A method for synthesizing degradable aliphatic polysulfone based on radical rearrangement reaction and polymer

Abstract

The application discloses a kind of degradable aliphatic polysulfone synthesis method and polymer based on radical rearrangement reaction, belong to chemical synthesis technical field.The alkenyl sulfone containing migration group is designed as polymerization monomer in the application, and continuous chain growth is realized by the alternating process of long-distance migration of unsaturated group and addition of alkenyl group by sulfone radical under the action of initiator, and aliphatic polysulfone with controllable sequence and high molecular weight is obtained, and the structure design of aliphatic polysulfone can be selectively provided by using different migration modes and migration groups, 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 vinyl sulfone monomer ring-opening polymerization are solved.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, and in particular to a method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction and the polymer thereof. Background Technology

[0002] Free radical polymerization of vinyl monomers is currently an effective method for preparing polyolefin materials. Various products with properties meeting practical application requirements can be obtained by simply modifying side groups. However, the all-carbon chain structure of polyolefin materials not only poses environmental pressure due to their recalcitrant degradation but also further hinders their functional applications. Heteroatoms, especially sulfur, introduced into the polymer backbone can endow polymer materials with many attractive properties, including high refractive index, biodegradability, high mechanical properties, and heavy metal ion adsorption. Among these, copolymerization of various olefins with sulfur dioxide is an efficient method for preparing sulfur-containing polymers (aliphatic polysulfones). However, due to the ceiling temperature (depolymerization occurs above this temperature), copolymerization of olefins with sulfur dioxide is mostly carried out at low temperatures, and the resulting polysulfones have relatively low molecular weights. Furthermore, for olefins with different structures, there are problems such as uncontrollable sequence structure (styrene / SO2 copolymers), poor heat resistance (conjugated olefins / SO2 copolymers), and the generation of cyclic sulfone byproducts (conjugated or non-conjugated olefins / SO2 copolymers). Meanwhile, when polar side groups are lacking, polysulfone exhibits very poor solubility (it can only dissolve in trifluoroacetic acid or concentrated sulfuric acid), which not only makes it difficult to obtain information on molecular weight and its distribution, but also further limits its processability and application range.

[0003] Cyclic vinyl sulfones (CVS) offer a monomer design approach for the direct preparation of polysulfones. CVS utilizes free radical ring-opening, directly employing sulfone radicals as chain-growing radicals, allowing for high conversion rates through thermally initiated polymerization. However, the aliphatic polysulfones obtained from CVS monomers suffer from poor solubility due to the difficulty in introducing polar groups. Furthermore, the random ring-opening during CVS polymerization leads to uncontrollable polymer sequences, and the newly formed C=C bonds on the main chain result in poor heat resistance. Therefore, preparing high-molecular-weight aliphatic polysulfones with controllable sequences remains challenging.

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

[0005] The main objective of this invention is to provide a method for synthesizing biodegradable aliphatic polysulfones and a polymer based on free radical rearrangement reaction, thereby solving the technical problems of complex synthesis methods, difficult-to-control product structure, and poor performance of aliphatic polysulfones.

[0006] To achieve the above objectives, this invention provides a method for synthesizing degradable aliphatic polysulfones based on free radical rearrangement reactions, comprising the following steps:

[0007] An alkenyl sulfone monomer, solvent, and initiator are mixed and polymerized under light or heat conditions to obtain a polymer solution. The polymer solution is then diluted with a diluent to obtain a diluted polymer solution. The diluted polymer solution is then added dropwise to a poor solvent, and after precipitation, an aliphatic polysulfone polymer is obtained.

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

[0009]

[0010] In the general formula of the structure:

[0011] m includes 1 or 2,

[0012] R1 includes hydrogen, C1 to C1. 10 Alkyl groups, C1-C 10 Substituted alkyl or halogen,

[0013] R2 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10 Substituted alkyl or halogen,

[0014] R3 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10 Substituted alkyl or halogen,

[0015] R4 includes an unsaturated group with migratory ability.

