Process for the preparation of sulfonamide polymers

Abstract

The application discloses a preparation method of a sulfonamide polymer, which comprises the following steps: mixing a sulfonamide compound, a compound with active hydrogen and a catalyst to perform a polymerization reaction, or mixing the sulfonamide compound, an epoxide compound, the compound with active hydrogen and the catalyst to perform a polymerization reaction, so as to obtain the sulfonamide polymer. Through designing a suitable N-sulfonylation monomer activation strategy and a catalytic system, the application can effectively activate an amide bond and implement active and controllable polymerization of the sulfonamide monomer. Meanwhile, the sulfonamide polymer and the preparation method thereof have the advantages of simple operation, mild conditions, atomic economy, high selectivity and wide applicability; and the obtained sulfonamide polymer has novel repeating unit structure, controllable molecular weight, narrow molecular weight distribution, rich adjustable side group functional groups and topological structure, good thermal stability and degradability.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis, and more specifically to a method for preparing sulfonamide polymers. Background Technology

[0002] Heterochain polymers consist of a backbone composed of carbon atoms and one or more heteroatoms, such as oxygen, nitrogen, sulfur, and phosphorus. Compared to pure carbon-chain polymers, different types of heteroatoms and bonding methods endow polymers with many new physical / chemical properties, leading to a wide variety of applications. For example, ether bonds formed by carbon and oxygen linked by single bonds exhibit high polarity and flexibility; corresponding polyether polymers are commonly used as nonionic surfactants and the soft segment of polyurethanes. Polyesters formed by carbon and oxygen linked by double and single bonds are degradable and crystallizable, and are considered environmentally friendly materials, finding wide applications in engineering plastics and fibers. Other heterochain polymers, such as nitrogen / phosphorus / sulfur-containing poly(thio)amides, poly(thiourea), and DNA, play indispensable roles in structural materials, functional materials, and genetics.

[0003] Chain polymerization of heterocyclic compounds is an important route for synthesizing heterochain polymers, typically characterized by ease of operation and atom economy. In this regard, epoxy monomers exhibit numerous advantages, including easy polymerization, rich structures and functional groups, wide availability, and high yield, leading to rapid development in their research and application. Starting with the ring-opening polymerization and copolymerization of epoxides, a series of heterochain polymers with diverse structures and main chain compositions have been constructed, including polyethers, (thio- / thioether-containing / selenium-containing) polyesters, poly(thio)carbonates, polyurethanes, polythioimide carbonates, polysulfone resins, and so on. Therefore, researching and developing new epoxy comonomers will further enrich the variety and properties of heterochain polymers. On the other hand, currently, copolymerizable monomers are mainly compounds containing oxo groups; only in recent years have nitrogen-containing isothiocyanates and a few other isocyanates been included in epoxy copolymerization reactions. Currently, lactams and lactimide derivatives also possess advantages such as high yield, structural diversity, and good stability, making them a large class of ideal raw materials for introducing nitrogen atoms into the polymer backbone. However, most lactam compounds are difficult to polymerize, and lactimides are even more difficult to use as monomers for ring-opening polymerization. Only ε-caprolactam has been extensively studied for ring-opening polymerization and is maturely applied in polyamide production, but effective methods for controlled polymerization are still lacking.

[0004] Epoxy reactive anionic (co)polymerization allows for precise control of molecular weight and polymer structure, yielding heterochain polymers with narrow distributions and well-defined structures. However, direct copolymerization of epoxides and lactimides under these polymerization conditions presents significant challenges. First, heterocyclic compounds containing active hydrogen atoms in amide bonds may act as "initiating monomers," meaning that in addition to undergoing their own ring-opening reaction, the amide group can also be hydrogen-extracted by a base to form new chain-growing active species, resulting in uncontrollable molecular weight and chain structure. Second, in chain copolymerization under the same catalytic conditions, the rates of several cross-growing reactions (reactions between active species formed by any comonomer and other comonomers) cannot differ too significantly; otherwise, the copolymerization reaction is difficult to occur. In fact, amide bonds are very stable; alkoxy anions formed from epoxy ring-opening rarely undergo nucleophilic ring-opening reactions with lactimides, while nitrogen anions readily induce epoxy ring-opening.

[0005] Therefore, there is an urgent need to develop a catalytic system and synthesis method suitable for the polymerization reactions of epoxides, lactams and lactimide derivatives, which has readily available raw materials, low cost, conforms to green economy, has high conversion rate, simple preparation method, strong controllability of molecular weight and structure, and is suitable for large-scale preparation. Summary of the Invention

[0006] In order to overcome the problems existing in the prior art, the purpose of this invention is to provide a method for preparing sulfonamide polymers and their applications.

[0007] The key to this invention lies in the use of a strongly electron-withdrawing and chemically stable sulfonyl group to activate the amide bond. The resulting N-sulfonyl lactam monomer (N-sulfonyl lactam monomer or N-sulfonyl lactam imide monomer, hereinafter referred to as sulfonamide compounds) readily undergoes a ring-opening reaction involving the breaking of the CN bond in the presence of a nucleophilic active species, which can further lead to polymerization. This method offers advantages such as ease of operation, mild conditions, atom economy, high selectivity, and wide applicability. Its advantages are: single-component or two-component catalysts enable controlled copolymerization of epoxides and N-sulfonyl lactams, exhibiting excellent catalytic activity and reaction control; active hydrogen compounds, acting as initiators, allow for precise control of the polymer's molecular weight, end-group structure, and topology, thereby obtaining a series of sulfonamide polymers with novel repeating units, rich structures, diverse side group and main chain components, controllable and narrowly distributed molecular weights, and good thermal stability and (bio)degradability.

