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CN-119978371-B - Degradable aliphatic polysulfone synthesis method and polymer based on free radical rearrangement reaction

CN119978371BCN 119978371 BCN119978371 BCN 119978371BCN-119978371-B

Abstract

The invention discloses a method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction and a polymer, belonging to the technical field of chemical synthesis. The invention designs alkenyl sulfone containing migration groups as a polymerization monomer, realizes continuous chain growth through the alternating process of remote migration of unsaturated groups and addition of sulfonyl radicals to alkenyl under the action of an initiator, obtains aliphatic polysulfone with controllable sequence and higher molecular weight, the method can also provide selectivity for structural design of the aliphatic polysulfone by adopting different migration modes and migration groups, and solves the problems of uncontrollable sequence, poor solubility, low molecular weight and the like in the traditional preparation of the aliphatic polysulfone by olefin/sulfur dioxide low-temperature copolymerization or ring-opening polymerization of the cyclic vinyl sulfone monomer.

Inventors

  • ZHU CHEN
  • Gao Kexiong
  • Song Silin

Assignees

  • 上海交通大学

Dates

Publication Date
20260508
Application Date
20250124

Claims (10)

  1. 1. The synthesis method of the degradable aliphatic polysulfone based on the free radical rearrangement reaction is characterized by comprising the following steps: mixing an alkenyl sulfone polymerization monomer, a solvent and an initiator, performing polymerization reaction under the initiation of light conditions or heat conditions to obtain a polymer solution, diluting the polymer solution with a diluent to obtain a diluted polymer solution, dripping the diluted polymer solution into an inferior solvent, and precipitating to obtain polymer aliphatic polysulfone; The alkenyl sulfone polymerization monomer comprises the following structural general formula: , In the general structural formula: m comprises 1 or 2 and is defined as the following, R 1 includes hydrogen, alkyl of C 1 ~C 10 , substituted alkyl of C 1 ~C 10 or halogen, R 2 includes hydrogen, alkyl of C 1 ~C 10 , substituted alkyl of C 1 ~C 10 or halogen, R 3 includes hydrogen, alkyl of C 1 ~C 10 , substituted alkyl of C 1 ~C 10 or halogen, R 4 comprises an unsaturated group with migration ability; The R 4 includes cyano, aryl, heteroaryl, oxime, alkenyl, alkynyl or carbonyl.
  2. 2. The method of synthesizing a degradable aliphatic polysulfone based on radical rearrangement of claim 1, wherein in R 1 : The R 1 includes an alkyl group of C 1 ~C 10 , the alkyl group of C 1 ~C 10 including methyl, ethyl, t-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl; or, the R 1 comprises a substituted alkyl of C 1 ~C 10 , the substituted alkyl of C 1 ~C 10 comprises a perfluoroalkyl of C 1 ~C 4 ; Or, the R 1 comprises a halogen, including bromine, chlorine, or iodine; and/or, in the R 2 : the R 2 includes an alkyl group of C 1 ~C 10 , the alkyl group of C 1 ~C 10 including methyl, ethyl, t-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl; Or, the R 2 comprises a substituted alkyl of C 1 ~C 10 , the substituted alkyl of C 1 ~C 10 comprises a perfluoroalkyl of C 1 ~C 4 ; or, the R 2 comprises a halogen, including bromine, chlorine, or iodine; and/or, in the R 3 : The R 3 includes an alkyl group of C 1 ~C 10 , the alkyl group of C 1 ~C 10 including methyl, ethyl, t-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl; Or, the R 3 comprises a substituted alkyl of C 1 ~C 10 , the substituted alkyl of C 1 ~C 10 comprises a perfluoroalkyl of C 1 ~C 4 ; or, the R 3 includes a halogen including bromine, chlorine, or iodine.
  3. 3. The method for synthesizing a degradable aliphatic polysulfone based on a radical rearrangement reaction according to claim 1, wherein the alkenyl sulfone polymerization monomer comprises any one of the following structural formulas: 、 、 、 、 、 、 、 、 、 、 、 、 、 。
  4. 4. The method for synthesizing the degradable aliphatic polysulfone based on the free radical rearrangement reaction according to claim 1, wherein the initiator comprises one or more of azo compounds, organic peroxides, oxidation/reduction initiators, trialkylboron/peroxides; and/or the molar concentration of the alkenyl sulfone polymerization monomer in the solvent is (1 mol: 3L) - (3 mol: 1L); and/or the molar ratio of the alkenyl sulfone polymerization monomer to the initiator is (10:1) - (200:1), And/or, carrying out polymerization reaction under the initiation of the thermal condition, wherein the thermal condition comprises heating to 40-100 ℃; And/or the reaction time of the polymerization reaction is 5-48 h; and/or, the polymerization reaction is carried out under the protection of nitrogen or argon; and/or the solvent comprises one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1, 4-dioxane and trifluoroacetic acid; And/or the inferior solvent comprises one or more of water, methanol, ethanol and ethyl acetate; And/or the diluent comprises one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1, 4-dioxane and trifluoroacetic acid.
