US-12617897-B2 - Method for preparing multi-component polymers through post-polymerization modification

US12617897B2US 12617897 B2US12617897 B2US 12617897B2US-12617897-B2

Abstract

A method for preparing multi-component polymers through post-polymerization modification, used to functionalize polysulfonyl imidate polymer including a dispersing polymer reactant, an electrophilic substitution reagent and a catalyst in an organic dispersant; adding acid-binding agent to react at room temperature for 4-48 h; obtaining the precipitate when the reaction finished; washing and drying the precipitate to get the functionalized multi-component polymers.

Inventors

Xinxiang Chen
Nan Zheng
Jianyu Sun
Junnan He
Rui Zhang
Wangze SONG
Junqiao YAN
Weixing Wang
Feng Hou

Assignees

JIANGSU ZHONGLI GROUP CO., LTD.
DALIAN UNIVERSITY OF TECHNOLOGY

Dates

Publication Date: 20260505
Application Date: 20211111
Priority Date: 20210608

Claims (7)

1 . A method for preparing a multi-component polymer through post-polymerization modification, used to functionalize a polysulfonyl imidate polymer, comprising: dispersing a polymer reactant, an electrophilic substitution reagent and a catalyst in an organic dispersant; adding an acid-binding agent to react at room temperature for 4-48 h; obtaining a precipitate when the reaction is completed; washing and drying the obtained precipitate to get the functionalized multi-component polymers; wherein the polymer reactant includes a structure as shown below: n is an integer from 1 to 50; the electrophilic substitution reagent is a para-substituted aromatic ring of trans-nitracrine with a formula structure as shown below, or an ester with glyoxylate group with a formula structure as shown below, or a Baylis-Hillman addition derivative with a formula structure as shown below, wherein Boc is tert-butyloxycarbonyl; wherein R 1 , R 2 and R 3 are electron-donating groups or electron-withdrawing groups; a molar ratio of the polymer reactant to the electrophilic reagent is 1:1-2; the multi-component polymers include a structure selected from the group consisting of: wherein the multi-component polymer has a molecular weight of 8000-31000 g/moL.
2 . The method of claim 1 , wherein the electrophilic substitution reagent is selected from the group consisting of
3 . The method of claim 1 , wherein the organic dispersant is tetrahydrofuran or N,N′-dimethylformamide.
4 . The method of claim 1 , wherein a concentration of the electrophilic substitution reagent in the organic dispersant is 0.1 M-0.4 M.
5 . The method of claim 1 , wherein the catalyst comprises copper bromide, an amount of copper bromide ranges from 0.01 M-0.1 M.
6 . The method of claim 1 , wherein the acid binding agent comprises triethylamine, and the amount of triethylamine ranges from 0.05 M-1 M.
7 . A method of further functionalizing the multi-component polymer prepared by the method of claim 1 , comprising: dispersing the multi-component polymers with the formula structure as shown below and the acid binding agent in the organic dispersant; wherein n is an integer from 1 to 50, and R 3 is an electron-donating group or electron-withdrawing group; adding electrophilic addition reagent and reacting at room temperature for 4 h; obtaining the precipitate when the reaction is completed; drying and washing the precipitate to obtain the further functionalized polymers with a formula structure as shown below: the acid binding agent is triethylamine, the organic dispersant is tetrahydrofuran or N,N′-dimethylformamide, and the electrophilic addition reagent is benzyl mercaptan.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is the National Stage Application of PCT/CN2021/130037, filed on Nov. 11, 2021, which claims the priority of the Chinese application No. 2021106340134, filed on Jun. 8, 2021, the content of which is incorporated into this specification by reference. FIELD OF THE INVENTION The present disclosure relates to a method for preparing functionalized polymers, and specifically to a method for preparing functionalized polymers by introducing electrophilic substitution groups through post-polymerization modifications. BACKGROUND OF THE INVENTION Functionalized polymers have been applied in various aspects of our daily lives, including organic electronics, chemical/biosensing, medical diagnostics, and bioimaging. The development of these polymers, which contain specific functional groups or structures that exhibit unique properties or respond to changes in the environment, has expanded the scope and applications of polymers. Functionalized polymers represent a significant advancement in polymer research. At present, the functionalization of polymers is mainly achieved in two ways, one is to directly polymerize monomers to form functionalized polymers, and the other is to introduce functionalized groups through post-modification of polymers. For the first approach, the monomer electronic and site blocking effects during the polymerization process can severely limit the growth of polymer chains, resulting in low polymerization reaction efficiency and small polymer molecular weight, which is not suitable for producing functional polymers with complex structures. For the second method, as early as 1840, Hancok and Ludersdorf has been applied to sulfur post-treatment of natural rubber to obtain high-performance elastic materials, after decades of development, from the preparation of simple functionalized polymers to the ability to synthesize functionalized polymers with complex structures, pouring many generations of technical research and development efforts, and for the synthesis of complex. For the synthesis of complex structured polymers, how to achieve the maximum efficiency of the polymerization process, the controlled structure of polymer products, and the green polymerization process and products are still the difficulties and focus of the continuous improvement of the synthesis method. For example, poly(sulfonyl imidate), its electrophilic substituted derivatives can be used as carriers for hydrophobic drug group loading and are important intermediates for pharmaceutical synthesis, but in the current technology, these poly(sulfonyl imidate) polymers are considered to have low polymerization activity and cannot be functionalized by post-modification (electrophilic substitution) of their α-positions. SUMMARY OF THE INVENTION To overcome the shortcomings of prior art methods, it is therefore an object of this disclosure to provide a method for preparing multiple-component polymers through post-polymerization modification. Specifically, this method is used to functionalize polysulfonyl imidate polymer in a one-pot synthesis for functional polymers. To achieve the above purpose, the present disclosure provides the following technical solutions: A method for preparing multi-component polymers through post-polymerization modification, used to functionalize polysulfonyl imidate polymer, includes: dispersing a polymer reactant, an electrophilic substitution reagent and a catalyst in an organic dispersant;adding an acid-binding agent to react at room temperature for 4-48 h;obtaining the precipitate when the reaction is completed;washing and drying the obtained precipitate to get the functionalized multi-component polymers;the polymer reactant includes a structure as shown below: wherein n is an integer from 1 to 50;the electrophilic substitution reagent is selected from the group consisting of para-substituent of the aromatic ring of trans-nitracrine with a formula structure as shown below, or esters with glyoxylate group with a formula structure as shown below, or Baylis-Hillman addition derivatives with a formula structure as shown below, wherein R1, R2 and R3 are electron-donating groups or electron-withdrawing groups;a molar ratio of the polymer reactant to the electrophilic reagent is 1:1-2. Furthermore, the multi-component polymers further include a structure selected from the group consisting of: wherein the multi-component polymers have a molecular weight of 8000-31000 g/moL. Furthermore, the electrophilic substitution reagent is selected from the group consisting of: Moreover, the organic dispersant is tetrahydrofuran or N,N′-dimethylformamide. Furthermore, the monomer concentration of the electrophilic reagent in the organic dispersant is 0.1 M-0.4 M. In addition, the catalyst includes cuprous bromide. Additionally, the acid binding agent includes triethylamine. This disclosure also provided a detailed description of further functionalizing the multi-compone