[0008] It should be noted that the key to the successful implementation of controlled copolymerization in this invention lies in the amide bond activation strategy. It is necessary to design a suitable N-sulfonyl monomer activation strategy and catalytic system so that both the epoxy and the lactimide can undergo ring-opening reactions, while fully suppressing chain exchange reactions (ester exchange) and chain transfer reactions to monomers during the polymerization process, so as to obtain a novel heterochain polymer with precise and controllable sequence structure.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] In a first aspect, the present invention provides a method for preparing sulfonamide polymers, characterized by comprising the following steps:

[0011] A sulfonamide polymer is obtained by mixing a sulfonamide compound, an active hydrogen compound, and a catalyst and carrying out a polymerization reaction.

[0012] Alternatively, sulfonamide compounds, epoxy compounds, active hydrogen compounds and catalysts can be mixed and polymerized to obtain sulfonamide polymers.

[0013] The molar ratio of the sulfonamide compound to the catalyst is 100:(0.01-5); the catalyst is selected from at least one of Lewis acid, Bronte acid, Lewis base, and Bronte base.

[0014] Specifically, the preparation method of the sulfonamide polymer can effectively activate amide bonds and controllably produce sulfonamide polymers with narrow molecular weight distribution, high atom utilization, and specific structure.

[0015] First scenario:

[0016] In some embodiments, the method for preparing sulfonamide polymers includes the following steps:

[0017] A sulfonamide polymer is obtained by mixing a sulfonamide compound, an active hydrogen compound, and a catalyst and carrying out a polymerization reaction.

[0018] The molar ratio of the sulfonamide compound to the catalyst is 10:(0.1–0.5); the catalyst is selected from at least one Lewis base or a Brownian base. Specifically, the sulfonamide compound is a monomer, and it is an N-sulfonyl lactone (imide) obtained by N-sulfonation of a heterocyclic compound containing a -(C=O)-NH- or -(C=O)-NH-(C=O)- structure.

[0019] In some embodiments, the sulfonamide compound is prepared by sulfonation of heterocyclic compound A, wherein compound A is selected from 2-azacyclobutanone, 2-pyrrolidone, 4,4-pentamethylene-2-pyrrolidone, 2-indolone, isoindolin-1-one, 2-azabicyclo[2.2.1]hept-5-en-3-one, indole-2,3-dione, 2-azahexanecycloone, 3,4-dihydro-2(1H)-quinolinone, C1-C18 1-alkyl-3-oxopiperazine, 1-ethylpiperazinedione, 3-morpholinone, 2,4-piperidinedione, glycine anhydride, and 3-oxopiperazine-1-carboxylic acid. At least one of the following: tert-butyl ester, 3-oxopiperazine-1-carboxylic acid benzyl ester, octanolamide, ε-caprolactam, 1,4-oxazetane-hepta-5-one, 1,4-thioazetane-hepta-5-one, hepta-lactam, laurolactam, succinimide, maleimide, cyclopentadienimide, cyclohexanediimide, phthalimide, 1,2,3,6-tetrahydrophthalimide, 2,4-thiazolidinedione, rhodanine, glutarimide, 3,3-dimethylglutarimide, 8-azaspiro[4.5]decane-7,9-dione, 2,4-imidazolinide, barbituric acid, and 1-methylbarbituric acid. Specifically, the specific structural formula is as follows:

[0020]

[0021] In compound (10), m is an integer and the value of m ranges from 0 to 17.

[0022] Preferably, the heterocyclic compound is selected from at least one of 2-pyrrolidone, 2-azhexanecycloone, ε-caprolactam, succinimide, and glutarimide.

[0023] In some embodiments, the sulfonamide compound is selected from one of the following compounds:

[0024]

[0025] Where k and L are both integers, and the value of k ranges from 1 to 12, and the value of L ranges from 1 to 3;

[0026] R is selected from one of the following: phenyl, benzyl, C1-C5 alkyl para-substituted phenyl, nitrophenyl, CF3-substituted phenyl, heteroaryl, CF3, CBr3, CCl3, F-substituted C1-C5 alkyl, Br-substituted C1-C5 alkyl, and Cl-substituted C1-C5 alkyl.

[0027] Preferably, k and L are both integers, and the value range of k is 1 to 6, and the value range of L is 1 to 3.

[0028] In some preferred embodiments, the sulfonamide compound is selected from one of the following compounds:

[0029]

[0030] In some embodiments, the molar ratio of the sulfonamide compound to the catalyst is 100:2.

