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A kind of polymerization method for preparing fluorine-containing alternating polymer by photocatalyst

The technology of a photocatalyst and a polymerization method is applied in the field of polymerization of preparing fluorine-containing alternating polymers through photocatalysts, which can solve the problems of few reports of brush-like polymers, and achieve the effects of green reaction and pollution avoidance.

Active Publication Date: 2020-04-03
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, there are very few reports on the preparation of brush polymers whose main chain is fluoropolymers, and it is also a difficulty in modifying fluoropolymers.

Method used

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  • A kind of polymerization method for preparing fluorine-containing alternating polymer by photocatalyst
  • A kind of polymerization method for preparing fluorine-containing alternating polymer by photocatalyst
  • A kind of polymerization method for preparing fluorine-containing alternating polymer by photocatalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Metal-free stepwise transfer-addition-terminated polymerization catalyzed by 2,4,6-triphenylmethoxypyranyl tetrafluoroborate (1b) in a mixed solvent system of dimethyl carbonate and acetonitrile

[0032] according to n A2 :n B1 :n 1b :n AsAc-Na = 100:100:10:50 initial molar ratio, bifunctional monomer A2 (1,6-diiodoperfluorohexane) (0.2769 g, 0.5 mmol), B1 (1,7-octadiene) (74.0 μL, 0.5 mmol), 2,4,6-tri-p-phenylmethoxypyranyl tetrafluoroborate (1b) (12.5 mg, 0.05 mmol), AsAc-Na (49.6 mg, 0.25 mmol) were added to In the mixed solvent system of acetonitrile and dimethyl carbonate (V 乙腈 :V 碳酸二甲酯 =1:3), add a stirring bar, and seal the tube directly after four deoxygenation operations. Then transfer the ampoule to a magnetic stirrer with a set speed (1800 rpm) and carry out photopolymerization at room temperature under LED blue light illumination. After reaching the given time (24 h), take out and open the airtight container, and use the polymerization system to Tet...

Embodiment 2

[0034] Effect of different organic photocatalysts on metal-free catalyzed free radical transfer-addition-termination polymerization in mixed solvent system of dimethyl carbonate and acetonitrile

[0035] Through the selection of various types of organic photocatalysts and a large number of literature research, we mainly use p-methoxybenzaldehyde (1a), 2,4,6-tri-p-benzyloxypyran Tetrafluoroborate (TPP+BF4-) (1b) and eosin Y (1c) were used as organic photocatalysts to catalyze the alternating copolymerization of perfluorodiiodide monomers and non-conjugated diene monomers. Since p-methoxybenzaldehyde (1a) acts as a photosensitizer, it mainly catalyzes the polymerization reaction through the energy transfer process, while 2,4,6-tri-p-benzyloxypyranyl tetrafluoroborate (1b) and Eosin Y (1c) has excellent photoredox properties and catalyzes the polymerization reaction mainly through a reversible electron transfer process. The specific catalytic effect results of these three are sh...

Embodiment 3

[0041] Using 2,4,6-tri-p-phenylmethoxypyranyl tetrafluoroborate (1b) as an organic photocatalyst, the effect of different solvent system ratios on metal-free catalyzed stepwise transfer-addition-termination polymerization

[0042] In view of the activity of perfluoro radicals and the reaction efficiency between functional groups, in the metal-free catalyzed radical transfer-addition-termination polymerization system of perfluoro diiodide monomers and non-conjugated diene monomers, the solvent The polarity of the polymer can affect the initiation efficiency of the entire polymerization process, the reaction rate and the degree of side reactions. In addition, since fluoropolymers are poorly soluble in conventional solvents, finding a solvent system with good solubility for the polymer is a key factor to improve the polymerization efficiency. According to the method recorded in Example 1, we plan to adopt different mixed solvent systems, such as tetrahydrofuran, dimethyl carbonat...

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Abstract

The invention provides a polymerization method for preparing fluorine-containing alternative polymer through a photocatalyst. The polymerization method includes following steps: (1), adding two bifunctional monomers A and B, organic photocatalyst and promoter into a mixed organic solvent system, stirring in a reaction container to enable the system to be homogeneous, and sealing the reaction container after deoxidizing for four times; (2), setting temperature of the reaction container to 25 DEG C, and allowing polymerization reaction for 1-200h through photocatalysis in a condition that rotating speed is 1500-2000rpm; (3), after the reaction is finished, adding tetrahydrofuran to dilute a polymerization system, pouring into methanol, precipitating, suction-filtering, and drying to obtain the fluorine-containing alternative polymer. The organic photocatalyst is used to replace a conventional metal photocatalyst, a free radical step-by-step polymerization novel method which is simple, economical, efficient and environment-friendly is designed, and a brand-new method is provided to obtain various fluorine-containing alternative polymers having different microstructures.

Description

technical field [0001] The invention relates to the technical field of sequential controllable polymerization, and relates to a polymerization method for preparing fluorine-containing alternating polymers through photocatalysts, and in particular to realizing the gradual transfer-addition- Termination (Organocatalyzed Transfer-Addition & Radical-Termination, O-START) aggregation. Background technique [0002] In view of the unique physical and chemical properties of fluorine atoms, fluorine-containing polymers are widely used in high-tech fields, and can be used to prepare thermoplastic materials, films and semiconductor materials. Among them, semifluoropolyolefin is a special kind of fluorine-containing polymer material. Its unique strict alternating structure of perfluorinated segments and alkane segments endows it with unique liquid crystal properties, and has been extensively studied since its inception. However, due to the harsh reaction conditions required by traditio...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G61/04C08G61/02C08G61/12
Inventor 程振平徐天驰张丽芬朱秀林
Owner SUZHOU UNIV
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