  5. 5. The method for synthesizing a degradable aliphatic polysulfone based on a radical rearrangement reaction according to claim 4, wherein the initiator comprises azo compounds including at least one of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azobicyclohexylcarbonitrile, dimethyl azobisisobutyrate; and/or the initiator comprises an organic peroxide comprising one or more of a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxyester, a diketone peroxide, a peroxydicarbonate; And/or the initiator comprises a redox initiator comprising at least one of dibenzoyl peroxide/N, N-dimethylaniline, dibenzoyl peroxide/N, N-dimethyl-p-toluidine, hydroperoxide/ascorbic acid; And/or the initiator comprises an oxidation/reduction initiator, wherein the oxidation/reduction initiator comprises an oxidant and a reducing agent, and the molar ratio of the oxidant to the reducing agent is (1:3) - (2:1); And/or the initiator comprises trialkylboron/peroxide comprising one or more of triethylboron, tri-n-butylboron, triisobutylboron, tri-sec-butylboron, the peroxide comprising one or more of hydrogen peroxide, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, diketones peroxides, peroxydicarbonates; And/or the initiator comprises trialkylboron/peroxide, wherein the molar ratio of the trialkylboron to the peroxide is (1:1) - (1:3).
  6. 6. The method of synthesizing a degradable aliphatic polysulfone based on a radical rearrangement reaction according to claim 5, wherein the oxidation/reduction initiator comprises a hydroperoxide/ascorbic acid, the hydroperoxide comprising one or more of isopropyl hydroperoxide, t-butyl hydroperoxide; And/or the organic peroxide comprises dialkyl peroxide, and the dialkyl peroxide comprises one or more of diisopropyl peroxide and di-tert-butyl peroxide; And/or the organic peroxide comprises diacyl peroxide, and the diacyl peroxide comprises one or more of dibenzoyl peroxide and lauroyl peroxide; and/or the organic peroxide comprises peroxyesters, the peroxyesters comprising one or more of tert-butyl peroxybenzoate and tert-butyl peroxyvalerate; And/or the organic peroxide comprises diketones, wherein the diketones comprise one or more of methyl ethyl ketone peroxide and cyclohexanone peroxide; And/or, the organic peroxide comprises peroxydicarbonate, the peroxydicarbonate comprises diisopropyl peroxydicarbonate peroxydicarbonic acid diisopropyl ester.
  7. 7. A polymer prepared by the method for synthesizing a degradable aliphatic polysulfone based on a radical rearrangement reaction according to any one of claims 1 to 6, characterized in that the polymer comprises the following structural formula: In the general structural formula: n comprises a positive integer; m comprises 1 or 2 and is defined as the following, R 1 includes hydrogen, alkyl of C 1 ~C 10 , substituted alkyl of C 1 ~C 10 or halogen, R 2 includes hydrogen, alkyl of C 1 ~C 10 , substituted alkyl of C 1 ~C 10 or halogen, R 3 includes hydrogen, alkyl of C 1 ~C 10 , substituted alkyl of C 1 ~C 10 or halogen, R 4 includes an unsaturated group having a migration ability.
  8. 8. The polymer of claim 7, wherein the polymer comprises at least one of the following structural formulas: 、 、 、 、 、 、 、 、 、 、 、 、 、 , wherein n in any of the structural formulas includes a positive integer.
  9. 9. The polymer of claim 8, wherein the polymer degrades under alkaline conditions to provide an alkenylsulfinate, and wherein the polymer degrades under alkaline conditions to provide an alkenylsulfinate comprising the steps of: And under the thermal condition, adding the polymer and strong base into a solvent, stirring and reacting to obtain a reaction product, and separating and purifying the reaction product to obtain the alkenyl sulfinate.
  10. 10. The polymer of claim 9, wherein the thermal conditions range in temperature from 20 ℃ to 80 ℃; And/or the concentration of the polymer in the solvent is 15 mg/mL-1000 mg/mL; And/or the stirring reaction time is 0.5-48 h; and/or the molar ratio of the sulfonyl group to the strong alkali in the polymer is 1 (5-1); And/or the solvent comprises an organic solvent comprising at least one of dichloromethane, chloroform, methanol, ethanol, 1, 4-dioxane, dimethyl sulfoxide, N-dimethylformamide; And/or the strong base comprises an inorganic alkali metal, wherein the inorganic alkali metal comprises at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; And/or the strong base comprises an organic strong base comprising at least one of potassium tert-butoxide, sodium methoxide, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), tetrabutylammonium hydroxide, tetramethylguanidine, 4-dimethylaminopyridine; And/or the yield of the alkenyl sulfinate is 70% -99%; And/or, the alkenyl sulfinate comprises the following structural general formula: , in the general structural formula of the alkenyl sulfinate, M is 1 or 2, R 4 comprises an unsaturated group with migration capability, and M + is an alkali metal cation or N positive ion.