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

[0017] R1 includes C1 to C 10 alkyl groups, wherein C1-C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl;

[0018] Alternatively, R1 includes C1 to C 10 The substituted alkyl groups, wherein C1-C 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups;

[0019] Alternatively, R1 may include a halogen, which may include bromine, chlorine, or iodine;

[0020] And / or, in said R2:

[0021] R2 includes C1 to C 10 alkyl groups, wherein C1-C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl;

[0022] Alternatively, R2 includes C1 to C 10 The substituted alkyl groups, wherein C1-C 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups;

[0023] Alternatively, R2 may include a halogen, which may include bromine, chlorine, or iodine;

[0024] And / or, in said R3:

[0025] R3 includes C1 to C 10 alkyl groups, wherein C1-C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl;

[0026] Alternatively, R3 includes C1 to C 10 The substituted alkyl groups, wherein C1-C 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups;

[0027] Alternatively, R3 may include a halogen, which may include bromine, chlorine, or iodine;

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

[0029] In some embodiments of the present invention, the alkenyl 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, redox initiators, and trialkylboron / peroxides;

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

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

[0034] And / or, the polymerization reaction occurs under the thermal conditions initiated by the thermal conditions, which include heating to 40°C to 100°C;

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

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

[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 inferior 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 comprises an azo compound, which includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovalerate, azobiscyclohexylformonitrile, and dimethyl azobisisobutyrate.

[0041] And / or, the initiator comprises an organic peroxide, which includes one or more of hydroperoxide, dialkyl peroxide, diacyl peroxide, ester peroxide, diketone peroxide, and dicarbonate peroxide;

[0042] And / or, the initiator includes a redox initiator, which includes at least one of benzoyl peroxide / N,N-dimethylaniline, benzoyl peroxide / N,N-dimethyl-p-toluidine, and hydroperoxide / ascorbic acid;

[0043] And / or, the initiator includes a redox initiator, which includes an oxidant and a reductant, wherein the molar ratio of the oxidant and the reductant is (1:3) to (2:1);

[0044] And / or, the initiator comprises trialkylboron / peroxide, wherein the trialkylboron comprises one or more of triethylboron, tri-n-butylboron, triisobutylboron, and trisec-butylboron, and the peroxide comprises one or more of hydrogen peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, ester peroxide, diketone peroxide, and dicarbonate peroxide;

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

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

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

[0048] And / or, the organic peroxide includes diacyl peroxide, which includes one or more of benzoyl peroxide and dodecyl peroxide;

[0049] And / or, the organic peroxide includes peroxide esters, and the peroxide esters include one or more of tert-butyl peroxide and tert-butyl peroxyvalerate;

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

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

[0052] The present invention also provides a polymer prepared by the biodegradable aliphatic polysulfone synthesis method based on free radical rearrangement reaction as described above, the polymer comprising the following general structural formula:

[0053]

[0054] In the general formula of the structure:

[0055] n includes positive integers;

[0056] m includes 1 or 2,

[0057] R1 includes hydrogen, C1 to C1. 10 Alkyl groups, C1-C 10 Substituted alkyl or halogen,

[0058] R2 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10 Substituted alkyl or halogen,

[0059] R3 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10Substituted alkyl or halogen,

[0060] R4 includes an unsaturated group with migratory 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 above structures includes a positive integer.

[0064] In some embodiments of the present invention, the polymer is degraded under alkaline conditions to obtain alkenyl sulfinates, and the degradation of the polymer under alkaline conditions to obtain alkenyl sulfinates includes the following steps:

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

[0066] In some embodiments of the present invention, the temperature range of the thermal conditions 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 0.5 h to 48 h;

[0069] And / or, the molar ratio of sulfone groups to strong bases in the polymer is 1:(5-1);

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

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

[0072] And / or, the strong base includes an organic strong base, which includes 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 alkenyl sulfinate is 70% to 99%;

[0074] And / or, alkenyl sulfinates include the following general structural formulas:

[0075]

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

[0077] The beneficial effects that this invention can achieve are:

[0078] This invention designs alkenyl sulfones containing migrating groups as polymerization monomers. Under the action of an initiator, continuous chain growth is achieved through an alternating process of unsaturated group long-range migration and sulfone radical addition to alkenyl groups, resulting in aliphatic polysulfones with controllable sequences and high molecular weights, even up to 199,000.

[0079] This invention also provides selectivity for the structural design of aliphatic polysulfones by employing different migration modes and migration groups.

