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Application of binaphthol derivatives in aspect of active free radical photopolymerization reaction

A technology of free radicals and derivatives, applied in the field of organic photocatalyst catalyzed controllable living radical polymerization, can solve the problems such as the molecular weight growth does not show a good linear trend, the theoretical molecular weight and the actual molecular weight deviation, and the polymer molecular weight control becomes weak. , to achieve the effect of polydispersity, long shelf life and easy operation

Active Publication Date: 2020-03-17
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 aspect of active free radical photopolymerization reaction
  • Application of binaphthol derivatives in aspect of active free radical photopolymerization reaction
  • Application of binaphthol derivatives in aspect of active free radical photopolymerization reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Example 1 Photopolymerization experiment of MMA initiated by 3,3'-para-trifluoromethyl substituted phenyl-1,1'-binaphthol / 2-bromophenyl ethyl acetate

[0034] According to the molar ratio [MMA]:[EBP]:[PC]=100:1:0.1, add the above-mentioned raw materials to a 10 ml Schlenk tube, respectively, the solvent N,N-dimethylacetamide (DMA) and monomer The volume ratio is 1:1. After sealing, the reaction mixture was degassed by freezing and pumping three times, so that the polymerization was carried out in an inert atmosphere. At room temperature, stir the reaction mixture with a magnetic stirrer, and irradiate the mixture with a purple LED (6 W) (control the distance from the center of the reaction tube to the light source to be 2 cm). At a certain time interval, a small amount of the reaction mixture was added to deuterated chloroform containing BHT (250 ppm) to terminate the polymerization, the conversion rate was monitored by nuclear magnetism, the remaining reaction liquid was...

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 do not add the above raw materials to a 10 ml Schlenk tube, solvent N, N-two The volume ratio of methylacetamide (DMA) to monomer is 1:1, sealed, and the reaction mixture is degassed by refrigerating and pumping three times, so that the polymerization proceeds in an inert atmosphere. Refer to Embodiment 1 for other operations.

[0042] Under the condition of [MMA]:[EBP]:[PC]=100:0.5:0.01, the reaction time was 5h, the monomer conversion rate reached 72.2%, the Mn=15900, PDI=1.53 of the polymerized product.

[0043] Under the condition of [MMA]:[EBP]:[PC]=100:0.5:0.02, reacted for 5h, the monomer conversion rate reached 74.3%, the polymerized product had Mn=16200, PDI=1.46.

[0044] Under the condition of [MMA]:[EBP]:[PC]=100:2:0.05, reacted for 5h, the monomer conversion rate reached 80.5%, the polymerized product had Mn=8000, PDI=1.20.

[0045] It shows that as the ratio of monomer and ini...

Embodiment 3

[0046] Example 3 Preparation of PMMA-Br macroinitiator

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

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Abstract

The invention discloses application of binaphthol derivatives in the aspect of active free radical photopolymerization reaction, and relates to the field of controllable active free radical polymerization catalyzed by organic photocatalysts, in particular to an organic catalytic system which takes 1, 1'-bi-2, 2'-naphthol derivatives as organic photocatalysts and generates activity-controllable free radical photopolymerization under visible light. According to the invention, a BINOL polymer is used as an organic photooxidation reduction catalyst, so that rapid reversible equilibrium between dormant species and an active chain can be achieved, the polymerization reaction has controllability, and a novel application method for the BINOL organic polymer in the organic photocatalytic active free radical polymerization is provided while a homopolymer and a block copolymer with characteristics of the controllable molecular weight and the low polydispersity can be prepared; and moreover, the organic catalytic system provided by the invention has the characteristics of high efficiency, low cost and easiness in operation, and the prepared polymer has the characteristics of the controllable molecular weight and the narrow polydispersity, and conforms to the production concept of environment-friendly green production.

Description

Technical field [0001] The invention relates to the field of organic photocatalyst catalyzed and controllable active free radical polymerization, in particular to 1,1'-bi-2,2'-naphthol (BINOL) derivatives as methacrylate monomers Organic photocatalyst, an organic catalytic system in which activity controllable free radical photopolymerization occurs 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 method of polymer synthesis, because it can be used to precisely design polymer molecules to prepare polymers with specific structures and properties. It has precise control of molecular weight and molecular structure. Controlled / living radical polymerization (CRP) has the characteristics of relatively mild reaction conditions, a wide range of applicable monomers, simple operation, low industrial cost, and a wide range of applications. It has unique advantage...

Claims

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Application Information

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Patent Type & Authority Applications(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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