Description

Degradable aliphatic polysulfone synthesis method and polymer based on free radical rearrangement reaction Technical Field The invention relates to the technical field of chemical synthesis, in particular to a method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction and a polymer. Background The use of vinyl monomers by free radical polymerization is currently an effective way to prepare polyolefin materials. Various products with the performance meeting the actual application requirements can be obtained through simple side group change. However, the full carbon chain structure makes polyolefin materials not only subject to environmental protection pressure of difficult degradation, but also further hinders the application of functionalization. The incorporation of heteroatoms, particularly elemental sulfur, into the polymer backbone imparts a number of attractive properties to the polymer material, including high refractive index, degradability, high mechanical properties, and heavy metal ion adsorption. Among them, copolymerization of various olefins with sulfur dioxide is an efficient means for preparing sulfur-containing polymers (aliphatic polysulfones). However, the copolymerization of olefins with sulfur dioxide is often carried out at low temperatures, and the resulting polysulfone is of lower molecular weight, affected by the ceiling temperature beyond which depolymerization occurs. Secondly, for olefins of different structures, there are problems of uncontrollable sequence structure (styrene/SO 2 copolymer), poor heat resistance (conjugated olefin/SO 2 copolymer), generation of cyclic sulfone by-products (conjugated or non-conjugated olefin/SO 2 copolymer) and the like, respectively. Meanwhile, polysulfones exhibit poor solubility (only in trifluoroacetic acid or concentrated sulfuric acid) in the absence of polar side groups, which not only results in difficult acquisition of molecular weight and its distribution information, but also further limits their processability and application range. Cyclic Vinyl Sulfone (CVS) provides a monomer design concept for the direct preparation of polysulfones. CVS directly uses sulfonyl radicals as chain growth free radicals through free radical ring opening, and the monomers can be polymerized through thermal initiation to obtain high conversion rate. However, since it is difficult to introduce polar groups into the CVS monomer, the resulting aliphatic polysulfone has poor solubility. In addition, random ring opening of CVS during polymerization results in uncontrollable polymer sequences and newly formed c=c bonds in the backbone resulting in poor heat resistance. Thus, preparing high molecular weight aliphatic polysulfones with sequence control remains challenging. Group Transfer Radical Polymerization (GTRP) is an emerging radical polymerization strategy that has been applied to the construction of sequence-controlled carbon chain polyolefins. Wherein efficient transfer of migrating groups and free base character matching provide conditions for rapid chain growth, enabling the synthesis of high molecular weight polymers. Meanwhile, in the small molecule reaction, the sulfone compound can form sulfone free radicals through smiles rearrangement, and the sulfone free radicals are used as chain growth free radicals, so that the construction of aliphatic polysulfone chains is feasible. Disclosure of Invention The invention mainly aims to provide a method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction and a polymer, which solve the technical problems of complex synthesis method, difficult control of product structure and poor performance of aliphatic polysulfone. In order to achieve the above object, the present invention provides a method for synthesizing a degradable aliphatic polysulfone based on a radical rearrangement reaction, comprising the steps of: mixing an alkenyl sulfone polymerization monomer, a solvent and an initiator, performing polymerization reaction under the initiation of light conditions or heat conditions to obtain a polymer solution, diluting the polymer solution with a diluent to obtain a diluted polymer solution, dripping the diluted polymer solution into an inferior solvent, and precipitating to obtain polymer aliphatic polysulfone; The alkenyl sulfone polymerization monomer comprises the following structural general formula: In the general structural formula: m comprises 1 or 2 and is defined as the following, R 1 includes hydrogen, alkyl of C 1～C10, substituted alkyl of C 1～C10 or halogen, R 2 includes hydrogen, alkyl of C 1～C10, substituted alkyl of C 1～C10 or halogen, R 3 includes hydrogen, alkyl of C 1～C10, substituted alkyl of C 1～C10 or halogen, R 4 includes an unsaturated group having a migration ability. In some embodiments of the invention, in the R 1: The R 1 includes an alkyl group of C 1～C10, the alkyl group of C 1～C10 including met