[0080] The alkenyl sulfone monomer prepared by this invention can be rapidly polymerized under free radical initiation conditions. The resulting aliphatic polysulfone has a molecular weight of (80-200) kg / mol, a molecular weight distribution width of 1.2-2.7, a glass transition temperature of 60℃-121℃, a 5% thermal decomposition temperature of 180℃-340℃, and a refractive index of (1.60-1.68), comparable to commercial polycarbonate, but with an Abbe number of (25-30), which is higher than that of commercial polycarbonate.

[0081] The aliphatic polysulfone developed in this invention contains groups with further reactivity, such as silicon-protected alkynyl groups which can be deprotected in the presence of tetrabutylammonium fluoride to obtain aliphatic polysulfones with terminal alkynyl groups as side groups. Simultaneously, the alkynyl and furan groups can be post-modified by the aliphatic polysulfones via Diels-Alder or Click reactions, respectively, to adjust its structural properties.

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

[0083] This invention solves the problems of uncontrollable sequence, poor solubility, and low molecular weight in the preparation of aliphatic polysulfones by traditional low-temperature copolymerization of olefins / sulfur dioxide or ring-opening polymerization of cyclic vinyl sulfone monomers. Attached Figure Description

[0084] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0085] Figure 1 This is a schematic diagram of the synthesis process of an alkenyl sulfone polymer monomer according to an embodiment of the present invention.

[0086] Figure 2 This is a schematic diagram of the synthesis process of an alkenyl sulfone polymer monomer according to another embodiment of the present invention.

[0087] Figure 3 The 1H NMR spectrum of the alkenyl sulfone polymer monomer in Example 6 of this invention;

[0088] Figure 4 The carbon NMR spectrum of the alkenyl sulfone polymer monomer in Example 6 of this invention;

[0089] Figure 5 The 1H NMR spectrum of the polymer obtained in Example 1 of this invention;

[0090] Figure 6 The 1H NMR spectrum of the polymer obtained in Example 3 of this invention;

[0091] Figure 7 The 1H NMR spectrum of the polymer obtained in Example 9 of this invention;

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

[0093] Figure 9 This is a rough 1H NMR spectrum of the degradation reaction in Example 17 of the present invention;

[0094] Figure 10 The above is the 1H NMR spectrum of the degradation product in Example 18 of this invention.

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

[0096] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0097] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0098] In this invention, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include at least one of that feature. Furthermore, the technical solutions of the various embodiments can be combined with each other, but only on the basis of being achievable by those skilled in the art. If the combination of technical solutions is contradictory or impossible to implement, such a combination of technical solutions should be considered non-existent and not within the scope of protection claimed by this invention.

[0099] This invention provides a method for synthesizing biodegradable aliphatic polysulfone based on free radical rearrangement reaction, comprising the following steps: mixing alkenyl sulfone monomers, solvents and initiators, and carrying out a polymerization reaction under light or heat conditions to obtain a polymer solution; diluting the polymer solution with a diluent to obtain a diluted polymer solution; and adding the diluted polymer solution dropwise into a poor solvent, followed by precipitation to obtain polymeric aliphatic polysulfone.

[0100] In this invention, the alkenyl sulfone polymer monomer includes the following general structural formula:

[0101]

[0102] In the above general structural formula, m includes 1 or 2, and R1 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10 The substituted alkyl or halogen, R2 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10 Substituted alkyl groups or halogens, R3 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10 The substituted alkyl or halogen, R4 includes an unsaturated group with migratory ability.

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

[0104] In the above general structural formula, R1 includes C1 to C 10 Substituted alkyl groups, C1-C10 The substituted alkyl groups include C1 to C2. 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups.

[0105] In the above general structural formula, R1 includes halogens, which include bromine, chlorine or iodine.

[0106] In the above general structural formula, R2 includes C1 to C2. 10 Alkyl groups, C1-C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl.

[0107] In the above general structural formula, R2 includes C1 to C2. 10 Substituted alkyl groups, C1-C 10 The substituted alkyl groups include C1 to C2. 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups.

[0108] In the above general formula, R2 includes halogens, which include bromine, chlorine or iodine.

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

[0110] In the above general structural formula, R3 includes C1 to C 10 Substituted alkyl groups, C1-C 10 The substituted alkyl groups include C1 to C2. 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups.

[0111] In the above general structural formula, R3 includes halogens, which include bromine, chlorine or iodine.

