09
JILIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The current technical status is that the reaction conditions are harsh, such as the reaction requires heating, the amount of catalyst used is large (the molar ratio of monomer to catalyst is generally about 100:1), and the use of precious metal catalysis is often accompanied by side reactions of transesterification. Not high, mostly between 2 and 100,000 g / mol, and the molecular weight distribution is wide (Robert M. Waymouth et al., Angew. Chem. Int. Ed. 2011, 50, 6388–6391; Didier Bourissou et al. Soc.2013,135,13306-13309; Andrew P.Dove et al., J.Am.Chem.Soc.,2015,137,14439–14445; Lang Jianping CN201510488607.3)

Method used

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  • A catalytic system for ring-opening polymerization of lactones with controllable activity
  • A catalytic system for ring-opening polymerization of lactones with controllable activity
  • A catalytic system for ring-opening polymerization of lactones with controllable activity

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] A kind of specific synthetic method of Lewis base described in embodiment 1 present invention

[0053] Synthesis of 1,3-Dimethyl-4,5-diphenyl-2-(2-propenyl)-2,3-dihydro-1H-imidazole.

[0054] 1) Synthesis of 2-isopropyl-4,5-diphenyl-1H-imidazole

[0055]

[0056] Take ammonium acetate (7.7g, 99.9mmol) in a 250mL pressure-resistant reaction flask, add methanol (150mL) and cool to 0°C, add isobutyraldehyde (3.6g, 49.9mmol) and dibenzoyl (10.5g, 49.9mmol) . Seal the reaction bottle, put it into an oil bath at 120°C and stir for 3h. Cool, concentrate methanol in vacuo, filter, wash with ether (3 x 30 mL), collect an off-white solid and dry in vacuo (8.0 g, 61.0%). 1 H NMR (300MHz, DMSO-d 6 )δ11.92(s,1H,NH),7.48–7.16(m,10H,Ph),3.01(sept,J=7.1Hz,1H,CHMe 2 ), 1.31 (d, J=7.1Hz, 6H, CHMe 2 ).

[0057] 2) Synthesis of 1,3-dimethyl-2-isopropyl-4,5-diphenylimidazolium iodide salt

[0058]

[0059] Take 2-isopropyl-4,5-diphenylimidazole (8.0g, 30.5mmol) in a 250mL roun...

Embodiment 2

[0063] The ring-opening polymerization of embodiment 2 δ-valerolactone (δ-VL)

[0064] There are three feeding methods in the polymerization process: 1. Pre-mix Lewis acid and Lewis base for 10 minutes, and then add monomer; 2. Pre-mix Lewis acid and monomer, and then add Lewis base; 3. Pre-mix Lewis base and monomer, and then Add Lewis acid. Regardless of the feeding method, the ring-opening polymerization of lactone can be well realized.

[0065] The polymerization reaction was carried out in a glove box, and δ-valerolactone (4.0g, 40mmol) was weighed, a suitable amount of solvent was placed in a 30ml reaction bottle (the total volume of the solution was 10mL), Lewis base and Lewis acid were added respectively, and the timing was started , and stirred for a period of time until the monomer was completely converted, the reaction bottle was taken out of the glove box, and 5% HCl / methanol solution was added to terminate the polymerization reaction. The polymer was filtered of...

Embodiment 3

[0072] The ring-opening polymerization of embodiment 3ε-caprolactone (ε-CL)

[0073] The polymerization reaction was carried out in a glove box, and an appropriate amount of solvent was weighed in a 30 milliliter reaction bottle (to keep the total volume of the solution at 10 mL), adding Lewis base and Lewis acid, stirring for 10 minutes, and then adding ε-caprolactone (4.56 g, 40mmol), and start timing, stirring for a period of time until the monomer is completely converted, the reaction bottle is taken out from the glove box, and 5% HCl / methanol solution is added to terminate the polymerization reaction. The polymer was filtered off, washed thoroughly with methanol, and dried under vacuum at 60°C to constant weight. The resulting polymer passed 1 H / 13 CNMR identification, molecular weight and molecular weight distribution of the polymer were measured by gel permeation chromatography and laser light scattering. 1 HNMR (500MHz, Chloroform-d) δ4.06 (t, J = 6.7Hz, 2H), 2.30 ...

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Abstract

The invention discloses an activity-controllable catalysis system for catalyzing inner ester ring opening polymerization, and belongs to the technical field of macromolecular synthesis. Inner ester serving as a monomer raw material is subjected to ring opening polymerization under the synergetic catalysis of Lewis acid and Lewis alkali under a condition of no use of a solvent or use of an organic solvent. The activity-controllable catalysis system has the advantages of readily available raw material, convenience for operation, mild reaction condition, quickness, high conversion rate and the like; furthermore, the use amount of a catalyst is small; the molecular weight of an obtained polymer is controllable, and the molecular weight distribution is narrow; the activity-controllable catalysis system realizes activity-controllable polymerization, and can realize copolymerization among different inner esters.

Description

technical field [0001] The invention belongs to the technical field of polymer synthesis, and in particular relates to an activity-controllable polymerization catalyst system, which can be applied to the activity-controllable ring-opening polymerization of lactones and the copolymerization between different lactones. Background technique [0002] Aliphatic polyester is a kind of polymer with good biocompatibility and biodegradability. Because of its structural repeating unit, there are multiple repeating non-polar methylene groups and a polar ester group, so the material is also It has good flexibility and processability, exhibits good mechanical properties, and is widely used in food packaging, plastic films, medical materials and other fields, so it has attracted more and more attention. Therefore, aliphatic polyester has always been a research hotspot in related fields such as chemistry and medical polymer materials. [0003] At present, the synthesis of aliphatic polyes...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G63/87C08G63/84C08G63/83C08G63/08
CPCC08G63/08C08G63/823C08G63/87
Inventor 张越涛何江华王前义
Owner JILIN UNIV
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