[0031] In some embodiments, the catalyst is an organic base selected from at least one of phosphazene bases, triaminophosphine, nitrogen-containing heterocyclic carbene, tertiary amines, amidine, guanidine, alkyllithium, phenyllithium, alkyl zinc, alkyl zinc halide, alkyl magnesium halide, aryl zinc halide, aryl magnesium halide, lithium di(trimethylsilyl)amino, sodium di(trimethylsilyl)amino, potassium di(trimethylsilyl)amino, lithium diisopropylamino, alkali metal alkoxides, alkali metal thiolates, lithium phenoxide, sodium phenoxide, potassium phenoxide, cesium phenoxide, lithium thiophene, sodium thiophene, potassium thiophene, cesium thiophene, quaternary ammonium bases, caustic bases, alkali metal salts, crown ether complexes, ammonium salts, quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts, and pyridinium salts. Specifically, the organic base is a Lewis base and / or a Brownian base.

[0032] Preferably, the phosphazene base is BEMP. t BuP1、 t BuP1(pyrr) t BuP2, EtP2 t At least one of BuP4, with the following specific structural formula:

[0033]

[0034] The triaminophosphine is at least one of HMTP, HETP, TMAP, and TIPAP, with the following specific structural formula:

[0035]

[0036] The nitrogen-containing heterocyclic carbene is at least one of the following structures:

[0037]

[0038] The tertiary amine is at least one of TEA, DABCO, PMDETA, ME6TREN, and sparteine, with the following specific structural formula:

[0039] The amidine is at least one of DBN and DBU, and its specific structural formula is as follows:

[0040] The guanidine is at least one of TBD, MTBD, TMG, and PMG, and its specific structural formula is as follows:

[0041]

[0042] Preferably, the alkyl lithium is selected from at least one of C1-C6 alkyl lithium and cyclopropyl lithium.

[0043] Preferably, the alkyl zinc is selected from at least one of C1 to C6 dialkyl zinc.

[0044] Preferably, the alkyl zinc halide is selected from at least one of C1-C8 alkyl zinc chloride, C1-C12 alkyl zinc bromide, and C3-C6 cycloalkyl zinc bromide.

[0045] Preferably, the alkyl magnesium halide is selected from at least one of C1-C18 alkyl magnesium chloride, C1-C18 alkyl magnesium bromide, methyl magnesium iodide, C3-C6 cycloalkyl magnesium chloride, and C3-C6 cycloalkyl magnesium bromide.

[0046] Preferably, the aryl zinc halide is selected from at least one of phenyl zinc bromide, 1-styrene zinc bromide, 2-pyridyl zinc bromide, 2-thienyl zinc bromide, phenyl zinc iodide, and 1-naphthyl zinc iodide.

[0047] Preferably, the aryl magnesium halide is selected from at least one of phenyl magnesium chloride, tolyl magnesium chloride, phenyl magnesium bromide, tolyl magnesium bromide, 2-pyridyl magnesium bromide, naphthyl magnesium bromide, cyclopentadienyl magnesium bromide, thiophene magnesium bromide, phenyl magnesium iodide, and thiophene magnesium iodide.

[0048] Preferably, the alkali metal alkoxide is selected from at least one of lithium tert-butoxide / sodium / potassium / cesium, lithium tert-amyloxide / sodium / potassium / cesium, and lithium trimethylsilyloxide / sodium / potassium.

[0049] Preferably, the alkali metal thiolate is selected from at least one of lithium thioethoxylithium and C1-C4 alkyl thiolate sodium / potassium.

[0050] Preferably, the quaternary ammonium base is selected from at least one of the following structures:

[0051] Among them, R 1 R 2 R 3 R 4 Each of the following can be independently represented as at least one of the following: C1-C16 alkyl, C3-C10 cycloalkyl, C6-C16 aryl, C3-C10 heterocyclic, heteroatom-substituted C3-C10 cycloalkyl, C5-C16 heteroaryl, and heteroatom-substituted C5-C16 aryl.

[0052] Specifically, the heteroatom is selected from at least one of B, N, O, Si, P, and S; the heteroatom in the heterocyclic group and the heteroaryl group is selected from at least one of B, N, O, Si, P, and S.

[0053] Preferably, the alkali metal salt is selected from at least one of lithium pivalate / sodium / potassium / cesium, lithium trifluoroacetate / sodium / potassium / cesium, potassium sorbate, potassium cinnamate, C1-C18 alkyl xanthate potassium, and lithium sulfonamide / sodium / potassium / cesium. The specific structural formula of lithium sulfonamide / sodium / potassium / cesium is as follows:

[0054] The " / " symbol means "or".

[0055] Preferably, the crown ether complex is selected from at least one of the following structures:

[0056]

[0057] Preferably, the ammonium salt is selected from at least one of ammonium acetate, ammonium pentovanate, and ammonium trifluoroacetate.

[0058] Preferably, the quaternary ammonium salt is selected from at least one of the following structures:

[0059]

[0060] Among them, R 1 R 2 R 3 R 4 Each of the following can be independently represented: alkyl group of C1 to C16, cycloalkyl group of C3 to C10, aryl group of C6 to C16, heterocyclic group of C3 to C16, heteroatom-substituted cycloalkyl group of C3 to C16, heteroaryl group of C5 to C16, and heteroatom-substituted aryl group of C5 to C16.

[0061] Specifically, the heteroatom is selected from at least one of B, N, O, Si, P, and S; the heteroatom in the heterocyclic group and the heteroaryl group is selected from at least one of B, N, O, Si, P, and S.

