Degradable aliphatic polysulfone synthesis method based on free radical rearrangement reaction and polymer

Abstract

The invention discloses a degradable aliphatic polysulfone synthesis method based on free radical rearrangement reaction and a polymer, and belongs to the technical field of chemical synthesis. According to the invention, alkenyl sulfone containing a migration group is designed as a polymerization monomer, continuous chain growth is realized through an alternating process of remote migration of unsaturated groups and addition of sulfonyl free radicals to alkenyl under the action of an initiator, aliphatic polysulfone with a controllable sequence and a relatively high molecular weight is obtained, and different migration modes and migration groups can be adopted, so that the aliphatic polysulfone with a controllable molecular weight can be obtained. The selectivity is provided for the structural design of the aliphatic polysulfone, and the problems of uncontrollable sequence, poor solubility, low molecular weight and the like of the conventional aliphatic polysulfone prepared by olefin / sulfur dioxide low-temperature copolymerization or cyclic vinyl sulfone monomer ring-opening polymerization are solved.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a synthesis method of degradable aliphatic polysulfone based on free radical rearrangement reaction and a polymer. Background Art

[0002] Using vinyl monomers through free radical polymerization is currently an effective way to prepare polyolefin materials. Various products with performance that meets the needs of practical applications can be obtained by simply changing the side groups. However, the full carbon chain structure not only makes polyolefin materials face the environmental pressure of difficult degradation, but also further hinders their functional application. Heteroatoms, especially sulfur elements, introduced into the polymer main chain can give polymer materials many attractive properties, 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 to prepare sulfur-containing polymers (aliphatic polysulfones). However, due to the influence of the ceiling temperature (depolymerization occurs above this temperature), the copolymerization of olefins and sulfur dioxide is mostly carried out at low temperatures, and the molecular weight of the resulting polysulfone is low. Secondly, for olefins with different structures, there are problems such as uncontrollable sequence structure (styrene / SO2 copolymer), poor heat resistance (conjugated olefin / SO2 copolymer) and the production of cyclic sulfone byproducts (conjugated or non-conjugated olefin / SO2 copolymer). At the same time, when the polar side groups are missing, polysulfone exhibits poor solubility (it can only be dissolved in trifluoroacetic acid or concentrated sulfuric acid), which not only makes it difficult to obtain information on the molecular weight and its distribution, but also further limits its processability and application range.

[0003] Cyclic vinyl sulfone (CVS) provides an idea for monomer design for the direct preparation of polysulfone. CVS uses free radical ring opening to directly use sulfone radicals as chain growth radicals, and the monomer can obtain a high conversion rate through thermally initiated polymerization. However, since it is difficult to introduce polar groups into the CVS monomer, the resulting aliphatic polysulfone has poor solubility. In addition, the random ring opening of CVS during the polymerization process leads to uncontrollable polymer sequence, and the newly formed C=C bonds on the main chain lead to poor heat resistance. Therefore, the preparation of high molecular weight aliphatic polysulfone with controllable sequence remains challenging.

[0004] Group transfer radical polymerization (GTRP) is an emerging free radical polymerization strategy that has been applied to the construction of sequence-controlled carbon chain polyolefins. Among them, the efficient transfer of migrating groups and the polarity matching of free radicals provide conditions for rapid chain growth, making the synthesis of high molecular weight polymers possible. At the same time, it has been proven in small molecule reactions that sulfone compounds can form sulfone radicals through smiles rearrangement, which can be used as chain growth radicals, making the construction of aliphatic polysulfone chains feasible. Summary of the invention

[0005] The main purpose of the present invention is to provide a method for synthesizing a degradable aliphatic polysulfone based on a free radical rearrangement reaction and a polymer, so as to solve the technical problems that the synthesis method of aliphatic polysulfone is complicated, the product structure is difficult to control, and the performance is poor.

[0006] To achieve the above object, the present invention provides a method for synthesizing a degradable aliphatic polysulfone based on a free radical rearrangement reaction, comprising the following steps:

[0007] The vinyl sulfone polymerization monomer, solvent and initiator are mixed, a polymerization reaction is carried out under light conditions or heat conditions to obtain a polymer solution, the polymer solution is diluted with a diluent to obtain a diluted polymer solution, and the diluted polymer solution is added dropwise to a poor solvent to obtain a polymer aliphatic polysulfone through precipitation;

[0008] The alkenyl sulfone polymer monomer comprises the following general structural formula:

[0009]

[0010] In the general structural formula:

[0011] m includes 1 or 2,

[0012] R1 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen,

[0013] R2 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen,

[0014] R3 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen,

[0015] R4 includes an unsaturated group having migration ability.

[0016] In some embodiments of the present invention, in said R1:

[0017] The R1 includes C1~C 10 The alkyl group of C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl;

[0018] Or, the R1 includes C1~C 10 The substituted alkyl group, the C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group;

[0019] Or, said R1 comprises halogen, said halogen comprises bromine, chlorine or iodine;

[0020] and / or, in said R2:

[0021] The R2 includes C1~C 10 The alkyl group of C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl;

[0022] Or, the R2 includes C1~C 10 The substituted alkyl group, the C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group;

[0023] Or, said R2 comprises halogen, said halogen comprises bromine, chlorine or iodine;

[0024] and / or, in said R3:

[0025] The R3 includes C1~C 10 The alkyl group of C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl;

[0026] Or, the R3 includes C1~C 10 The substituted alkyl group, the C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group;

[0027] Or, said R3 comprises halogen, said halogen comprises bromine, chlorine or iodine;

[0028] And / or, said R4 includes cyano, aryl, heteroaryl, oxime, alkenyl, alkynyl or carbonyl.

[0029] In some embodiments of the present invention, the vinyl sulfone polymer monomer comprises any of the following structural formulas:

[0030]

[0031] In some embodiments of the present invention, the initiator includes one or more of azo compounds, organic peroxides, oxidation / reduction initiators, trialkyl boron / peroxides;

[0032] and / or, the molar concentration of the vinyl sulfone polymerization monomer in the solvent is (1 mol:3L) to (3 mol:1L);

[0033] and / or, the molar ratio of the vinyl sulfone polymerization monomer to the initiator is (10:1) to (200:1),

[0034] and / or, a polymerization reaction occurs under the thermal conditions, wherein the thermal conditions include heating to 40° C. to 100° C.;

[0035] And / or, the reaction time of the polymerization reaction is 5h to 48h;

[0036] And / or, the polymerization reaction is carried out under the protection of nitrogen or argon;

[0037] And / or, the solvent includes one or more of N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,4-dioxane, and trifluoroacetic acid;

[0038] And / or, the poor solvent includes one or more of water, methanol, ethanol, and ethyl acetate;

[0039] And / or, the diluent includes one or more of N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,4-dioxane, and trifluoroacetic acid.