[0112] In some embodiments, R4 includes cyano, aryl, heteroaryl, oxime, alkenyl, alkynyl, or carbonyl groups, which have migratory capabilities and facilitate the preparation of degradable aliphatic polysulfones via free radical rearrangement reactions.

[0113] The alkenyl sulfone polymer monomer of the present invention includes unsaturated groups with migratory capabilities. These unsaturated groups can be used as polymer monomers, and under the action of an initiator, continuous chain growth is achieved through alternating processes of long-range migration of unsaturated groups and addition of sulfone radicals to the alkenyl group, resulting in aliphatic polysulfones with controllable sequences and high molecular weights, even up to 199,000. Furthermore, the present invention can provide selectivity for the structural design of aliphatic polysulfones by employing different migration modes and migrating groups.

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

[0115] This invention further provides a method for preparing an alkenyl sulfone polymer monomer, but this is not to be considered a limitation of the invention. (See reference...) Figure 1 The synthesis process of the alkenyl sulfone polymer monomer is as follows: compound a reacts with elemental sulfur by strong base dehydrogenation and then acidification to obtain the corresponding thiol b. Thiol b and alkenyl halide c react under alkaline conditions or with alkenyl alcohol d via Mitsunobu reaction to obtain alkenyl ether e. Alkenyl ether e is oxidized to obtain alkenyl sulfone polymer monomer f containing migrating groups.

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

[0117] In this invention, thiols can be prepared by compound a or can be purchased directly, including 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole or 2-mercaptopyrimidine, etc.

[0118] This invention uses the synthesis of butenyl furan sulfone as an example to illustrate the specific steps of synthesizing alkenyl sulfone monomers, but this should not be considered a limitation of the invention. (Refer to...) Figure 2 Its reaction route includes the following steps:

[0119] Step 1: Synthesis of thiol a

[0120] Under nitrogen or argon protection at -78°C, n-butyllithium (200 mmol) was added dropwise to a tetrahydrofuran solution of furan (1.0 equivalent, 13.6 g, 200 mmol, 0.5 M). After the addition was complete, the mixture was stirred at room temperature for 1 h. Then, the temperature was lowered to -78°C, and elemental sulfur (6.412 g, 200 mmol) was added, followed by stirring at room temperature for 1 h. Finally, 200 mL of 2 M hydrochloric acid was added to quench the reaction and acidified for 0.5 h. The mixture was extracted three times with diethyl ether (200 mL × 3). The organic phases were combined, dried over anhydrous magnesium sulfate, and the diethyl ether was removed by vacuum distillation to obtain the crude product of thiol a, which was directly added to the next reaction without further purification.

[0121] Step 2: Synthesis of alkenyl sulfide b

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

[0123] Step 3: Synthesis of alkenyl sulfone C

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

[0125] refer to Figure 3 and Figure 4 , Figure 3 and Figure 4 The 1H and 1C NMR spectra of the alkenyl furan sulfone monomer prepared above confirm that the alkenyl furan sulfone monomer was successfully prepared.

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

[0127]

[0128] The characterization of the above-mentioned alkenyl sulfone polymer monomers is 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 azo compounds, organic peroxides, redox initiators, and trialkylboron / peroxides. It should be noted that a redox initiator refers to an initiator comprising both a reducing agent and an initiator, wherein the oxidizing agent and the reducing agent are combined as an initiator; a trialkylboron / peroxide refers to an initiator comprising both trialkylboron and a peroxide, wherein the trialkylboron and the peroxide are combined as an initiator.

[0145] In some embodiments, the azo compounds include at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovalerate, azobiscyclohexylformitrile, and dimethyl azobisisobutyrate.

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

[0147] In some embodiments, the oxidation / reduction initiator includes one or more of benzoyl peroxide (BPO) / N,N-dimethylaniline, benzoyl peroxide (BPO) / N,N-dimethyl-p-toluidine, and hydroperoxide / ascorbic acid. It should be noted that the oxidation / reduction initiator includes both oxidizing and reducing agents. Therefore, benzoyl peroxide (BPO) / N,N-dimethylaniline refers to a combination of benzoyl peroxide (BPO) and N,N-dimethylaniline as an initiator; benzoyl peroxide (BPO) / N,N-dimethyl-p-toluidine refers to a combination of benzoyl peroxide (BPO) and N,N-dimethyl-p-toluidine as an initiator; and hydroperoxide / ascorbic acid refers to a combination of peroxide and ascorbic acid as an initiator.