[0062] Preferably, the quaternary phosphonium salt is selected from at least one of the following structures:

[0063]

[0064] Among them, R 1 R 2 R 3 R 4Each of the following can be independently represented: alkyl group of C1 to C16, cycloalkyl group of C3 to C10, aryl group of C6 to C16, heterocyclic group of C3 to C16, heteroatom-substituted cycloalkyl group of C3 to C16, heteroaryl group of C5 to C16, and heteroatom-substituted aryl group of C5 to C16.

[0065] Specifically, the heteroatom is selected from at least one of B, N, O, Si, P, and S; the heteroatom in the heterocyclic group and the heteroaryl group is selected from at least one of B, N, O, Si, P, and S.

[0066] Preferably, the imidazolium salt is selected from at least one of the following structures:

[0067]

[0068] Among them, R 1 R 2 Each of the following can be independently represented: alkyl group of C1 to C16, cycloalkyl group of C3 to C10, aryl group of C6 to C16, heterocyclic group of C3 to C16, heteroatom-substituted cycloalkyl group of C3 to C16, heteroaryl group of C5 to C16, and heteroatom-substituted aryl group of C5 to C16.

[0069] Specifically, the heteroatom is selected from at least one of B, N, O, Si, P, and S; the heteroatom in the heterocyclic group and the heteroaryl group is selected from at least one of B, N, O, Si, P, and S.

[0070] Preferably, the pyridinium salt is selected from at least one of the following structures:

[0071]

[0072] Among them, R 1 It represents at least one of the following: C1-C16 alkyl, C3-C10 cycloalkyl, C6-C16 aryl, C3-C16 heterocyclic, heteroatom-substituted C3-C16 cycloalkyl, C5-C16 heteroaryl, and heteroatom-substituted C5-C16 aryl.

[0073] Specifically, the heteroatom is selected from at least one of B, N, O, Si, P, and S; the heteroatom in the heterocyclic group and the heteroaryl group is selected from at least one of B, N, O, Si, P, and S.

[0074] In some embodiments, the catalyst is selected from Lewis bases and Bronte bases; preferably, the catalyst is selected from one of the following compounds:

[0075]

[0076] Specifically, the sulfonamide compounds of the present invention can be used to carry out ring-opening polymerization reactions using a single-component catalyst. Through a simple preparation process, sulfonamide compounds with narrow molecular weight distribution, strict alternating sequence structure, and well-defined structure can be synthesized under controlled conditions.

[0077] In some embodiments, the molar ratio of the sulfonamide compound to the active hydrogen compound is (80-120):(1-4).

[0078] In some preferred embodiments, the molar ratio of the sulfonamide compound to the active hydrogen compound is 100:(1-4).

[0079] In some embodiments, the polymerization reaction is carried out at a temperature of 90–110°C.

[0080] In some embodiments, the polymerization reaction takes 40 to 60 hours.

[0081] In some embodiments, the active hydrogen compound includes at least one group selected from amino, imino, amide, imino, sulfonamide, sulfonylimino, hydroxyl, phenolic hydroxyl, mercapto, carboxyl, and thiocarboxyl, and the active hydrogen refers to H in the above groups.

[0082] In some preferred embodiments, the active hydrogen compound is selected from at least one of carboxylic acids, alcohols, and phenols.

[0083] In some preferred embodiments, the active hydrogen compound is selected from at least one of the following compounds:

[0084]

[0085] In some embodiments, the polymerization reaction is carried out under conditions with or without solvent.

[0086] In some embodiments, the polymerization reaction is carried out under solvent-containing or solvent-free conditions. Specifically, the organic solvent is at least one selected from benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, n-hexane, cyclohexane, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, cyclopentyl methyl ether, anisole, and γ-butyrolactone.

[0087] In some embodiments, the preparation method of the sulfonamide polymer further includes the steps of: adding a terminator to terminate the reaction, diluting the initial product, purifying, and drying. Preferably, the terminator is acetic acid.

[0088] The second scenario:

[0089] In some embodiments, the method for preparing the sulfonamide polymer includes the following steps:

[0090] A sulfonamide polymer is obtained by mixing sulfonamide compounds, epoxy compounds, active hydrogen compounds and a catalyst and carrying out a polymerization reaction.

[0091] The molar ratio of the sulfonamide compound to the catalyst is 10:(0.01-0.5).

[0092] The catalyst is selected from at least one of Lewis acids, Bronte acids, Lewis bases, and Bronte bases.

[0093] Specifically, adding epoxy compounds to achieve copolymerization can enrich the structure and function of polymers.

[0094] In some embodiments, the molar ratio of the sulfonamide compound to the epoxy compound is 1:(0.8 to 1.8).

[0095] In some preferred embodiments, the molar ratio of the sulfonamide compound to the epoxy compound is 1:(1 to 1.7).

[0096] In some embodiments, the molar ratio of the sulfonamide compound to the active hydrogen compound is (10-800):(1-4).

[0097] In some preferred embodiments, the molar ratio of the sulfonamide compound to the active hydrogen compound is (20-300):1.

[0098] In some embodiments, the molar ratio of the sulfonamide compound to the catalyst is 10:(0.01 to 0.45).