[0040] In some embodiments of the present invention, the initiator includes an azo compound, and the azo compound includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, azobiscyclohexylcarbonitrile, and dimethyl azobisisobutyrate;

[0041] And / or, the initiator comprises an organic peroxide, and the organic peroxide comprises one or more of a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxyester, a diketone peroxide, and a peroxydicarbonate;

[0042] And / or, the initiator comprises an oxidation / reduction initiator, and the oxidation / reduction initiator comprises at least one of dibenzoyl peroxide / N,N-dimethylaniline, dibenzoyl peroxide / N,N-dimethyl-p-toluidine, and hydroperoxide / ascorbic acid;

[0043] And / or, the initiator comprises an oxidation / reduction initiator, the oxidation / reduction initiator comprises an oxidant and a reductant, and the molar ratio of the oxidant to the reductant is (1:3) to (2:1);

[0044] And / or, the initiator comprises trialkyl boron / peroxide, the trialkyl boron comprises one or more of triethyl boron, tri-n-butyl boron, tri-isobutyl boron, tri-sec-butyl boron, and the peroxide comprises one or more of hydrogen peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, diketone peroxide, and peroxydicarbonate;

[0045] And / or, the initiator comprises trialkyl boron / peroxide, and the molar ratio of the trialkyl boron to the peroxide is (1:1) to (1:3).

[0046] In some embodiments of the present invention, the oxidation / reduction initiator comprises hydroperoxide / ascorbic acid, and the hydroperoxide comprises one or more of isophenylpropyl hydroperoxide and tert-butyl hydroperoxide;

[0047] And / or, the organic peroxide includes a dialkyl peroxide, and the dialkyl peroxide includes one or more of diisopropyl peroxide and di-tert-butyl peroxide;

[0048] And / or, the organic peroxide includes diacyl peroxide, and the diacyl peroxide includes one or more of dibenzoyl peroxide and dodecanoyl peroxide;

[0049] And / or, the organic peroxide includes a peroxyester, and the peroxyester includes one or more of tert-butyl perbenzoate and tert-butyl pervalerate;

[0050] And / or, the organic peroxide includes diketone peroxide, and the diketone peroxide includes one or more of methyl ethyl ketone peroxide and cyclohexanone peroxide;

[0051] And / or, the organic peroxide includes peroxydicarbonate, and the peroxydicarbonate includes one or more of diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.

[0052] The present invention also provides a polymer prepared by the above-mentioned method for synthesizing a degradable aliphatic polysulfone based on a free radical rearrangement reaction, wherein the polymer comprises the following general structural formula:

[0053]

[0054] In the general structural formula:

[0055] n includes positive integers;

[0056] m includes 1 or 2,

[0057] R1 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen,

[0058] R2 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen,

[0059] R3 includes hydrogen, C1~C 10 Alkyl, C1~C 10substituted alkyl or halogen,

[0060] R4 includes an unsaturated group having migration ability.

[0061] In some embodiments of the present invention, the polymer comprises at least one of the following structural formulas:

[0062]

[0063] Wherein, n in any of the structural formulas comprises a positive integer.

[0064] In some embodiments of the present invention, the polymer is degraded under alkaline conditions to obtain olefin sulfinate, and the polymer is degraded under alkaline conditions to obtain olefin sulfinate comprising the following steps:

[0065] Under heat conditions, a polymer aliphatic polysulfone and a strong base are added to a solvent, and the reaction is stirred to obtain a reaction product, and the reaction product is separated and purified to obtain the olefin sulfinate.

[0066] In some embodiments of the present invention, the temperature range of the thermal condition is 20°C to 80°C;

[0067] and / or, the concentration of the polymer in the solvent is 15 mg / ml to 1000 mg / mL;

[0068] And / or, the stirring reaction time is 0.5h to 48h;

[0069] and / or, the molar ratio of sulfone group to strong base in the polymer is 1:(5-1);

[0070] And / or, the solvent comprises an organic solvent, and the organic solvent comprises at least one of dichloromethane, chloroform, methanol, ethanol, 1,4-dioxane, dimethyl sulfoxide, and N,N-dimethylformamide;

[0071] And / or, the strong base comprises an inorganic alkali metal, and the inorganic alkali metal comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., preferably potassium hydroxide;

[0072] And / or, the strong base comprises an organic strong base, and the organic strong base comprises at least one of potassium tert-butoxide, sodium methoxide, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetrabutylammonium hydroxide, tetramethylguanidine, and 4-dimethylaminopyridine;

[0073] and / or, the yield of the olefin sulfinate is 70% to 99%;

[0074] And / or, the olefin sulfinate comprises the following general structural formula:

[0075]

[0076] In the general structural formula of the alkenyl sulfinate, m is 1 or 2, R4 includes an unsaturated group having migration ability, and M + It is an alkali metal cation or a N positive ion.

[0077] The beneficial effects that can be achieved by the present invention are:

[0078] The present invention designs alkenyl sulfone containing a migration group as a polymerization monomer, and realizes continuous chain growth through the alternating process of long-range migration of unsaturated groups and addition of sulfone free radicals to alkenyl groups under the action of an initiator, thereby obtaining aliphatic polysulfone with controllable sequence and high molecular weight, which can even be as high as 199,000.

[0079] The present invention can also provide selectivity for the structural design of aliphatic polysulfone by adopting different migration modes and migration groups.

[0080] The vinyl sulfone polymerization monomer prepared by the invention can be rapidly polymerized under free radical initiation conditions, and the molecular weight of the obtained aliphatic polysulfone can reach (80-200) kg / mol, the molecular weight distribution width is 1.2-2.7, the glass transition temperature is 60-121°C, the 5% thermal weight loss decomposition temperature is 180-340°C, and the refractive index is (1.60-1.68), which is comparable to commercial polycarbonate, but the Abbe number is (25-30), which is higher than the Abbe number of commercial polycarbonate.

