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Novel RAFT reagent based on pyridine, and preparation method and application thereof

A vinylpyridine, a new type of technology, applied in the preparation and application of RAFT reagents, can solve the problems of no RAFT regulator, and the stability cannot be too strong, and achieve excellent free radical polymerization regulation ability and high addition and fragmentation activity. Effect

Active Publication Date: 2018-06-01
HANGZHOU JIHUA POLYMER MATERIAL CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The R group should first be a good leaving group, and the formed R radical should be able to smoothly initiate the chain growth reaction of the monomer, and also need to be able to stabilize the free radical, but its stability should not be too strong
[0004] The reported dithioester RAFT agents are mainly based on benzene rings, pyrroles and alkanes, but no pyridine-based RAFT modulators

Method used

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  • Novel RAFT reagent based on pyridine, and preparation method and application thereof
  • Novel RAFT reagent based on pyridine, and preparation method and application thereof
  • Novel RAFT reagent based on pyridine, and preparation method and application thereof

Examples

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preparation example Construction

[0024] General embodiment: the preparation method of the novel RAFT reagent based on pyridine of the present invention comprises the following steps:

[0025] (1) Add 10-20 molar parts of magnesium bars, 30-60 molar parts of anhydrous ether and account for 0.1% of the mass of magnesium bars in the reactor with nitrogen feeding device, reflux condensing device, constant pressure dropping device and stirring device. -0.5% iodine, place the reactor in an ice-water bath under the protection of nitrogen, and while stirring (50-100rpm), add dropwise (1-2mL / min) 10-20 molar parts of halogenated aromatic hydrocarbons and 15-30 Mole parts of the mixture of anhydrous ether, continue to stir for 1-2h after the dropwise addition. Then heat to 40-45°C, react for 3-5h; after cooling to room temperature, place it in an ice-water bath, add dropwise (0.2-0.5mL / min) 10-20 mole parts of carbon disulfide and 20-40 mole parts of tetrahydrofuran After the dropwise addition is completed, the reacti...

Embodiment 1

[0029](1) add 10 molar parts of magnesium bar, 30 molar parts of anhydrous ether and the iodine that accounts for 0.1% of magnesium bar quality in the reactor that has nitrogen feed device, reflux condensing unit, constant pressure dripping device and stirring device, Under the state of nitrogen protection, place the reactor in an ice-water bath, and while stirring (50rpm), add dropwise (1mL / min) a mixture of 10 molar parts of benzyl chloride and 15 molar parts of anhydrous ether, and continue to Stir for 1h. Then heat to 40°C and react for 3 hours; after cooling to room temperature, place it in an ice-water bath, add dropwise (0.2mL / min) a mixture of 10 molar parts of carbon disulfide and 20 molar parts of tetrahydrofuran, and continue the reaction after the dropwise addition is completed 3h.

[0030] (2) The mixture obtained in step (1) is placed in a liquid separation device, after standing for 12 hours, the lower liquid phase is collected, 20 wt% hydrochloric acid with 11...

Embodiment 2

[0034] (1) Add 20 molar parts of magnesium bar, 60 molar parts of anhydrous ether and account for 0.5% iodine of magnesium bar mass in the reactor with nitrogen gas feeding device, reflux condensing device, constant pressure dripping device and stirring device, nitrogen gas Place the reactor in an ice-water bath in a protected state, and while stirring (100rpm), add dropwise (2mL / min) a mixture of 20 molar parts of benzyl bromide and 30 molar parts of anhydrous ether, and continue stirring after the addition is complete 2h. Then heat to 45°C and react for 5h; after cooling to room temperature, place it in an ice-water bath, add dropwise (0.5mL / min) a mixture of 20 mole parts of carbon disulfide and 40 mole parts of tetrahydrofuran, and continue the reaction after the dropwise addition is completed 5h.

[0035] (2) The mixture obtained in step (1) is placed in a separatory device, after standing for 24 hours, the lower liquid phase is collected, 20 wt% hydrochloric acid of 15....

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Abstract

The invention discloses a novel RAFT reagent based on pyridine, and a preparation method and application thereof, belonging to the field of RAFT reagents. The preparation method comprises the following steps: (1) adding magnesium strips, anhydrous ether and iodine, adding a mixture of halogenated aromatic hydrocarbons and anhydrous ether drop by drop, carrying out stirring and a heating reaction,then adding a mixture of carbon disulfide and tetrahydrofuran drop by drop after cooling, and then continuing the reaction; (2) subjecting a mixture obtained in the previous to standing, collecting alower liquid phase, adding hydrochloric acid into the liquid phase for acidification, adding anhydrous ether for extraction of an upper organic phase, and carrying out reduced-pressure distillation toremove anhydrous ether and tetrahydrofuran so as to obtain dithiocarboxylic acid; and (3) adding dithiocarboxylic acid and vinylpyridine into a reaction apparatus, adding carbon tetrachloride, and successively carrying out a reaction, separation and purification so as to obtain the finished RAFT reagent. The novel pyridine-based RAFT agent has higher addition fragmentation activity and excellentfree radical polymerization regulation ability for vinylpyridine monomers, and can be used for preparing polymers with designed molecular weight and narrow molecular weight distribution.

Description

technical field [0001] The invention relates to the technical field of preparation and application of RAFT reagents, in particular to a novel pyridine-based RAFT reagent and its preparation method and application. Background technique [0002] Poly 2(or 4)-vinylpyridine is a class of multipurpose functional polymer materials. Poly 2(or 4)-vinylpyridine is weakly basic, and the pyridine ring has N atoms and there are lone pairs of electrons on the N atoms, so it is thermodynamically unstable. It can be prepared through some polymer chemical reactions to prepare fine Polymer chemicals can be easily modified to be acidic, basic, or amphoteric, and can also be simply connected with the required ligands to generate polymer compounds with various properties. Compared with ordinary styrene polymers, poly 2 (or 4)-vinylpyridine has many unique advantages and functions, and can be used in the preparation of drug carriers, coatings, functional membranes, polymer electrolytes, surfact...

Claims

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Application Information

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IPC IPC(8): C08F2/38C08F126/06C07D213/32
CPCC07D213/32C08F2/38C08F126/06C08F2438/03
Inventor 钱涛刘海龙
Owner HANGZHOU JIHUA POLYMER MATERIAL CO LTD