[0099] In some preferred embodiments, when the catalyst is a single-component catalyst, the molar ratio of the sulfonamide compound to the catalyst is 10:(0.03–0.33); when the catalyst is a two-component catalyst, the molar ratio of the sulfonamide compound to the total molar amount of the catalyst is 10:(0.11–0.4). Specifically, the single-component catalyst is an acid or a base; the two-component catalyst is composed of an acid and a base; the acid is selected from Lewis acids and Bronte acids, and the base is selected from Lewis bases and Bronte bases.

[0100] In some embodiments, the catalyst comprises a Lewis base or a Brownian base, wherein the Lewis base or Brownian base is selected from at least one of the following: phosphazene bases, triaminophosphine, nitrogen-containing heterocyclic carbene, tertiary amines, amidine, guanidine, alkyllithium, phenyllithium, alkyl zinc, alkyl zinc halide, alkyl magnesium halide, aryl zinc halide, aryl magnesium halide, lithium di(trimethylsilyl)amino, sodium di(trimethylsilyl)amino, potassium di(trimethylsilyl)amino, lithium diisopropylamino, alkali metal alkoxides, alkali metal thiolates, lithium phenoxide, sodium phenoxide, potassium phenoxide, cesium phenoxide, lithium thiophene, sodium thiophene, potassium thiophene, cesium thiophene, quaternary ammonium bases, caustic bases, alkali metal salts, crown ether complexes, ammonium salts, quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts, and pyridinium salts. The specific structures of the relevant compounds can be found in the description of the "first case" above.

[0101] In some embodiments, the catalyst further includes a Lewis acid or a Bronte acid, wherein the Lewis acid or Bronte acid is selected from at least one of trialkylboron, organoboronic acid esters, boron trifluoride, organoaluminum compounds, aluminum trichloride, ferric chloride, urea, and thiourea.

[0102] Preferably, the trialkylboron is at least one selected from trimethylboron, triethylboron, triisopropylboron, tri-n-butylboron, trisec-butylboron, β-isopinenoyl-9-boronbicyclo[3.3.1]nonane, triphenylboron, and tri(pentafluorophenyl)boron, with the following specific structural formula:

[0103]

[0104] The organoboroester is at least one selected from diethylmethoxyboron, diisopropoxymethylboron, ethylboron pinacol, cyclohexylboron pinacol, trimethylcyclotriboroxane, triphenylcyclotriboroxane, C1-C10 trialkylboronate, and triphenyl borate, with the following specific structural formula:

[0105] Where n is an integer, and its value ranges from 0 to 9.

[0106] Preferably, the organoaluminum compound is selected from at least one of the following structural formulas:

[0107]

[0108] Q1, Q2, and Q3 are each independently selected from one of Cl, Br, OR, SR, and N(R)2; R is each independently selected from at least one of C1 to C8 alkyl, phenyl, and pentafluorophenyl.

[0109] Preferably, the structural formula of the urea or thiourea is as follows:

[0110]

[0111] Wherein, R1 and R2 are each independently selected from at least one of H, C1-C16 alkyl, phenyl, benzyl, heteroatom-substituted C1-C16 alkyl, heteroatom-substituted phenyl, heteroatom-substituted benzyl, C3-C16 heterocyclic, heteroatom-substituted C3-C16 heterocyclic, C5-C16 heteroaryl, and heteroatom-substituted C5-C16 heteroaryl;

[0112] Specifically, the heteroatom is selected from at least one of B, N, O, F, Si, P, S, Cl, and Br; the heteroatom in the heterocyclic group and the heteroaryl group is selected from at least one of B, N, O, Si, P, and S.

[0113] In some preferred embodiments, the catalyst is selected from at least one of the following structural formulas:

[0114]

[0115] In some preferred embodiments, the catalyst is triethylamine (TEA).

[0116] In some preferred embodiments, the catalyst is composed of a Lewis base and a Lewis acid; and the molar ratio of the Lewis base to the Lewis acid is 1:(0.1 to 2).

[0117] Specifically, when the molar ratio of the Lewis base to the Lewis acid is 1:(0.1 to 0.8), the sulfonamide polymer has a strictly alternating sequence structure, satisfying the characteristics of an alternating copolymer; when the molar ratio of the Lewis base to the Lewis acid is 1:(1.2 to 1.8), the alternating structural units and ether linkage units in the sulfonamide polymer are arranged randomly, and there are fewer continuous units.

[0118] Preferably, in these embodiments, the Lewis base is At least one of the Lewis acids, wherein the Lewis acid is At least one of them.

[0119] Specifically, both the sulfonamide compounds and the epoxy compounds are monomers that can be activated by a suitable catalyst system to undergo ring-opening reactions and polymerization reactions with precisely controllable sequence structures.

[0120] In some embodiments, the sulfonamide compound is prepared by sulfonation of heterocyclic compound A, wherein compound A is selected from 2-azacyclobutanone, 2-pyrrolidone, 4,4-pentamethylene-2-pyrrolidone, 2-indolone, isoindolin-1-one, 2-azabicyclo[2.2.1]hept-5-en-3-one, indole-2,3-dione, 2-azahexanecycloone, 3,4-dihydro-2(1H)-quinolinone, C1-C18 1-alkyl-3-oxopiperazine, 1-ethylpiperazinedione, 3-morpholinone, 2,4-piperidinedione, glycine anhydride, and 3-oxopiperazine-1-carboxylic acid. At least one of the following: tert-butyl ester, 3-oxopiperazine-1-carboxylic acid benzyl ester, octanolamide, ε-caprolactam, 1,4-oxazetane-5-one, 1,4-thioazetane-5-one, heptanolamide, laurolactam, succinimide, maleimide, cyclopentadienylimide, cyclohexanediylimide, phthalimide, 1,2,3,6-tetrahydrophthalimide, 2,4-thiazolidinedione, rhodanine, glutarimide, 3,3-dimethylglutarimide, 8-azaspiro[4.5]decane-7,9-dione, 2,4-imidazolinide, barbituric acid, and 1-methylbarbituric acid.