[0081] The aliphatic polysulfone developed by the present invention contains groups with further reaction ability, such as the alkynyl group protected by the silicon group can be deprotected in the presence of tetrabutylammonium fluoride to obtain an aliphatic polysulfone with a terminal alkynyl group as a side group. At the same time, the alkynyl group and the furan group can be respectively post-modified on the aliphatic polysulfone through Diels-Alder or Click reaction to adjust its structural properties.

[0082] The aliphatic polysulfone developed by the invention can be rapidly degraded or even completely degraded under strong alkaline conditions, and can also obtain an olefin sulfinate as a main degradation product with a high conversion rate of 70% to 99%.

[0083] The invention solves the problems of uncontrollable sequence, poor solubility and low molecular weight in the preparation of aliphatic polysulfone by traditional olefin / sulfur dioxide low-temperature copolymerization or ring-opening polymerization of cyclic vinyl sulfone monomer. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0085] Figure 1 The figure is a schematic diagram of the synthesis process of vinyl sulfone polymerization monomer according to one embodiment of the present invention.

[0086] Figure 2 The figure is a schematic diagram of the synthesis process of vinyl sulfone polymerization monomer according to another embodiment of the present invention.

[0087] Figure 3 is the H NMR spectrum of the vinyl sulfone polymer monomer in Example 6 of the present invention;

[0088] Figure 4 is the NMR carbon spectrum of the vinyl sulfone polymerization monomer in Example 6 of the present invention;

[0089] Figure 5 is the H NMR spectrum of the polymer prepared in Example 1 of the present invention;

[0090] Figure 6 is the H-NMR spectrum of the polymer prepared in Example 3 of the present invention;

[0091] Figure 7 is the H NMR spectrum of the polymer prepared in Example 9 of the present invention;

[0092] Figure 8 is the GPC curve of the polymer obtained in Example 9 of the present invention;

[0093] Fig. 9 is a crude H NMR spectrum of the degradation reaction in Example 17 of the present invention;

[0094] Fig.10 This is the H NMR spectrum of the degradation product in Example 18 of the present invention.

[0095] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0096] It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention.

[0097] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0098] In the present invention, descriptions such as "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in the field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0099] The invention provides a method for synthesizing a degradable aliphatic polysulfone based on a free radical rearrangement reaction, comprising the following steps: mixing an olefin sulfone polymerization monomer, a solvent and an initiator, causing a polymerization reaction under light conditions or heat conditions to obtain a polymer solution, diluting the polymer solution with a diluent to obtain a diluted polymer solution, and dripping the diluted polymer solution into a poor solvent to obtain a polymer aliphatic polysulfone through precipitation.

[0100] In the present invention, the vinyl sulfone polymer monomer comprises the following general structural formula:

[0101]

[0102] In the above structural formula, m includes 1 or 2, R1 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R2 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R3 includes hydrogen, C1~C 10 Alkyl, C1~C 10 R4 includes an unsaturated group having migration ability.

[0103] In the above structural formula, R1 includes C1~C 10 Alkyl, C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl.

[0104] In the above structural formula, R1 includes C1~C 10 Substituted alkyl, C1~C10 The substituted alkyl groups include C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group.

[0105] In the above general structural formula, R1 includes halogen, and the halogen includes bromine, chlorine or iodine.

[0106] In the above general structural formula, R2 includes C1~C 10 Alkyl, C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl.

[0107] In the above general structural formula, R2 includes C1~C 10 Substituted alkyl, C1~C 10 The substituted alkyl groups include C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group.

[0108] In the above general structural formula, R2 includes halogen, and the halogen includes bromine, chlorine or iodine.

[0109] In the above general structural formula, R3 includes C1~C 10 Alkyl, C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl.

[0110] In the above general structural formula, R3 includes C1~C 10 Substituted alkyl, C1~C 10 The substituted alkyl groups include C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group.

[0111] In the above general structural formula, R3 includes halogen, and the halogen includes bromine, chlorine or iodine.

[0112] In some embodiments, R4 includes cyano, aryl, heteroaryl, oxime, alkenyl, alkynyl or carbonyl, and the above groups have migration ability, which helps to prepare degradable aliphatic polysulfone through free radical rearrangement reaction.

[0113] The vinyl sulfone polymerization monomer of the present invention includes an unsaturated group with migration ability, which can be used as a polymerization monomer. Under the action of an initiator, continuous chain growth is achieved through the alternating process of long-range migration of the unsaturated group and addition of the sulfone free radical to the vinyl group, thereby obtaining an aliphatic polysulfone with a controllable sequence and a high molecular weight, even up to 199,000. In addition, the present invention can also provide selectivity for the structural design of the aliphatic polysulfone by adopting different migration modes and migration groups.

[0114] The preparation method of the vinyl sulfone polymer monomer of the present invention can be prepared by a preparation method well known to those skilled in the art.

[0115] The present invention further provides a method for preparing an olefin sulfone polymerization monomer, but this is not considered as a limitation of the present invention. Figure 1 The synthesis process of the vinyl sulfone polymerization monomer is as follows: compound a undergoes a strong base hydrogen extraction reaction with sulfur and then acidifies to obtain the corresponding thiol b; thiol b and vinyl halide c react with vinyl alcohol d under alkaline conditions or through Mitsunobu reaction to obtain vinyl ether e; vinyl ether e is oxidized to obtain vinyl sulfone polymerization monomer f containing a migration group.

[0116] In some embodiments, compound a includes furan, 2,3-benzofuran, tert-butylacetylene or silicon-protected acetylene.

[0117] In the present invention, the thiol can be prepared from compound a or directly purchased, including 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole or 2-mercaptopyrimidine.

[0118] The present invention now takes the synthesis of butenyl furan sulfone as an example to illustrate the specific steps of synthesizing vinyl sulfone monomers, but this is not considered to be a limitation of the present invention. Figure 2 , the reaction route includes the following steps:

[0119] Step 1: Synthesis of Thiol a

[0120] At -78°C, under nitrogen or argon protection, n-butyl lithium (200 mmol) was added dropwise to a tetrahydrofuran solution of furan (1.0 equivalent, 13.6 g, 200 mmol, 0.5 M), and after the addition was completed, the mixture was stirred at room temperature for 1 h. Next, elemental sulfur (6.412 g, 200 mmol) was added after cooling to -78°C, and then stirred at room temperature for 1 h. Finally, 200 mL of 2M hydrochloric acid was added to quench the reaction and acidify for 0.5 h, and the mixture was extracted with ether 3 times (200 mL × 3). The organic phases were combined and dried with anhydrous magnesium sulfate, and the ether was removed by distillation under reduced pressure to obtain the crude product of thiol a, which was directly used for the next step without purification.