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

[0149] In some embodiments, the initiator comprises trialkylboron / peroxide, wherein the trialkylboron comprises one or more of triethylboron, tri-n-butylboron, triisobutylboron, and trisec-butylboron, and the peroxide comprises one or more of hydrogen peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxide ester, diketone peroxide, and dicarbonate peroxide.

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

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

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

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

[0154] In some embodiments, the organic peroxide includes peroxide esters, which include one or more of tert-butyl peroxide and tert-butyl peroxyvalerate.

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

[0156] In some embodiments, the organic peroxide includes dicarbonate peroxide, which includes one or more of diisopropyl peroxide and dicyclohexyl peroxide.

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

[0158] In some embodiments, the molar ratio of alkenyl sulfone polymerization monomer to 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 thermally initiated conditions, including heating to 40°C to 100°C.

[0160] In some embodiments, the reaction time of the polymerization reaction 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 inferior 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 precipitation to obtain aliphatic polysulfone polymer, a washing treatment is performed to improve the purity of the aliphatic polysulfone. The washing agent used includes ethanol.

[0166] In some embodiments, the aliphatic polysulfone is washed and then dried, which can be done in a vacuum oven at 105°C to 115°C for 9 to 11 hours to obtain aliphatic polysulfone in solid powder form.

[0167] The present invention also provides a polymer, namely aliphatic polysulfone, prepared by the above-described method for synthesizing degradable aliphatic polysulfone based on free radical rearrangement reaction, wherein the aliphatic polysulfone comprises the following general structural formula:

[0168]

[0169] In the above general structural formula of aliphatic polysulfone, n includes a positive integer, m includes 1 or 2, and R1 includes hydrogen, C1~C1. 10 Alkyl groups, C1-C 10 The substituted alkyl or halogen, R2 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10 Substituted alkyl groups or halogens, R3 includes hydrogen, C1 to C2. 10 Alkyl groups, C1-C 10 The substituted alkyl or halogen, R4 includes an unsaturated group with migratory ability.

[0170] In the above general structural formula of aliphatic polysulfone, R1 is C1 to C2. 10 Alkyl groups, C1-C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl.

[0171] In the above general structural formula of aliphatic polysulfone, R1 is C1 to C2. 10 Substituted alkyl groups, C1-C 10 The substituted alkyl groups include C1 to C2. 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups.

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

[0173] In the above general structural formula, R2 represents C1 to C2. 10 Alkyl groups, C1-C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl.

[0174] In the above general structural formula of aliphatic polysulfone, R2 is C1 to C2. 10 Substituted alkyl groups, C1-C 10 The substituted alkyl groups include C1 to C2. 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups.

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

[0176] In the above general structural formula of aliphatic polysulfone, R3 is C1 to C2. 10 Alkyl groups, C1-C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl.

[0177] In the above general structural formula of aliphatic polysulfone, R3 is C1 to C2. 10 Substituted alkyl groups, C1-C 10 The substituted alkyl groups include C1 to C2. 10 The substituted alkyl groups include C1 to C4 perfluoroalkyl groups.

[0178] In the above-mentioned general structural formula of aliphatic polysulfone, R3 is a halogen, which includes bromine, chlorine or iodine.

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

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

[0181]

[0182] Wherein, n in any of the above structures includes a positive integer.

[0183] This invention designs alkenyl sulfones containing migrating groups as polymerization monomers. Under the action of an initiator, continuous chain growth is achieved through an alternating process of unsaturated group long-range migration and sulfone radical addition to alkenyl groups, resulting in aliphatic polysulfones with controllable sequences and high molecular weights, even up to 199,000.

[0184] This invention provides selectivity for the structural design of aliphatic polysulfones by employing different migration modes and migration groups.

[0185] The alkenyl sulfone monomer prepared by this invention can be rapidly polymerized under free radical initiation conditions, resulting in aliphatic polysulfones with molecular weights ranging from 80 to 200 kg / mol, a molecular weight distribution width of 1.2 to 2.7, a glass transition temperature of 60°C to 121°C, and a 5% thermogravimetric decomposition temperature of 180°C to 340°C. In some embodiments, the prepared aliphatic polysulfone has a refractive index of 1.60 to 1.68, comparable to commercial polycarbonate, but an Abbe number of 25 to 30, which is higher than that of commercial polycarbonate.

