Application of Binaphthol Derivatives in Living Radical Photopolymerization

A technology of derivatives and free radicals, which is applied in the field of organic photocatalysts to catalyze controllable active free radical polymerization, can solve problems such as the molecular weight growth does not show a good linear trend, the deviation between theoretical molecular weight and actual molecular weight, and the weakening of polymer molecular weight control. , to achieve the effects of controllable molecular weight, long modification and easy operation

Active Publication Date: 2021-09-24
FUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the catalytic efficiency of this system is low, and it needs long-term light to achieve a certain conversion rate, and the electron-donating amine system also leads to an increase in polymerization side reactions, weakening the control of polymer molecular weight, and the theoretical molecular weight and actual molecular weight appear larger. Deviation, the growth of molecular weight during polymerization does not show a good linear trend, and the control of polydispersity is also poor (PDI>1.40)
The amount of catalyst is large, generally 5% - 80% of the monomer amount is required, and it cannot be reduced to one-thousandth (1%) or less

Method used

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  • Application of Binaphthol Derivatives in Living Radical Photopolymerization
  • Application of Binaphthol Derivatives in Living Radical Photopolymerization
  • Application of Binaphthol Derivatives in Living Radical Photopolymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Example 1 3,3'-para-trifluoromethyl substituted phenyl-1,1'-binaphthol / ethyl 2-bromophenylacetate initiated photopolymerization experiment of MMA

[0034]According to the molar ratio [MMA]:[EBP]:[PC]=100:1:0.1, add the above raw materials into 10 ml Schlenk tube respectively, the volume of solvent N,N-dimethylacetamide (DMA) and monomer The ratio is 1:1. Sealed and the reaction mixture was degassed by refrigerated pumping three times, allowing the polymerization to proceed under an inert atmosphere. At room temperature, the reaction mixture was well stirred with a magnetic stirrer, and the mixture was irradiated by a purple LED (6 W) (the distance from the center of the reaction tube to the light source was controlled to be 2 cm). At a certain time interval, take a small amount of the reaction mixture and add it to deuterated chloroform containing BHT (250ppm) to terminate the polymerization, monitor the conversion rate by NMR, settle the remaining reaction solution in...

Embodiment 2

[0041] According to the molar ratio [MMA]:[EBP]:[PC]=100:0.5:0.01, 100:0.5:0.02 and 100:2:0.05, add the above raw materials into 10 ml Schlenk tube, solvent N,N-di The volume ratio of methylacetamide (DMA) to monomer was 1:1, sealed, and the reaction mixture was degassed by cryo-pumping three times, so that the polymerization was carried out in an inert atmosphere. Refer to Embodiment 1 for other operations.

[0042] Under the condition of [MMA]:[EBP]:[PC]= 100:0.5:0.01, after 5 hours of reaction, the monomer conversion rate reached 72.2%, and the Mn=15900 and PDI=1.53 of the polymerization product.

[0043] Under the condition of [MMA]:[EBP]:[PC]= 100:0.5:0.02, after 5 hours of reaction, the monomer conversion rate reached 74.3%, and the Mn=16200 and PDI=1.46 of the polymerization product.

[0044] Under the condition of [MMA]:[EBP]:[PC]= 100:2:0.05, after 5 hours of reaction, the monomer conversion rate reached 80.5%, and the Mn=8000 and PDI=1.20 of the polymerization produ...

Embodiment 3

[0046] The preparation of embodiment three PMMA-Br macroinitiators

[0047] Dissolve MMA (2.00 mL, 18.8 mmol, 1000 eq.), EBP (65.6 μL, 376 μmol, 20 eq.) and photocatalyst (18.8 μmol, 1 eq.) in 3.00 mL DMA and add the above materials into a 10 ml Schlenk tube , sealed, and the reaction mixture was degassed by cryo-evacuation three times, allowing the polymerization to proceed under an inert atmosphere. Refer to Embodiment 1 for other operations. After reacting for 4 hours, the reaction solution was poured into 150 mL methanol and stirred for 5 hours. The resulting precipitate was then isolated by vacuum filtration and washed with an appropriate amount of methanol. The polymer was then redissolved in a minimal amount of DMA, settled again by pouring into 100 mL of methanol, and stirred for 3 hours. The product was collected again by vacuum filtration and dried under reduced pressure to obtain a white powder (Mn = 5.00 kDa, PDI = 1.22), and the obtained PMMA polymer was dissol...

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Abstract

Application of binaphthol derivatives in living radical photopolymerization. The invention relates to the field of organic photocatalyst catalyzed controllable active free radical polymerization, in particular to 1,1'-bi-2,2'-naphthol derivatives used as organic photocatalysts to undergo active controllable free radical photopolymerization under visible light organic catalytic system. The present invention uses BINOL-based polymers as organic photoredox catalysts, which can achieve rapid reversible balance between dormant species and active chains, making the polymerization reaction controllable, and can prepare homopolymers with controllable molecular weight and low polydispersity. At the same time as compound and block copolymer, it also provides a new application method for BINOL organic polymers in organic photocatalytic active radical polymerization; the organic photocatalytic system involved in the present invention has high efficiency, low cost, easy operation, The prepared polymer has the characteristics of controllable molecular weight and narrow polydispersity, which conforms to the production concept of environment-friendly green production.

Description

technical field [0001] The invention relates to the field of organic photocatalyst catalyzed controllable active free radical polymerization, in particular to the use of 1,1'-bi-2,2'-naphthol (BINOL, binaphthol) derivatives as methacrylate monomers Organic photocatalyst, an organic catalytic system that undergoes active controllable radical photopolymerization under visible light. Background technique [0002] Since Szwarc et al. proposed the concept of living polymerization in 1956, living polymerization has become the most effective polymer synthesis method, because it can prepare polymers with specific structures and properties through precise design of polymer molecules, and truly realize precise control of molecular weight and molecular structure. Controlled / living radical polymerization (CRP) has the characteristics of relatively mild reaction conditions, wide range of applicable monomers, simple operation, low industrial cost, and wide application range of products, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F120/14C08F2/48C08F293/00
CPCC08F2/48C08F120/14C08F293/00
Inventor 廖赛虎马强
Owner FUZHOU UNIV
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