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A kind of method for preparing diselenide polymer

A technology of polymer and diselenide, which is applied in the field of polymer synthesis, can solve the problems of small selection range of monomers, narrow selection range, poor solubility of polymers, etc., and achieve simple and controllable preparation process, convenient structure modification, monomer The effect of wide applicability

Inactive Publication Date: 2017-02-08
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] (1) Preparation by condensation polymerization of dihalogenated hydrocarbons and sodium diselenide: Mikawa, R. et al. used dihalogenated hydrocarbons and sodium diselenide as raw materials to prepare diselenide polymers by condensation polymerization (see: Mikawa, R.; Nogami, T.; Hasegawa, T. 1986. Jpn Kokai Tokkyo Koho JP 6128527); the polymers synthesized by this method have small molecular weight and uncontrollable molecular weight distribution;
[0007] (2) Acidic or alkaline hydrolysis of diselenide cyanate, followed by condensation polymerization preparation: Morgan, G. T. et al. used diselenide cyanate as raw material to prepare diselenide polymer through hydrolysis reaction and condensation polymerization (see : Morgan, G.T.; Burstall, F. H. J. Chem. Soc . 1929, 1096); the precursor synthesis of this type of polymer is relatively difficult, and the range of monomer selection is small;
[0008] (3) Preparation of aryl diselenide polymer by double Grignard reagent method: Günther, W. H. H. et al. used dibromobenzene as raw material to prepare aryl diselenide polymer through Grignard reaction (see: Günther, W. H. H.; Salzman, M. N. Ann. N. Y. Acad. Sci . 1972,192 , 25); The polymers synthesized by this type of method usually have poor solubility and are difficult to apply in practice;
[0010] To sum up, the current existing methods can synthesize diselenide polymers, but there are some problems, such as the selection range of monomers is narrow, and the synthesized The polymer molecular weight and structure cannot be precisely controlled, or polymer materials with predetermined molecular weight and selenium content cannot be synthesized, which limits the research and application of diselenide polymers

Method used

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  • A kind of method for preparing diselenide polymer
  • A kind of method for preparing diselenide polymer
  • A kind of method for preparing diselenide polymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] (1) Preparation of O-(4-methoxyphenyl)-Se-benzyl diselenocarbonate

[0044] Add 1.24g (10mmol) p-methoxyphenol, 0.56g (10mmol) KOH and 5mL dimethyl sulfoxide into a 50mL round bottom flask, stir at room temperature until KOH is completely dissolved, then add 1.72g (10mmol) CSe dropwise 2 DMSO (5 mL) solution, after 10 min of reaction, 1.27 g (10 mmol) benzyl chloride was added, and the reaction was terminated after 2 hours. Add 50 mL of water to the reaction solution, extract with dichloromethane (25 mL*2), combine the organic layers, wash once with saturated brine, dry the organic layer over anhydrous sodium sulfate, concentrate, and obtain the pure product by column chromatography.

[0045] In the same way, phenol, carbon diselenide and α-bromophenylacetic acid methyl ester can be synthesized as raw materials O -Phenyl- Se -(α-methylphenylacetate) diselenocarbonate.

[0046] (2) O -(4-Methoxyphenyl)- Se Preparation of diselenocarbonate-terminated polystyrene with...

Embodiment 2

[0058] (1) Preparation of diselenocarbonate-terminated polymethyl methacrylate

[0059]

[0060] Molar ratio [methyl methacrylate] 0 / [ O -(4-Methoxyphenyl)- Se -(α-methylphenylacetate) diselenocarbonate] 0 / [Azobisisobutylcyanide] 0 = 60 / 1 / 0.5, add azobisisobutyronitrile in turn, O -(4-Methoxyphenyl)- Se -(α-methyl phenylacetate) diselenocarbonate, methyl methacrylate in a 5 mL ampoule, seal the tube, and carry out bulk polymerization: place the sealed ampoule at a constant temperature (60°C ) for 15 hours in an oil bath; after the reaction, take out the sealed tube, immediately cool it with cold water, open the sealed tube, dissolve it with 2-5 mL of tetrahydrofuran, drop it into 250 mL of methanol, precipitate, suction filter, vacuum Oven drying, obtain diselenocarbonate-terminated polymethyl methacrylate, measured number average molecular weight is 8600g / mol, and theoretical number average molecular weight is 6200 g / mol, and molecular weight distribution is 1.45, ...

Embodiment 3

[0066] (1) Preparation of diselenocarbonate-terminated polyvinyl acetate

[0067]

[0068] According to the ratio [vinyl acetate] 0 / [ O -(4-Methoxyphenyl)- Se -(α-methylphenylacetate) diselenocarbonate] 0 / [Azobisisobutylcyanide] 0 = 200 / 1 / 1, add azobisisobutyronitrile successively, O -(4-Methoxyphenyl)- Se -(α-methylphenylacetate) diselenocarbonate, vinyl acetate in a 5 mL ampoule, seal the tube, and perform bulk polymerization: place the sealed ampoule at a constant temperature (70°C) After the reaction, take out the sealed tube, cool it with cold water immediately, open the sealed tube, dissolve it with 2~5mL of tetrahydrofuran, drop it into 250mL of n-hexane to precipitate, filter it with suction, and dry the filter residue in a vacuum oven. Diselenated carbonate-terminated polyvinyl acetate was obtained, the measured number average molecular weight was 2400 g / mol, the theoretical number average molecular weight was 2700 g / mol, the molecular weight distribution w...

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Abstract

The invention discloses a method for preparing diselenide polymer, comprising the following steps: a polymerization system is prepared, a free radical polymerization reaction is carried out, and separation and purification are conducted so as to obtain a polymer with high terminal functionality; and after dissolved, the polymer with high terminal functionality reacts with an aliphatic primary amine solution to obtain a polymer containing a diselenide structure. The polymerization system contains a monomer, a regulating agent and an initiator, wherein the monomer is a monomer capable of free radical polymerization and the regulating agent is a synthesized disdeno-carbonic ester compound. As the used polymerization method has the characteristic of 'active' / controllable polymerization, the synthesized diselenide structured polymer has characteristics of narrow molecular weight distribution, simple synthesis, wide applicability of the monomer and the like. The whole preparation process is simple, controllable, efficient and environmentally friendly. The method is suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of macromolecule synthesis, and relates to a method for preparing a polymer containing a diselenide structure by using diselenocarbonate to regulate free radical polymerization and aminolysis reaction. Background technique [0002] Most organoselenium compounds have strong physiological activity and are widely used in medicine and synthetic chemistry. Because selenium has many unique properties, people have tried to introduce selenium into molecular chains in synthetic polymers for a long time, and have discovered many interesting properties and developed a wealth of applications. [0003] The diselenide polymer can be formed by introducing the selenide structure into the backbone of the polymer chain. Diselenide has efficient redox responsiveness. By adding reducing agent or oxidizing agent, the polymer can be made to have efficient redox responsiveness. Through the change of polymer chain structure and th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G81/02C08F112/08C08F120/14C08F118/08C08F2/02
Inventor 潘向强高峰朱健朱秀林张正彪张伟程振平周年琛
Owner SUZHOU UNIV