[0186] The aliphatic polysulfone developed in this invention contains groups with further reactivity, such as silicon-protected alkynyl groups which can be deprotected in the presence of tetrabutylammonium fluoride to obtain aliphatic polysulfones with terminal alkynyl groups as side groups. Simultaneously, the alkynyl and furan groups can be post-modified by the aliphatic polysulfones via Diels-Alder or Click reactions, respectively, to adjust its structural properties.

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

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

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

[0190] In some embodiments, the temperature range of the thermal conditions is 20°C to 80°C, such as 20°C, 25°C, 30°C, 35°C, 40°C, 50°C, 60°C, 79°C, 80°C, etc., which can not only degrade by heating, but also meet the degradation requirements under room temperature conditions.

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

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

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

[0194] In some embodiments, the solvents used to degrade the aliphatic polysulfone polymer to obtain alkenyl sulfinates include organic solvents, such as dichloromethane, chloroform, methanol, ethanol, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, etc.

[0195] In some embodiments, strong bases include inorganic alkali metal hydroxides and / or organic strong bases.

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

[0197] In some embodiments, the strong base includes an organic strong base, which includes 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, alkenyl sulfinate, is 70% to 99%.

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

[0200]

[0201] In the above general structural formula of alkenyl sulfinates, m is 1 or 2, R4 includes an unsaturated group with migratory ability, and M + This includes alkali metal cations or nitrogen ions.

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

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

[0204] Examples 1 to 14

[0205] The preparation methods of the polymers in Examples 1 to 14 include the following steps:

[0206] 6 mmol of alkenyl sulfone monomer was placed in a 10 mL glass reaction flask with a tetrafluoroethylene-lined cap, and the nitrogen gas was repeatedly purged three times. The solvent was N,N-dimethylformamide (DMF). When the initiator was a triethylboron (TEB) / tert-butyl peroxide (TBPB) composite initiator system, the amount of TEB / TBPB was 3.0 mol% / 3.6 mol% (based on 100% of the total molar amount of alkenyl sulfone monomer); when the initiator was benzoyl peroxide (BPO), the amount of BPO was 3.0 mol% (based on 100% of the total molar amount of alkenyl sulfone monomer), and the reaction time was 24 h. The heating conditions in Table 1 were followed. After the reaction was completed, 50 μL of the reaction solution was dissolved in 0.5 mL 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 ¹H NMR. The remaining reaction solution was diluted with 3 mL of DMF or trifluoroacetic acid and then added dropwise to 100 mL of ethanol to precipitate the polymer. The precipitated solid was filtered, washed three times with ethanol, and then dried in a vacuum oven at 110 °C for 10 h to obtain pure polymer aliphatic polysulfone solid powder. Figure 5 , Figure 6 and Figure 7 The 1H NMR spectra of the aliphatic polysulfones obtained in Examples 1, 3, and 9 are shown below. Figure 8 The image shows the GPC curve of the aliphatic polysulfone obtained in Example 9.

[0207] Table 1. Structures of alkenyl sulfone polymonomers and polymers in Examples 1-14

[0208]

[0209]

[0210] Table 2 Polymerization reaction 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] Example 15

[0216] In this embodiment, butene benzothiazole sulfone from Example 1 is used as the polymerization monomer to synthesize the polymer:

[0217] 3.0 mmol of butene benzothiazole sulfone and initiator azobisisobutyronitrile (3.0 mol%, based on 100% of the total molar amount of butene benzothiazole sulfone) were added to a 10 mL glass reaction flask with a tetrafluoroethylene-lined cap, and the nitrogen atmosphere was repeatedly purged three times. 1.0 mL of 1,4-dioxane was added as a solvent. The polymerization reaction was heated and stirred at 65 °C for 24 h. After the reaction was completed, 50 μL of the reaction solution was dissolved in 0.5 mL 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 ¹H 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, 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 embodiment, the monomer conversion rate is 63%, the number-average molecular weight of the polymer is 55,100, and the distribution width is 1.35.