[0121] Step 2: Synthesis of alkenyl sulfide b

[0122] The above thiol a was dissolved in N,N-dimethylformamide (1M), potassium carbonate (41.5g, 300mmol) and 4-bromo-1-butene (24.4mL, 240mmol) were added at room temperature, and stirring was continued for 2h. Then, 400mL of water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate (200mL×3), and the organic phases were combined and washed once with a saturated aqueous NaCl solution. Finally, the mixture was dried over anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain the crude product of alkenyl sulfide b, which was directly put into the next step without purification.

[0123] Step 3: Synthesis of vinyl sulfone c

[0124] The above alkenyl sulfide b was dissolved in anhydrous ethanol (0.5M), and ammonium molybdate tetrahydrate (24.7g, 20mmol) was added. Then, 35% aqueous hydrogen peroxide solution (1000mmol) was added dropwise at 0°C, and stirring was continued for 1h after the addition was completed. Then, the mixture was stirred at room temperature for 5h. Then, 500mL of water was added to dilute the reaction solution, and the mixture was extracted three times with ethyl acetate (200mL×3), the organic phases were combined and dried over anhydrous magnesium sulfate, the aqueous phase was quenched with sodium thiosulfate aqueous solution, and the solvent was removed by reduced pressure distillation to obtain the crude product of alkenyl sulfone c. Finally, pure alkenyl furan sulfone monomer (28.1g, 75.4% total yield) was obtained after column chromatography purification (petroleum ether / ethyl acetate=10 / 1, v / v).

[0125] refer to Figure 3 and Figure 4 , Figure 3 and Figure 4 These are respectively the H NMR spectrum and C NMR spectrum of the alkenyl furan sulfone monomer prepared above, which can prove that the alkenyl furan sulfone monomer has been prepared.

[0126] In some embodiments, the vinyl sulfone polymer monomer comprises any of the following structural formulas:

[0127]

[0128] The above-mentioned vinyl sulfone polymerization monomer is characterized as follows:

[0129] 1 H NMR(500MHz, CDCl3)δ8.22(d,J=7.5Hz,1H),8.02(d,J=7.5Hz,1H),7.70-7.56(m, 2H),5.84-5.72(m,1H),5.17-5.03(m,2H),3.66-3.56(m,2H),2.70-2.60(m,2H).

[0130] 1H NMR(400 MHz,CDCl3)δ7.93-7.85(m,1H),7.72-7.64(m,1H),7.61-7.46(m,2H),5.85-5.70(m,1H),5.16-5.03(m,2H),3.65-3.58(m,2H),3.73-3.64(m,2H).

[0131] 1 H NMR(500 MHz,CDCl3)δ7.72(d,J=8.5 Hz,1H),7.59(d,J=8.5Hz,1H),7.56-7.48(m,2H),7.37(t,J=7.5 Hz,1H),5.81-5.70(m,1H),5.13 -5.02(m,2H),3.44-3.33(m,2H),2.61-2.50(m,2H).

[0132] 1 H NMR(500 MHz,CDCl3)δ5.89-5.76(m,1H),5.20-5.08(m,2H),3.30-3.20(m,2H),2.73-2.62(m,2H),1.20-1.07(m,21H).

[0133] 1 H NMR(400 MHz,CDCl3)δ7.84(d,J=8.0 Hz,1H),7.49-7.40(m,2H),7.41-7.35(m,1H),5.88-5.75(m,1H),5.20-5.05(m,2H),4.12(s,3H),3.78-3.68(m,2H),2.74-2.64(m,2H).

[0134] 1 H NMR(500 MHz,CDCl3)δ5.89-5.78(m,1H),

[0135] 5.21-5.09(m,2H),3.27-3.18(m,2H),2.63(dd,J=16.0,8.0 Hz,2H),1.30(d,J=1.0 Hz,9H).

[0136] 1H NMR(500 MHz,CDCl3)δ7.88(d,J=8.0 Hz,1H),7.67(d,J=8.5 Hz,1H),7.56(t,J=8.0 Hz,1H),7.49(t,J=7.5 Hz,1H),5.78-5.66(m,1H),5.11-5.00(m,2H),3.56-3.48(m,2H),2.23(dd,J=14.0,7.0 Hz,2H),2.06-1.98(m,2H).

[0137] : 1 H NMR(400 MHz,CDCl3)δ7.84(d,J=8.0 Hz,1H),

[0138] 7.49-7.41(m,2H),7.41-7.36(m,1H),5.84-5.70(m,1H),5.13-5.01(m,2H),4.12(s,3H),3.69-3.60(m,2H),2.31-2.21(m,2H),2.12-1.99(m,2H).

[0139] 1 H NMR(500 MHz,CDCl3)δ8.21(d,J=7.5 Hz,1H),8.01(d,J=9.0 Hz,1H),7.66-7.55(m,2H),5.75-5.67(m,1H),5.10-4.98(m,2H),3.54 -3.45(m,2H),2.25-2.16(m,2H),1.99(dt,J=15.5,7.5 Hz,2H).

[0140] 1 H NMR(500 MHz,CDCl3)δ7.72(d,J=8.0 Hz,1H),7.59(d,J=8.5 Hz,1H),7.54-7.47(m,2H),7.40-7.34(m,1H),5.76-5.64(m,1H),5.08-4.96(m,2H),3.34-3.23(m,2H),2.24-2.11(m,2H),1.97-1.86(m,2H).

[0141] 1H NMR(500MHz, CDCl3)δ8.93(d,J=5.0Hz,2H),7.57(t,J=5.0Hz,1H),5.78-5.65(m,1H), 5.08-4.95(m,2H),3.56-3.44(m,2H),2.20(dd,J=14.0,7.0Hz,2H),1.98-1.88(m,2H).

[0142] 1 H NMR (500MHz, CDCl3) δ5.82-5.67(m,1H),5.12-5.00(m,2H),3.19-3.07(m,2H),2.23(dd,J=14.0,7.0Hz,2H),2.05-1.91(m,2H),1.29(s,9H).