[0121] Preferably, the heterocyclic compound A is selected from at least one of 2-pyrrolidone, 2-azhexanecycloone, ε-caprolactam, succinimide, and glutarimide.

[0122] In some embodiments, the sulfonamide compound is selected from one of the following compounds:

[0123] The sulfonamide compound is selected from one of the following compounds:

[0124]

[0125] Where k and L are both integers, and the value of k ranges from 1 to 12, and the value of L ranges from 1 to 3;

[0126] R is selected from one of the following: phenyl, benzyl, C1-C5 alkyl para-substituted phenyl, nitrophenyl, CF3-substituted phenyl, heteroaryl, CF3, CBr3, CCl3, F-substituted C1-C5 alkyl, Br-substituted C1-C5 alkyl, and Cl-substituted C1-C5 alkyl.

[0127] Preferably, k and L are both integers, and the value range of k is 1 to 6, and the value range of L is 1 to 3.

[0128] In some preferred embodiments, the sulfonamide compound is selected from one of the following structural formulas:

[0129]

[0130] In some embodiments, the epoxy compound is selected from at least one of ethylene oxide, linear alkyl ethylene oxide with 1 to 20 alkyl carbon atoms, styrene oxide, cyclohexane oxide, 4-vinylcyclohexane oxide, limonene oxide, linear alkyl glycidyl ether with 1 to 16 alkyl carbon atoms, tert-butyl glycidyl ether, epichlorohydrin, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, trifluoropropylene oxide, 3,4-epoxy-1-butene, glycidyl methacrylate, and glycidyl cinnamate. The specific structural formula is as follows:

[0131] In compound (2), t is an integer and the value of t ranges from 0 to 19.

[0132] In some preferred embodiments, the epoxy compound is selected from at least one of the following structural formulas:

[0133]

[0134] In some embodiments, the active hydrogen compound includes at least one group selected from amino, imino, amide, imino, sulfonamide, sulfonylimino, hydroxyl, phenolic hydroxyl, mercapto, carboxyl, and thiocarboxyl, and the active hydrogen refers to H in the above groups.

[0135] In some preferred embodiments, the active hydrogen compound is selected from at least one of carboxylic acids, alcohols, and phenols.

[0136] In some preferred embodiments, the active hydrogen compound is selected from one of the following structural formulas:

[0137]

[0138] In some embodiments, the polymerization reaction is carried out at a temperature of 15–120°C.

[0139] In some preferred embodiments, the polymerization reaction is carried out at a temperature of 18–100°C.

[0140] In some preferred embodiments, the polymerization reaction is carried out at 20–25°C. Specifically, the preparation method enables the controlled synthesis of sulfonamide polymers with specific structures under relatively mild conditions at room temperature.

[0141] In some embodiments, the polymerization reaction takes 3 to 90 hours.

[0142] In some preferred embodiments, the polymerization reaction takes 5 to 80 hours. Specifically, when the catalyst is a single-component catalyst, the polymerization reaction takes 32 to 80 hours, and when the catalyst is a two-component catalyst, the polymerization reaction takes 5 to 24 hours.

[0143] In some embodiments, the polymerization reaction is carried out under conditions with or without solvent.

[0144] In some embodiments, the polymerization reaction is carried out under solvent-containing or solvent-free conditions. Specifically, the organic solvent is at least one selected from benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, n-hexane, cyclohexane, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, cyclopentyl methyl ether, anisole, and γ-butyrolactone.

[0145] In some embodiments, the preparation method of the sulfonamide polymer further includes the steps of: adding a terminator to terminate the reaction, diluting the initial product, purifying, and drying. Preferably, the terminator is acetic acid.

[0146] Secondly, the present invention provides the application of the preparation method described in the first aspect in the synthesis of sulfonamide polymers.

[0147] In some embodiments, the molecular weight distribution index of the sulfonamide polymers obtained by the method is 1.05 to 1.20.

[0148] In some preferred embodiments, the molecular weight distribution index of the sulfonamide polymers obtained by the method is 1.07 to 1.17.

[0149] In some embodiments, the method can controllably produce sulfonamide polymers by designing a reasonable catalytic system. These sulfonamide polymers have the characteristics of "strict alternating sequence structure" or "irregular arrangement of alternating structural units and ether bond units with few repeating units".

[0150] The beneficial effects of the present invention are: the sulfonamide polymers and their preparation methods of the present invention have the advantages of simple operation, mild conditions, atom economy, high selectivity and wide applicability; the obtained sulfonamide polymers have novel repeating unit structures, controllable molecular weight and narrow molecular weight distribution, rich and tunable side group functional groups and topological structures, good thermal stability and (bio)degradability.