[0219] Example 16

[0220] This embodiment still uses butenebenzothiazole sulfone from Example 1 as the polymer monomer to synthesize the polymer:

[0221] 0.6 mmol of butene benzothiazole sulfone and benzoyl peroxide (3.0 mol%, based on 100% of the total molar amount of butene benzothiazole sulfone) were added to a 4 mL glass reaction flask with a tetrafluoroethylene-lined cap, and the nitrogen atmosphere was repeatedly purged three times. 0.2 mL of DMF was added as a solvent. Finally, N,N-dimethyl-p-toluidine (3.0 mol%, based on 100% of the total molar amount of butene benzothiazole sulfone) was added as a reducing agent. The polymerization reaction was initiated at 30 °C using a redox initiation system and stirred for 24 h. After the reaction was complete, 50 μL of the reaction solution was dissolved in 0.5 mL 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 ¹H 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, 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 embodiment, the monomer conversion rate is 66%, the number-average molecular weight of the polymer is 61,400, and the distribution width is 1.40.

[0223] Example 17

[0224] This embodiment provides a method for degrading the aliphatic polysulfone polymer obtained in Example 1 under strongly alkaline conditions. 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 flask with a tetrafluoroethylene-lined cap. 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). Figure 9 As shown, after stirring at room temperature for 3 hours, 10 mg of trimethoxybenzene was added as an internal standard, and the reaction was carried out by... 1 ¹H NMR analysis revealed that the polymer had degraded, with alkenyl sulfinic acid being the main degradation product in 77% yield.

[0226] Example 18

[0227] This embodiment provides a method for degrading the aliphatic polysulfone polymer obtained in Example 1 under strongly alkaline conditions. The specific preparation steps are as follows:

[0228] Add 0.4 g of potassium hydroxide (85% purity, calculated as 1 equivalent based on the sulfone group in the polymer) and 10 mL of methanol to a 25 mL glass reaction flask with a tetrafluoroethylene-lined cap. After the potassium hydroxide is completely dissolved, add 1.52 g of the polymer. Stir at 60 °C for 0.5 h; the polymer degrades to obtain a clear, transparent solution. Slowly add diethyl ether to the reaction solution; after the degradation product precipitates, filter and wash three times with diethyl ether, then transfer to a vacuum oven to dry at 80 °C for 10 h.

[0229] like Figure 10 As shown, the degradation products were determined by NMR to be... Its yield is 99%.

[0230] The above are merely preferred embodiments of the present invention and do not limit the scope of the patent. Any equivalent structural or procedural transformations made based on the description and drawings of the present invention, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of the present invention.

Claims

1. A method for synthesizing biodegradable aliphatic polysulfone based on free radical rearrangement reaction, characterized in that, Includes the following steps: An alkenyl sulfone monomer, solvent, and initiator are mixed and polymerized under light or heat conditions to obtain a polymer solution. The polymer solution is then diluted with a diluent to obtain a diluted polymer solution. The diluted polymer solution is then added dropwise to a poor solvent, and after precipitation, an aliphatic polysulfone polymer is obtained. The alkenyl sulfone polymer monomer includes the following general structural formula: ， In the general formula of the structure: m includes 1 or 2, R1 includes hydrogen, C1~C1. 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 unsaturated groups with migratory capabilities; The R4 group includes cyano, aryl, heteroaryl, oxime, alkenyl, alkynyl, or carbonyl.

2. The method for synthesizing biodegradable aliphatic polysulfone based on free radical rearrangement reaction according to claim 1, characterized in that, In R1: R1 includes C1~C 10 alkyl groups, the C1~C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl; Alternatively, R1 includes C1~C 10 The substituted alkyl groups, wherein C1~C 10 The substituted alkyl groups include C1-C4 perfluoroalkyl groups; Alternatively, R1 may include a halogen, which may include bromine, chlorine, or iodine; And / or, in said R2: R2 includes C1~C 10 alkyl groups, the C1~C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl; Alternatively, R2 includes C1~C 10 The substituted alkyl groups, wherein C1~C 10 The substituted alkyl groups include C1-C4 perfluoroalkyl groups; Alternatively, R2 may include a halogen, which may include bromine, chlorine, or iodine; And / or, in said R3: R3 includes C1~C 10 alkyl groups, the C1~C 10 The alkyl groups include methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl; Alternatively, R3 includes C1~C 10 The substituted alkyl groups, wherein C1~C 10 The substituted alkyl groups include C1-C4 perfluoroalkyl groups; Alternatively, R3 may include a halogen, which may include bromine, chlorine, or iodine.