[0143] 1 H NMR (500MHz, CDCl3) δ5.81-5.68(m,1H),5.13-5.01(m,2H),3.23-3.10(m,2H),2.24(dd,J=14.0,7.0Hz,2H),2.08-1.97(m,2H),1.20-1.03(m,21H).

[0144] In some embodiments, the initiator includes one or more of an azo compound, an organic peroxide, an oxidation / reduction initiator, and a trialkyl boron / peroxide. It should be noted that the oxidation / reduction initiator refers to an oxidation / reduction initiator including a reducing agent and an initiator, and the oxidant and the reducing agent are compounded as an initiator; the trialkyl boron / peroxide refers to an initiator including a trialkyl boron and a peroxide, and the trialkyl boron and the peroxide are compounded as an initiator.

[0145] In some embodiments, the azo compound includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, azobiscyclohexylcarbonitrile, and dimethyl azobisisobutyrate.

[0146] In some embodiments, the organic peroxide includes one or more of a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxyester, a diketone peroxide, and a peroxydicarbonate.

[0147] In some embodiments, the oxidation / reduction initiator includes one or more of dibenzoyl peroxide (BPO) / N,N-dimethylaniline, dibenzoyl oxide (BPO) / N,N-dimethyl-p-toluidine, and hydroperoxide / ascorbic acid. It should be noted that the oxidation / reduction initiator includes an oxidant and a reductant, therefore, dibenzoyl peroxide (BPO) / N,N-dimethylaniline refers to dibenzoyl peroxide (BPO) and N,N-dimethylaniline compounded as an initiator, dibenzoyl oxide (BPO) / N,N-dimethyl-p-toluidine refers to dibenzoyl oxide (BPO) and N,N-dimethyl-p-toluidine compounded as an initiator, and hydroperoxide / ascorbic acid refers to peroxide and ascorbic acid compounded as an initiator.

[0148] In some embodiments, the oxidation / reduction initiator comprises an oxidant and a reductant, and the molar ratio of the oxidant to the reductant is (1:3) to (2:1).

[0149] In some embodiments, the initiator comprises a trialkyl boron / peroxide, wherein the trialkyl boron comprises one or more of triethyl boron, tri-n-butyl boron, tri-isobutyl boron, and tri-sec-butyl boron, and the peroxide comprises one or more of hydrogen peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, diketone peroxide, and peroxydicarbonate.

[0150] In some embodiments, the initiator includes trialkyl boron / peroxide, wherein the molar ratio of trialkyl boron to peroxide is (1:1) to (1:3).

[0151] In some embodiments, the oxidation / reduction initiator comprises hydroperoxide / ascorbic acid, wherein the hydroperoxide comprises one or more of isophenylpropyl hydroperoxide and tert-butyl hydroperoxide.

[0152] In some embodiments, the organic peroxide includes a dialkyl peroxide, and the dialkyl peroxide includes one or more of diisopropyl peroxide and di-tert-butyl peroxide.

[0153] In some embodiments, the organic peroxide includes diacyl peroxide, and the diacyl peroxide includes one or more of dibenzoyl peroxide and dodecanoyl peroxide.

[0154] In some embodiments, the organic peroxide comprises a peroxyester, and the peroxyester comprises one or more of tert-butyl perbenzoate and tert-butyl pervalerate.

[0155] In some embodiments, the organic peroxide includes a diketone peroxide, and the diketone peroxide includes one or more of methyl ethyl ketone peroxide and cyclohexanone peroxide.

[0156] In some embodiments, the organic peroxide comprises a peroxydicarbonate, and the peroxydicarbonate comprises one or more of diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.

[0157] In some embodiments, the molar concentration of the vinyl sulfone polymerization monomer in the solvent is (1 mol:3L) to (3 mol:1L), which can be 1 mol:3L, 1 mol:2L, 1 mol:1L, 2 mol:1L, 3 mol / 1L, etc.

[0158] In some embodiments, the molar ratio of the vinyl sulfone polymerization monomer to the initiator is (10:1) to (200:1), and can be 10:1, 30:1, 50:1, 100:1, 150:1, 200:1, etc.

[0159] In some embodiments, the polymerization reaction occurs under thermal initiation, which includes heating to 40°C to 100°C.

[0160] In some embodiments, the polymerization reaction time is 5 h to 48 h.

[0161] In some embodiments, the polymerization reaction is carried out under nitrogen or argon protection.

[0162] In some embodiments, the solvent used in the polymerization reaction includes at least one of N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,4-dioxane, and trifluoroacetic acid.

[0163] In some embodiments, the poor solvent includes at least one of water, methanol, ethanol, and ethyl acetate.

[0164] In some embodiments, the diluent used to dilute the polymer includes at least one of N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,4-dioxane, and trifluoroacetic acid.

[0165] In some embodiments, after the aliphatic polysulfone polymer is obtained by precipitation, it is further subjected to a washing treatment to improve the purity of the aliphatic polysulfone, and the washing agent used for washing includes ethanol.

[0166] In some embodiments, the aliphatic polysulfone is further dried after washing, and can be dried in a vacuum oven at 105° C. to 115° C. for 9 h to 11 h to obtain a solid powdered aliphatic polysulfone.

[0167] The present invention also provides a polymer prepared by the above-mentioned free radical rearrangement reaction-based degradable aliphatic polysulfone synthesis method, namely, aliphatic polysulfone, and the aliphatic polysulfone includes the following general structural formula:

[0168]

[0169] In the above-mentioned general structural formula of aliphatic polysulfone, n comprises a positive integer, m comprises 1 or 2, R1 comprises hydrogen, C1 to C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R2 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R3 includes hydrogen, C1~C 10 Alkyl, C1~C 10 R4 includes an unsaturated group having migration ability.

[0170] In the above-mentioned general structural formula of aliphatic polysulfone, R1 is C1~C 10 Alkyl, C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl.

[0171] In the above-mentioned general structural formula of aliphatic polysulfone, R1 is C1~C 10 Substituted alkyl, C1~C 10 The substituted alkyl groups include C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group.

[0172] In the above-mentioned general structural formula of aliphatic polysulfone, R1 is a halogen, and the halogen includes bromine, chlorine or iodine.

[0173] In the above structural formula, R2 is C1~C 10 Alkyl, C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl.