[0151] Specifically:

[0152] (1) This invention uses the sulfonation products of lactimide (heterocyclic compounds containing -(C=O)-NH- or -(C=O)-NH-(C=O)- structures) as monomer sources to carry out controlled ring-opening polymerization or strict alternating copolymerization with epoxides, providing a structural design and synthesis platform for obtaining different types of polymer material properties.

[0153] (2) The intramer(imide), sulfonyl group, and epoxy alkane containing the -(C=O)-NH- or -(C=O)-NH-(C=O)- structure in this invention are widely available and extremely diverse. By any combination of two or more comonomers, a series of novel sulfonamide polymers can be obtained, with extremely rich main chain and side group structures, which can be flexibly designed according to application scenarios to meet different needs.

[0154] (3) The present invention relates to a wide variety of single-component and two-component catalysts, especially two-component catalysts. By changing the combination, ratio, and feeding method of various bases and acids, the catalytic activity, selectivity, and copolymerization method can be flexibly adjusted and optimized for different combinations of monomers with varying structures and activities and target polymer structures. For example, the ratio of base to acid can significantly regulate the copolymerization rate of epoxy and N-sulfonyl lactam (imide) monomers, and the sequence structure of the main chain (alternating, random, gradient, or conical) can be flexibly designed to adjust the (thermo)mechanical properties and degradability of the copolymer.

[0155] (4) The catalytic method used in this invention is mild and efficient, with excellent chemical selectivity and controllability, completely avoiding side reactions such as epoxy self-growth and transesterification, and synthesizing strictly alternating copolymers. Moreover, this method does not have problems such as catalyst metal poisoning (no heavy metal pollution) and difficulty in product separation and purification, and has natural advantages in biological applications.

[0156] (5) This invention features the active characteristics of anionic polymerization, and can use structurally abundant active hydrogen compounds as initiators. The molecular weight of the product is controllable and has a narrow distribution, with a wide molecular weight range. The feeding methods include direct mixing and continuous stepwise feeding, which simplifies the synthesis process of polymers with specific molecular weights, sequence structures, and functions, and improves production efficiency. It can design and prepare sulfonamide polymers with terminal functionalization, block, star, dendritic, hyperbranched, and other topological structures.

[0157] (6) This invention can be carried out under solvent-free or low-solvent conditions, has a wide operating temperature range, improves the ease of operation, flexibility and safety, and is suitable for industrial production. Attached Figure Description

[0158] Figure 1 This is a SEC diagram of the copolymer synthesized in Example 7.

[0159] Figure 2 The copolymer synthesized in Example 7 1 H NMR spectrum.

[0160] Figure 3 The image shows the MALDI-TOF MS plot of the copolymer synthesized in Example 7.

[0161] Figure 4 This is a SEC diagram of the copolymer synthesized in Example 10.

[0162] Figure 5 The copolymer synthesized in Example 10 1 H NMR spectrum.

[0163] Figure 6 The image shows the MALDI-TOF MS plot of the copolymer synthesized in Example 10.

[0164] Figure 7 The image shows the MALDI-TOF MS plot of the polymer synthesized in Example 11. Detailed Implementation

[0165] The present invention will be further described in detail below through specific embodiments.

[0166] Unless otherwise specified, RT in the reaction formulas of the following examples represents room temperature, which is 20-25°C; the glass reactors in the examples are all cleaned, dried at 200°C, and cooled to room temperature (20-25°C) before they can be used for the preparation of sulfonamide polymers; the numerical values ​​in the reaction formulas of the examples represent the molar number of raw materials fed; the "molecular weight dispersion" and "molecular weight distribution index" in the examples both represent the ratio of weight-average molecular weight to number-average molecular weight (i.e., Mw / Mn), and this value is approximately close to 1, indicating a narrower molecular weight distribution; the structural formula of the sulfonamide polymer in each example... Each represents a repeating unit structure; the values ​​of n and m in each embodiment only indicate that the sulfonamide polymer has a repeating unit structure, and the range of values ​​of n and m in different embodiments may not be the same, and the values ​​of n and m of polymers in the same embodiment may not be the same.

[0167] In the following examples, the conversion rates of N-sulfonyl lactam monomers and epoxy monomers, as well as the polymer structural characteristics, were measured using a Bruker AV400 liquid NMR spectrometer with deuterated chloroform as the solvent. N-sulfonyl lactam monomers refer to either N-sulfonyl lactam monomers or N-sulfonyl lactam monomers. The relative molecular weight and molecular weight dispersion of the polymers were measured using an Agilent 1260 Infinity volume exclusion chromatograph with tetrahydrofuran as the mobile phase, a column temperature of 35°C, and a flow rate of 1 mL / min. Calibration curves were prepared using a series of polystyrene or polyethylene oxide standard samples.

[0168] In this embodiment of the invention, the specific structural formulas and abbreviations of the materials used are as follows (the CAS numbers in the figures are for reference only):

[0169]

[0170] Example 1

[0171] The reaction formula involved in this embodiment is as follows:

[0172]

[0173] In the formula, Tf represents trifluoromethanesulfonyl group, and RT represents room temperature.

