Method for preparing amphiphilic block copolymer through cooperation of light-operated free radical polymerization and ring-opening copolymerization

A technology of block copolymers and free radicals, applied in the field of synthesis of amphiphilic polymers, can solve problems such as the inability to realize the regulation of the molecular weight of the two blocks and limited types of monomers

Pending Publication Date: 2021-10-08
ANYANG INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Recently, the simultaneous preparation of amphiphilic polymers by using two polymerization forms in one pot has attracted much attention. The amphiphilic block polymer of polypyrrolidone and polycaprolactone was obtained. However, both polymerizations in this method depend on the influence of temperature. Only when the temperature meets the requirements of the two polymerization forms at the same time can the two polymerizations be carried out simultaneously. , and the molecular weight or ratio of the two blocks is heavily dependent on the original feed ratio, and other methods cannot achieve the regulation of the molecular weight of the two blocks (Macromolecules 2013,46,1291-1295); Zhao Junpeng et al. used phosphazene base (t-BuP 1 ) as a catalyst to catalyze the copolymerization of cyclic acid anhydride and ethylene oxide, the copolymerization activity of the two is extremely high, and the alternating polyester is obtained first, and the excess ethylene oxide is further ring-opened and polymerized under the "self-buffering" effect of the catalyst to obtain a hydrophilic Water-based polyether, thus obtaining amphiphilic block polymers, this method corresponds to extremely limited types of monomers, and the types of available amphiphilic polymers are extremely limited (ACS MacroLett.2017,6,1094-1098)

Method used

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  • Method for preparing amphiphilic block copolymer through cooperation of light-operated free radical polymerization and ring-opening copolymerization
  • Method for preparing amphiphilic block copolymer through cooperation of light-operated free radical polymerization and ring-opening copolymerization
  • Method for preparing amphiphilic block copolymer through cooperation of light-operated free radical polymerization and ring-opening copolymerization

Examples

Experimental program
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Effect test

Embodiment 1

[0034] In a nitrogen-filled glove box, a stirrer was placed in the dry polymerization reaction tube in turn, and the chain transfer agent initiator 4-cyano-4-[(dodecylsulfanylthiocarbonyl)thiocarbonyl]valeric acid was added. (TTC-COOH) (80mg, 0.2mmol), (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO) (17.4mg, 0.05mmol), N-isopropylacrylamide ( 1.13g, 10mmol), cyclopentane oxide (0.44mL, 5mmol), phthalic anhydride (recrystallization and then sublimation) (0.74g, 5mmol), THF solution of triethylboron (TEB) (10μL, 0.1 mmol), phosphazene base (t-BuP1) (10 μL, 0.04 mmol), THF (2 ml). After the feeding is completed, shake evenly to completely dissolve the monomer, chain transfer agent, initiator and catalyst. Take it out and put it in a 60°C oil bath to react under magnetic stirring, while using 3mw / cm 2 The intensity was 405nm wavelength blue light irradiation while heating for 24 hours. After the reaction, a small amount of crude product was taken for nuclear magnetic test ...

Embodiment 2

[0037] Other polymerization conditions in this example are the same as in Example 1, and 4-cyano-4-[(dodecylsulfanylthiocarbonyl)thiocarbonyl]valeric acid (TTC-COOH) is still used as chain transfer agent initiator , the different blue light irradiation time was changed to 0h, the heating time was unchanged, the reaction was carried out in an oil bath at 60°C for 24h, the categories and proportions of other materials were the same, the conversion rate of phthalic anhydride monomer was >99%, and the molecular weight of the obtained polymer was 7.8kDa, molecular weight distribution is 1.56, only heating without light, see attached figure 1 Medium data 2.

Embodiment 3

[0039] Other polymerization conditions in this example are the same as in Example 1, and 4-cyano-4-[(dodecylsulfanylthiocarbonyl)thiocarbonyl]valeric acid (TTC-COOH) is still used as chain transfer agent to initiate The difference is that the blue light intensity is unchanged and the irradiation time is changed to 12h, the heating time is unchanged, and the reaction is carried out in an oil bath at 60°C for 24h. The conversion rate of phthalic anhydride monomer is >99%, the molecular weight of the obtained polymer is 14.7kDa, and the molecular weight distribution is 1.64.

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Abstract

The invention discloses a method for preparing an amphiphilic block copolymer through cooperation of light-operated free radical polymerization and ring-opening copolymerization, which comprises the following steps: simultaneously adding a Lewis acid-base pair catalytic system consisting of a reversible addition chain transfer reagent containing hydroxyl or carboxyl, a photoinitiator, a hydrophilic vinyl monomer, a Lewis acid-base pair system composed of Lewis acid and Lewis base, an epoxy compound, and a cyclic acid anhydride. The chain transfer reagent is used as a ring-opening polymerization initiator, and a Lewis acid-base pair is used as a catalyst to catalyze ring-opening copolymerization of cyclic anhydride and epoxide, so that the chain transfer agent is attached to the tail end of polyester. Meanwhile, visible light or ultraviolet light is irradiated, the photoinitiator is decomposed to generate free radicals, free radical polymerization of allyl monomers is achieved, and hydrophilic polyolefin chains and polyester chains are subjected to addition through reversible addition of a chain transfer agent, so that the amphiphilic block polymer is formed. The preparation method is simple and easy to operate, the production cost is low, certain biodegradability is achieved, the polymerization process is easy to control, and the product structure can be accurately regulated and controlled.

Description

technical field [0001] The invention belongs to the technical field of polymer synthesis, and relates to a method for synthesizing an amphiphilic polymer, in particular to a one-pot method for the ring-opening copolymerization of cyclic acid anhydride and epoxide catalyzed by photo-controlled reversible addition chain transfer radical polymerization in conjunction with Lewis acid-base pair catalysis Methods for the preparation of amphiphilic block copolymers. Background technique [0002] Amphiphilic polymer material refers to a polymer system that contains both hydrophilic and hydrophobic segments, and has both polymer stability and low-molecular surface activity. Using its self-assembly properties, polymer brushes with nanostructures can be prepared, Star polymers, polymer NPs, polymer nanofibers, polymer membranes, etc., are used in nanomaterial (L-B) membranes, polymer liquid crystals, drug targeting and sustained release, polymer alloys, tertiary oil recovery and chemic...

Claims

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Application Information

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IPC IPC(8): C08F293/00
CPCC08F293/005C08F2438/03
Inventor 王利军王艳飞王芳王建广郭尧宋海香茹宗玲邱明艳
Owner ANYANG INST OF TECH
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