[0174] In the above-mentioned general structural formula of aliphatic polysulfone, R2 is C1~C 10 Substituted alkyl, C1~C 10 The substituted alkyl groups include C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group.

[0175] In the above-mentioned general structural formula of aliphatic polysulfone, R2 is a halogen, and the halogen includes bromine, chlorine or iodine.

[0176] In the above-mentioned general structural formula of aliphatic polysulfone, R3 is C1~C 10 Alkyl, C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl.

[0177] In the above-mentioned general structural formula of aliphatic polysulfone, R3 is C1~C 10 Substituted alkyl, C1~C 10 The substituted alkyl groups include C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group.

[0178] In the above structural formula of aliphatic polysulfone, R3 is halogen, and halogen includes bromine, chlorine or iodine.

[0179] In some embodiments, R4 in the above aliphatic polysulfone structural formula includes cyano, aryl, heteroaryl, oxime, alkenyl, alkynyl or carbonyl.

[0180] In some embodiments, the polymer aliphatic polysulfone comprises at least one of the following structural formulas:

[0181]

[0182] Wherein, n in any of the structural formulas comprises a positive integer.

[0183] The present invention designs alkenyl sulfone containing a migration group as a polymerization monomer, and realizes continuous chain growth through the alternating process of long-range migration of unsaturated groups and addition of sulfone free radicals to alkenyl groups under the action of an initiator, thereby obtaining aliphatic polysulfone with controllable sequence and high molecular weight, which can even be as high as 199,000.

[0184] The invention provides selectivity for the structural design of aliphatic polysulfone by adopting different migration modes and migration groups.

[0185] The vinyl sulfone monomer prepared by the present invention can be rapidly polymerized under free radical initiation conditions, and the molecular weight of the obtained aliphatic polysulfone can reach (80-200) kg / mol, the molecular weight distribution width is 1.2-2.7, the glass transition temperature is 60° C.-121° C., and the 5% thermal weight loss decomposition temperature is 180° C.-340° C. In some embodiments, the prepared aliphatic polysulfone has a refractive index of (1.60-1.68), which is comparable to commercial polycarbonate, but has an Abbe number of (25-30), which is higher than the Abbe number of commercial polycarbonate.

[0186] The aliphatic polysulfone developed by the present invention contains groups with further reaction ability, such as the alkynyl group protected by the silicon group can be deprotected in the presence of tetrabutylammonium fluoride to obtain an aliphatic polysulfone with a terminal alkynyl group as a side group. At the same time, the alkynyl group and the furan group can be respectively post-modified on the aliphatic polysulfone through Diels-Alder or Click reaction to adjust its structural properties.

[0187] The aliphatic polysulfone developed by the invention can be rapidly degraded or even completely degraded under strong alkaline conditions, and can obtain an olefin sulfinate as a main degradation product with a high conversion rate of 70% to 99%.

[0188] The invention solves the problems of uncontrollable sequence, poor solubility and low molecular weight in the preparation of aliphatic polysulfone by traditional olefin / sulfur dioxide low-temperature copolymerization or ring-opening polymerization of cyclic vinyl sulfone monomer.

[0189] In some embodiments, the olefin sulfinate obtained by degradation of aliphatic polysulfone comprises the following steps: adding aliphatic polysulfone and a strong base to a solvent under thermal conditions, stirring the reaction to obtain a reaction product, and separating and purifying the reaction product to obtain the olefin sulfinate.

[0190] In some embodiments, the temperature range of the thermal condition is 20°C to 80°C, for example 20°C, 25°C, 30°C, 35°C, 40°C, 50°C, 60°C, 79°C, 80°C, etc., which can not only be degraded by heating, but also meet the degradation requirements even at room temperature.

[0191] In some embodiments, the stirring reaction time is 0.5 h to 48 h.

[0192] In some embodiments, the concentration of the polymer aliphatic polysulfone in the solvent is 15 mg / ml to 1000 mg / mL.

[0193] In some embodiments, the molar ratio of sulfone group to strong base in the polymer aliphatic polysulfone is 1:(5-1).

[0194] In some embodiments, the solvent used to degrade the polymer aliphatic polysulfone to obtain the olefin sulfinate includes an organic solvent, and the organic solvent includes dichloromethane, chloroform, methanol, ethanol, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, etc.

[0195] In some embodiments, the strong base comprises an inorganic alkali metal hydroxide and / or an organic strong base.

[0196] In some embodiments, the strong base includes an inorganic alkali metal hydroxide, and the inorganic alkali metal hydroxide includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., preferably potassium hydroxide.

[0197] In some embodiments, the strong base comprises an organic strong base, and the organic strong base comprises at least one of potassium tert-butoxide, sodium methoxide, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetrabutylammonium hydroxide, tetramethylguanidine, and 4-dimethylaminopyridine, preferably potassium tert-butoxide.

[0198] In some embodiments, the yield of the degradation product olefin sulfinate is 70% to 99%.

[0199] In some embodiments, the olefin sulfinate obtained after degradation of the polymer aliphatic polysulfone comprises the following general structural formula:

[0200]

[0201] In the above-mentioned general structural formula of olefin sulfinate, m is 1 or 2, R4 includes an unsaturated group having migration ability, and M + Includes alkali metal cations or N cations.

[0202] In some embodiments, R4 in the above alkenyl sulfinate structure formula includes cyano, aryl, heteroaryl, oxime, alkenyl, alkynyl or carbonyl.

[0203] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the following specific embodiments are only used to explain the present invention, and are not used to limit the present invention.

