Method of preparing hyperbranched polythioether

Abstract

The invention relates to a method of preparing hyperbranched polythioether based on selective thiol-ene and thiol-epoxy click chemistry. According to the method, difunctional glycidyl acrylate monomers and trifunctional mercaptan are used as raw materials, and hyperbranched polythioether with a controlled skeleton and end group is synthesized by a one-pot method. The hyperbranched polythioether click chemical preparation method has the advantages that the raw material is easy to obtain, the steps are simple, the polymerization rate is rapid, the controllability is good, the skeleton of the prepared hyperbranched polythioether can be controlled, and the end group can be effectively controlled to be thiol or epoxy by using the monomeric molar ratio; functional modification can be further conducted, and the hyperbranched polythioether with particular characteristics is prepared.

Description

technical field [0001] The invention relates to the field of organic polymers, in particular to a method for preparing hyperbranched polysulfides. Background technique [0002] Due to the existence of sulfur atoms, sulfur-containing hyperbranched polymers have special functionalities that conventional hyperbranched polymers (HBP) do not have, and have received more and more attention. The thiol click chemistry reaction has gradually become the main reaction for the preparation of sulfur-containing hyperbranched polymers due to its high reactivity, mild and efficient reaction, and wide monomer applicability. At present, the preparation methods of hyperbranched polymers mainly include AB 2 and A 2 +B 3 Two methods, while the synthesis of sulfur-containing hyperbranched polymers is based on AB 2 law. Among them, Gao Chao et al. (Han J, Zhao B, Tang A, et al. Polymer Chemistry, 2012, 3(7): 1918-1925.) from Zhejiang University used 3,6-dioxa-octane-1,8- Dimercapto and propa...

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Problems solved by technology

Among them, Gao Chao et al. (Han J, Zhao B, Tang A, et al. Polymer Chemistry, 2012, 3(7): 1918-1925.) from Zhejiang University used 3,6-dioxa-octane-1,8- Dimercapto and propargyl bromide were used as raw materials to prepare AB with mercapto at one end and alkyne at one end 2 monomer, and then use mercapto-alkyne click chemistry to convert AB 2 The hyperbranched polythioether whose end group is an alkyne is prepared by monomer polymerization, which can be applied in fields such as metal ion adsorption, oil resistance, and oxidation resistance resin; Gadwal et al. (Gadwal I, Binder S, Stuparu M C, et al.Macromolecules, 2014,47(15):5070-5080.) AB containing two epoxy groups and one mercapto group was prepared by a series of organic synthesis 2 monomer, and then prepared hyperbranched polythioether with epoxy end group by using mercapto-epoxy click chemistry reaction; but because AB 2 There are very few types of monomers, and the monomer preparation process is cumbersome, while A 2 +B 3 The lack of selectivity in the polymerization system has the risk of gelation during the polymerization process, which severely limits the preparation and application of hyperbranched polysulfides

In addition, limited by the monomer structure and polymerization system, the currently reported AB 2 and A 2 +B 3 Most systems can only prepare hyperbranched polysulfides with specific skeletons and end groups, and it is difficult to simultaneously control the skeleton and end groups of hyperbranched polysulfides, thus limiting the functions and application fields of hyperbranched polysulfides

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