A kind of living/controllable radical polymerization method of water-soluble monomer

A technology of water-soluble monomers and polymerization methods, which is applied in the field of active/controllable free radical polymerization of water-soluble monomers in water, can solve the problems of poor controllability of polymerization reactions, and achieve difficult decomposition, increased reaction efficiency, and low reaction components little effect

Active Publication Date: 2016-03-30
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, many side reactions tend to take place in water, resulting in poor polymerization control (see TsarevskyN.V., PintauerT., MatyjaszewskiK., Deactivation efficiency and degree of control over polymerization in ATRP inproticsolvents, Macromolecules2004,37:9768-9778 and Tsarevsky N.V., Braunecker W.A., Vacca A., Gans P., Matyjaszewski K., Competitive equilibriainatom transfer radical polymerization, Macromol. Symp.,2007, 248:60-70)

Method used

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  • A kind of living/controllable radical polymerization method of water-soluble monomer
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  • A kind of living/controllable radical polymerization method of water-soluble monomer

Examples

Experimental program
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Effect test

Embodiment 1

[0029] Example 1: Preparation of 1-cyano-1-methylethyl N,N-diethyldithiocarbamate.

[0030] In a three-neck round bottom flask, add tetraethylthiuram disulfide (TETD) (9.03 g, 0.030 mol), azobisisobutyronitrile (AIBN) (7.5 g, 0.045 mol) and 100 mL of toluene, and flush with nitrogen Deoxygenation was performed for 30 minutes, followed by reaction at 55° C. for 65 hours in a nitrogen atmosphere. The white precipitate was removed by filtration, and the toluene was removed by rotary evaporation to obtain a crude product. The crude product was distilled under reduced pressure at 107~115°C and 1mmHg to obtain a light yellow product, which 1 H-NMR (400MHz, CDCl3 ) spectrum and IR (KBr) spectrum such as figure 1 and figure 2 shown.

Embodiment 2

[0031] Example 2: Polymerization of polyethylene glycol monomethyl ether methacrylate at 70°C.

[0032] With 3mL water as solvent, PEGMEMA (1mL, 2.28mmol), Cu(OAc) 2 (2.2mg, 0.012mmol) and MANDC (5.1mg, 0.024mmol) were added to a 5mL ampoule, nitrogen gas was passed through the ampoule for 20 minutes to remove the oxygen in it, the mouth of the bottle was melted and sealed in time, and the ampoule was placed in Polymerization was carried out in an oil bath at 70°C. After reacting for 2 hours, take it out and put it in ice water, open the ampoule, freeze-dry the reaction solution to remove water, dissolve it in THF, precipitate it in about 200mL of n-hexane, pour off the upper solution after standing still, and dry it. to obtain the desired polymer.

Embodiment 3

[0033] Example 3: Polymerization of hydroxyethyl methacrylate at 70°C.

[0034] With 1.5mL water and 1.5mL methanol as solvent, HEMA (1mL, 8.25mmol), Cu(OAc) 2 (8.0mg, 0.044mmol), MANDC (18.5mg, 0.085mmol) were added to a 5mL ampoule, and neon gas was passed through the ampoule for 20 minutes to remove the oxygen in it, and the mouth of the bottle was melted and sealed in time, and the ampoule was placed Polymerization was carried out in an oil bath at 70°C. After reacting for 2 hours, take it out and put it in ice water, open the ampoule bottle, freeze-dry the reaction solution to remove water, dissolve it in DMF, precipitate it in about 200mL of n-hexane, let it stand, filter it with suction, and dry it to get the Polymer is required.

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Abstract

The invention discloses a living / controllable free radical polymerization method of a water-soluble monomer, which comprises the following steps: adding a water-soluble monomer, a pseudohalogen initiator, a catalyst and a solvent into a polymerization reaction vessel, and removing the water-soluble monomer with an inert gas Seal the polymerization reaction container after oxygen, and then carry out the polymerization reaction at 20~90°C for 0.5~53 hours, wherein the molar ratio between the water-soluble monomer, the pseudohalogen initiator and the catalyst is 50~1000:1:0.005~0.5 . The present invention makes full use of the special effect between the catalyst copper acetate and the initiator dithiocarbamate, constructs a simple and efficient active / controllable free radical polymerization system in water, and successfully obtains the molecular weight can be designed and the molecular weight distribution is relatively Narrow water-soluble polymers and amphiphilic block copolymers. In addition, the polymerization method of the present invention avoids the use of expensive ligands, which reduces production costs; at the same time, it does not need any additives, which simplifies the polymerization operation.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and relates to a general synthesis method for easily and rapidly obtaining water-soluble polymers and amphiphilic block copolymers with programmable molecular weight and narrow molecular weight distribution, in particular to a water-soluble monomer in Living / Controlled Radical Polymerization Method in Water. Background technique [0002] Vinyl water-soluble monomers such as polyethylene glycol monomethyl ether methacrylate, hydroxyethyl methacrylate, N,N-dimethylaminoethyl methacrylate and N,N-dimethylacrylamide, It is a common free radical polymerization functional monomer, which can be either homopolymerized or copolymerized. Because its corresponding polymer has a lot of special properties in aspects such as biocompatibility, hydrophilicity, thereby has extensive application in biological material and chemical industry field (referring to SiegwartD.J., OhJ.K., MatyjaszewskiK., ATRPinthedesig...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F2/00C08F120/28C08F120/34C08F120/54C08F293/00
Inventor 程振平蒋红娟张丽芬朱秀林
Owner SUZHOU UNIV
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