[0204] Example 1 to Example 14

[0205] The preparation method of the polymer of Example 1 to Example 14 comprises the following steps:

[0206] 6mmol of vinyl sulfone polymerization monomer was placed in a 10mL glass reaction bottle with a tetrafluoroethylene lined lid, and the nitrogen was repeatedly replaced three times. The solvent is N,N-dimethylformamide (DMF). When the initiator is a triethylboron (TEB) / tert-butyl perbenzoate (TBPB) composite initiator system, its dosage is TEB / TBPB=3.0mol% / 3.6mol% (based on the total molar amount of vinyl sulfone polymerization monomer 100%); when the initiator is dibenzoyl peroxide (BPO), its dosage is 3.0mol% (based on the total molar amount of vinyl sulfone polymerization monomer 100%), and the reaction time is 24h. Operate according to the heating conditions in Table 1. After the reaction is completed, take 50μL of the reaction solution and dissolve it in 0.5mL of deuterated dimethyl sulfoxide and pass through 1 The monomer conversion rate is determined by the ratio of the characteristic peaks of the monomer and the polymer in H NMR. The remaining reaction solution is diluted with 3 mL of DMF or trifluoroacetic acid and then dripped into 100 mL of ethanol to precipitate the polymer. The precipitated solid is filtered and washed three times with ethanol, and then dried in a vacuum oven at 110°C for 10 hours to obtain a pure polymer aliphatic polysulfone solid powder. Figure 5 , Figure 6 and Figure 7 The nuclear magnetic hydrogen spectra of the aliphatic polysulfone obtained in Example 1, Example 3 and Example 9 are respectively, Figure 8 This is the GPC curve of the aliphatic polysulfone obtained in Example 9.

[0207] Table 1 Monomer structure and polymer structure of alkenyl sulfone polymerization in Examples 1 to 14

[0208]

[0209]

[0210] Table 2 Polymerization conditions of Examples 1 to 14

[0211]

[0212]

[0213] Table 3 Monomer conversion rate and polymer number average molecular weight (M) of Examples 1 to 14 n ) and distribution Glass transition temperature (T g ) and 5% thermal weight loss temperature (T d,5％ )

[0214]

[0215] Embodiment 15

[0216] This example uses the butylene benzothiazole sulfone in Example 1 as a polymerization monomer to synthesize a polymer:

[0217] 3.0mmol of butylenebenzothiazole sulfone and initiator azobisisobutyronitrile (3.0mol%, based on the total molar amount of butylenebenzothiazole sulfone 100%) were added to a 10mL glass reaction bottle with a tetrafluoroethylene lined lid, and the nitrogen was repeatedly replaced three times. 1.0mL of 1,4-dioxane was added as a solvent. The polymerization reaction was heated and stirred at 65°C for 24h. After the reaction was completed, 50μL of the reaction solution was dissolved in 0.5mL of deuterated dimethyl sulfoxide and passed through 1 The monomer conversion rate was determined by the ratio of the characteristic peaks of monomer and polymer in H NMR. The remaining reaction solution was diluted with 2 mL of 1,4-dioxane, and then added dropwise to 50 mL of ethanol to precipitate the polymer. The precipitated solid was filtered and washed three times with ethanol, and then dried in a vacuum oven at 110°C for 10 h to obtain a pure polymer solid powder.

[0218] In this example, the monomer conversion rate is 63%, the polymer number average molecular weight is 55100, and the distribution width is 1.35.

[0219] Example 16

[0220] This example still uses the butylene benzothiazole sulfone in Example 1 as a polymerization monomer to synthesize a polymer:

[0221] 0.6mmol of butenebenzothiazole sulfone and the oxidant dibenzoyl peroxide (3.0mol%, based on 100% of the total molar amount of butenebenzothiazole sulfone) were added to a 4mL glass reaction bottle with a tetrafluoroethylene lined lid, and the nitrogen was repeatedly replaced three times. 0.2mL of DMF was added as a solvent. Finally, the reducing agent N,N-dimethyl-p-toluidine (3.0mol%, based on 100% of the total molar amount of butenebenzothiazole sulfone) was added. The polymerization reaction was initiated at 30°C by a redox initiator system and stirred for 24h. After the reaction was completed, 50μL of the reaction solution was dissolved in 0.5mL of deuterated dimethyl sulfoxide and passed through 1 The monomer conversion rate was determined by the ratio of the characteristic peaks of monomer and polymer in H NMR. The remaining reaction solution was diluted with 1 mL of DMF, and then added dropwise to 5 mL of ethanol to precipitate the polymer. The precipitated solid was filtered and washed three times with ethanol, and then dried in a vacuum oven at 110°C for 10 h to obtain a pure polymer solid powder.

[0222] In this example, the monomer conversion rate is 66%, the polymer number average molecular weight is 61400, and the distribution width is 1.40.

[0223] Embodiment 17

[0224] This example provides a method for degrading the aliphatic polysulfone polymer obtained in Example 1 under strong alkaline conditions, and the specific preparation steps are as follows:

[0225] Take 15 mg of the aliphatic polysulfone obtained in Example 1 and add it to a 4 mL glass reaction bottle with a tetrafluoroethylene lined lid. Add 0.5 mL of deuterated dimethyl sulfoxide to completely dissolve the polymer. Then add 8.8 μL of DBU (based on the sulfone groups in the polymer, the amount of DBU added is 1 equivalent). Fig. 9 As shown, after stirring at room temperature for 3 h, 10 mg of trimethoxybenzene was added as an internal standard. 1 H NMR analysis showed that the polymer had been degraded, and olefin sulfinic acid was obtained as the main degradation product with a yield of 77%.

[0226] Embodiment 18

[0227] This example provides a method for degrading the aliphatic polysulfone polymer obtained in Example 1 under strong alkaline conditions, and the specific preparation steps are as follows:

[0228] Take 0.4g potassium hydroxide (purity 85%, calculated based on the sulfone group in the polymer, the addition amount is 1 equivalent) and 10mL of methanol and add them to a 25mL glass reaction bottle with a tetrafluoroethylene lined lid. After the potassium hydroxide is completely dissolved, add 1.52g of polymer. Stir at 60℃ for 0.5h, and the polymer degrades to obtain a clear and transparent solution. Slowly add ether to the reaction solution, wait for the degradation product to precipitate, filter it, wash it three times with ether, and then transfer it to a vacuum oven at 80℃ for 10h.

[0229] like Fig.10 As shown, the degradation products were determined by NMR. The yield was 99%.

[0230] The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction, characterized in that: The following steps are involved: The vinyl sulfone polymerization monomer, solvent and initiator are mixed, a polymerization reaction is carried out under light conditions or heat conditions to obtain a polymer solution, the polymer solution is diluted with a diluent to obtain a diluted polymer solution, and the diluted polymer solution is added dropwise to a poor solvent to obtain a polymer aliphatic polysulfone through precipitation; The alkenyl sulfone polymer monomer comprises the following general structural formula: In the general structural formula: m includes 1 or 2, R1 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R2 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R3 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R4 includes an unsaturated group having migration ability.