3. The method for synthesizing biodegradable 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 biodegradable 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, redox initiators, and trialkylboron / peroxides; And / or, the molar concentration of the alkenyl sulfone polymer monomer in the solvent is (1 mol: 3 L) ~ (3 mol: 1 L). And / or, the molar ratio of the alkenyl sulfone polymerization monomer to the initiator is (10:1) to (200:1). And / or, the polymerization reaction occurs under the thermal conditions initiated by the thermal conditions, which 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 nitrogen or argon protection; 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 inferior 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 biodegradable aliphatic polysulfone based on free radical rearrangement reaction according to claim 4, characterized in that, The initiator includes an azo compound, which includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovalerate, azobiscyclohexylformonitrile, and dimethyl azobisisobutyrate. And / or, the initiator comprises an organic peroxide, which includes one or more of hydroperoxide, dialkyl peroxide, diacyl peroxide, ester peroxide, diketone peroxide, and dicarbonate peroxide; And / or, the initiator includes a redox initiator, which includes at least one of benzoyl peroxide / N,N-dimethylaniline, benzoyl peroxide / N,N-dimethyl-p-toluidine, and hydroperoxide / ascorbic acid; And / or, the initiator includes a redox initiator, which includes an oxidant and a reductant, wherein the molar ratio of the oxidant to the reductant is (1:3) to (2:1). And / or, the initiator comprises trialkylboron / peroxide, wherein the trialkylboron comprises one or more of triethylboron, tri-n-butylboron, triisobutylboron, and trisec-butylboron, and the peroxide comprises one or more of hydrogen peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, ester peroxide, diketone peroxide, and dicarbonate peroxide; And / or, the initiator comprises trialkylboron / peroxide, wherein the molar ratio of the trialkylboron to the peroxide is (1:1) to (1:3).

6. The method for synthesizing biodegradable aliphatic polysulfone based on free radical rearrangement reaction according to claim 5, characterized in that, The oxidation / reduction initiator includes hydroperoxide / ascorbic acid, and the hydroperoxide includes one or more of isopropyl hydroperoxide and tert-butyl hydroperoxide; And / or, the organic peroxide includes dialkyl peroxide, which includes one or more of diisopropyl peroxide and ditert-butyl peroxide; And / or, the organic peroxide includes diacyl peroxide, which includes one or more of benzoyl peroxide and dodecyl peroxide; And / or, the organic peroxide includes peroxide esters, and the peroxide esters include one or more of tert-butyl peroxide and tert-butyl peroxyvalerate; And / or, the organic peroxide includes diketene peroxide, which includes one or more of methyl ethyl ketone peroxide and cyclohexanone peroxide; And / or, the organic peroxide includes dicarbonate peroxide, which includes one or more of diisopropyl peroxide and dicyclohexyl peroxide.

7. A polymer prepared by the biodegradable aliphatic polysulfone synthesis method based on free radical rearrangement reaction as described in any one of claims 1 to 6, characterized in that, The polymer includes the following general structural formula: In the general formula of the structure: n includes positive integers; m includes 1 or 2, R1 includes hydrogen, C1~C1. 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 with migratory ability.

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

9. The polymer according to claim 8, characterized in that, The polymer is degraded under alkaline conditions to obtain alkenyl sulfinate, and the degradation of the polymer under alkaline conditions to obtain alkenyl sulfinate includes the following steps: Under thermal conditions, the polymer and a strong base are added to a solvent and stirred to obtain a reaction product. The reaction product is then separated and purified to obtain the alkenyl sulfinate.

10. The polymer according to claim 9, characterized in that, The temperature range of the thermal conditions is 20℃~80℃; 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 0.5 h to 48 h; And / or, the molar ratio of sulfone groups to strong bases in the polymer is 1:(5~1); And / or, the solvent includes an organic solvent, which includes 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, which includes at least one of sodium hydroxide, potassium hydroxide, and lithium hydroxide; And / or, the strong base includes an organic strong base, which includes 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 alkenyl sulfinate is 70% to 99%; And / or, alkenyl sulfinates include the following general structural formulas: ， In the general structural formula of the alkenyl sulfinate, m is 1 or 2, R4 includes an unsaturated group with migratory ability, and M + It is an alkali metal cation or a nitrogen ion.

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