2. The method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction according to claim 1, characterized in that: In the R1: The R1 includes C1~C 10 The alkyl group of C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl; Or, the R1 includes C1~C 10 The substituted alkyl group, the C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group; Or, said R1 comprises halogen, said halogen comprises bromine, chlorine or iodine; and / or, in said R2: The R2 includes C1~C 10 The alkyl group of C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl; Or, the R2 includes C1~C 10 The substituted alkyl group, the C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group; Or, said R2 comprises halogen, said halogen comprises bromine, chlorine or iodine; and / or, in said R3: The R3 includes C1~C 10 The alkyl group of C1~C 10 The alkyl group includes methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl or adamantyl; Or, the R3 includes C1~C 10 The substituted alkyl group, the C1~C 10 The substituted alkyl group includes a C1-C4 perfluoroalkyl group; Or, said R3 comprises halogen, said halogen comprises bromine, chlorine or iodine; And / or, said R4 includes cyano, aryl, heteroaryl, oxime, alkenyl, alkynyl or carbonyl.

3. The method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction according to claim 1, characterized in that: The alkenyl sulfone polymer monomer includes any of the following structural formulas:

4. The method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction according to claim 1, characterized in that: The initiator includes one or more of azo compounds, organic peroxides, oxidation / reduction initiators, trialkyl boron / peroxides; and / or, the molar concentration of the vinyl sulfone polymerization monomer in the solvent is (1 mol:3L) to (3 mol:1L); and / or, the molar ratio of the vinyl sulfone polymerization monomer to the initiator is (10:1) to (200:1), and / or, a polymerization reaction occurs under the thermal conditions, wherein the thermal conditions include heating to 40° C. to 100° C.; And / or, the reaction time of the polymerization reaction is 5h to 48h; And / or, the polymerization reaction is carried out under the protection of nitrogen or argon; And / or, the solvent includes one or more of N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,4-dioxane, and trifluoroacetic acid; And / or, the poor solvent includes one or more of water, methanol, ethanol, and ethyl acetate; And / or, the diluent includes one or more of N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,4-dioxane, and trifluoroacetic acid.

5. The method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction according to claim 4, characterized in that: The initiator comprises an azo compound, and the azo compound comprises at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, azobiscyclohexylcarbonitrile, and dimethyl azobisisobutyrate; And / or, the initiator comprises an organic peroxide, and the organic peroxide comprises one or more of a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxyester, a diketone peroxide, and a peroxydicarbonate; And / or, the initiator comprises an oxidation / reduction initiator, and the oxidation / reduction initiator comprises at least one of dibenzoyl peroxide / N,N-dimethylaniline, dibenzoyl peroxide / N,N-dimethyl-p-toluidine, and hydroperoxide / ascorbic acid; And / or, the initiator comprises an oxidation / reduction initiator, the oxidation / reduction initiator comprises an oxidant and a reductant, and the molar ratio of the oxidant to the reductant is (1:3) to (2:1); And / or, the initiator comprises trialkyl boron / peroxide, the trialkyl boron comprises one or more of triethyl boron, tri-n-butyl boron, tri-isobutyl boron, tri-sec-butyl boron, and the peroxide comprises one or more of hydrogen peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, diketone peroxide, and peroxydicarbonate; And / or, the initiator comprises trialkyl boron / peroxide, and the molar ratio of the trialkyl boron to the peroxide is (1:1) to (1:3).

6. The method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction according to claim 5, characterized in that: The oxidation / reduction initiator comprises hydroperoxide / ascorbic acid, and the hydroperoxide comprises one or more of isophenylpropyl hydroperoxide and tert-butyl hydroperoxide; And / or, the organic peroxide includes a dialkyl peroxide, and the dialkyl peroxide includes one or more of diisopropyl peroxide and di-tert-butyl peroxide; And / or, the organic peroxide includes diacyl peroxide, and the diacyl peroxide includes one or more of dibenzoyl peroxide and dodecanoyl peroxide; And / or, the organic peroxide includes a peroxyester, and the peroxyester includes one or more of tert-butyl perbenzoate and tert-butyl pervalerate; And / or, the organic peroxide includes diketone peroxide, and the diketone peroxide includes one or more of methyl ethyl ketone peroxide and cyclohexanone peroxide; And / or, the organic peroxide includes peroxydicarbonate, and the peroxydicarbonate includes one or more of diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.

7. A polymer prepared by the method for synthesizing a degradable aliphatic polysulfone based on a free 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 includes positive integers; m includes 1 or 2, R1 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R2 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R3 includes hydrogen, C1~C 10 Alkyl, C1~C 10 substituted alkyl or halogen, R4 includes an unsaturated group having migration ability.

8. The polymer according to claim 7, characterized in that The polymer comprises at least one of the following structural formulas: Wherein, n in any of the structural formulas comprises a positive integer.

9. The polymer according to claim 8, characterized in that The polymer is degraded under alkaline conditions to obtain olefin sulfinate, and the polymer is degraded under alkaline conditions to obtain olefin sulfinate comprising the following steps: Under hot conditions, the polymer and a strong base are added to a solvent, stirred for reaction to obtain a reaction product, and the reaction product is separated and purified to obtain the olefin sulfinate.

10. The polymer according to claim 9, characterized in that The temperature range of the thermal condition is 20°C to 80°C; and / or, the concentration of the polymer in the solvent is 15 mg / ml to 1000 mg / mL; And / or, the stirring reaction time is 0.5h to 48h; and / or, the molar ratio of sulfone group to strong base in the polymer is 1:(5-1); And / or, the solvent comprises an organic solvent, and the organic solvent comprises at least one of dichloromethane, chloroform, methanol, ethanol, 1,4-dioxane, dimethyl sulfoxide, and N,N-dimethylformamide; And / or, the strong base includes an inorganic alkali metal, and the inorganic alkali metal includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., preferably potassium hydroxide; And / or, the strong base comprises an organic strong base, and the organic strong base comprises at least one of potassium tert-butoxide, sodium methoxide, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetrabutylammonium hydroxide, tetramethylguanidine, and 4-dimethylaminopyridine; and / or, the yield of the olefin sulfinate is 70% to 99%; And / or, the olefin sulfinate comprises the following general structural formula: In the general structural formula of the alkenyl sulfinate, m is 1 or 2, R4 includes an unsaturated group having migration ability, and M + It is an alkali metal cation or a N cation.

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