[0174] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0175] In a nitrogen atmosphere, 1 mmol of cis-butenediol (BEDO), 1 mmol of TEA, and 35 mL of tetrahydrofuran were added to a glass reactor. Then, 300 mmol of N-trifluoromethanesulfonylpyrrolidone (TfBL) and 300 mmol of trifluoropropylene oxide (TfPO) were added. The glass reaction vessel was sealed, a magnetic stirrer was turned on, and the reaction was carried out at room temperature (20–25 °C) for 80 h to obtain the initial product (colorless viscous liquid). The reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane. Then, n-hexane was added to precipitate the product. The solid was collected and dried in a vacuum oven at 50 °C for 12 h to obtain the product (i.e., sulfonamide polymer).

[0176] Through testing and analysis, the conversion rates of TfBL and TfPO in this embodiment were both 100%, and the product... 1 No chemical shift signals for polyethers and polyamides were observed in the 1H NMR spectrum, indicating that the self-polymerization reactions of both comonomers were sufficiently suppressed. Combined with matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) and carbon NMR spectroscopy of the products in this embodiment... 13The CNMR test results fully demonstrate that the product structure is well-defined and is a strictly alternating sequence structure. The specific structure of the product is shown below:

[0177] represent * indicates a connection or substitution position, and Tf indicates a trifluoromethanesulfonyl group, which indicates that the structures at both ends of the polymer are the same or similar.

[0178] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate was 98.9 kg / mol. The number-average molecular weight of the above product was determined to be 70.8 kg / mol by SEC (size exclusion chromatography), and the molecular weight distribution index was 1.12.

[0179] Example 2

[0180] The reaction formula involved in this embodiment is as follows:

[0181]

[0182] In the formula, Ts represents p-toluenesulfonyl group.

[0183] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0184] In a nitrogen atmosphere, 1 mmol of benzoic acid (BA) and 1 mmol of... t BuP2, a tetrahydrofuran solution containing 0.2 mmol of triethylboron (TEB) (concentration 1 mol / L), and 3 mL of toluene were added to a glass reactor. Then, 30 mmol of N-p-toluenesulfonyl succinimide (TsSI) and 30 mmol of cyclohexane oxide (CHO) were added. The glass reaction vessel was sealed, and a magnetic stirrer was turned on. The reaction was carried out at 100 °C for 40 h to obtain the initial product (a colorless viscous liquid). The reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane. Methanol was then added to precipitate the product. The solid was collected and dried in a vacuum oven at 50 °C for 12 h to obtain the final product (i.e., a sulfonamide polymer).

[0185] Through testing and analysis, the conversion rates of N-p-toluenesulfonyl succinimide (TsSI) and cyclohexane oxide (CHO) in this embodiment were both 100%, and the products... 1 H NMR spectrum combined with matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) and carbon NMR spectrum ( 13 The C NMR test results fully demonstrate that the product has a strictly alternating sequence structure, and the specific structure of the product is shown below:

[0186] Ts represents p-toluenesulfonyl group.

[0187] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate is 10.7 kg / mol. The number-average molecular weight of the above product, determined by SEC (size exclusion chromatography), is 6.2 kg / mol, and the molecular weight distribution index is 1.08.

[0188] Example 3

[0189] The reaction formula involved in this embodiment is as follows:

[0190]

[0191] In the formula, Tf represents trifluoromethanesulfonyl group.

[0192] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0193] In a nitrogen atmosphere, 1 mmol of BA and 1 mmol of t BuP2 and 3 mL of toluene were added to a glass reactor; then 30 mmol of N-trifluoromethanesulfonylglutarimide (TfGI) and 30 mmol of cyclohexane oxide (CHO) were added. The glass reaction vessel was sealed, and the magnetic stirrer was turned on. The reaction was carried out at 100 °C for 48 h to obtain the initial product (colorless viscous liquid). The reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane. Methanol was then added to precipitate the product. The solid was collected and placed in a vacuum oven at 50 °C for 12 h to obtain the product (i.e., sulfonamide polymer).

[0194] Through testing and analysis, the conversion rates of TfGI and CHO in this embodiment were both 88%, and the product... 1 H NMR spectrum combined with MALDI-TOF spectrum and 13 The results of the C NMR spectrum fully demonstrate that the product has a strictly alternating sequence structure, and the specific structure of the product is shown below:

[0195] Tf represents trifluoromethanesulfonyl group.

[0196] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate is 9.2 kg / mol. The number-average molecular weight of the above product, determined by SEC (size exclusion chromatography), is 5.5 kg / mol, and the molecular weight distribution index is 1.08.

[0197] Example 4

[0198] The reaction formula involved in this embodiment is as follows:

[0199]

[0200] In the formula, Tf represents trifluoromethanesulfonyl group.

[0201] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0202] In a nitrogen atmosphere, 1 mmol of cis-butenediol (BEDO) and 0.5 mmol of... t BuP1 was added to a glass reactor; 60 mmol of N-trifluoromethanesulfonyl azithionone (TfVL) and 100 mmol of ethylene oxide (EO) were then added. The glass reaction vessel was sealed, and a magnetic stirrer was turned on. The reaction was carried out at 60 °C for 36 h to obtain the initial product (a colorless viscous liquid). The reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane. Methanol was then added to precipitate the product. The solid was collected and placed in a vacuum oven at 50 °C for 12 h to dry under vacuum, thus obtaining the product (i.e., sulfonamide polymer).

[0203] Through testing and analysis, the conversion rates of TfVL and EO in this embodiment were 100% and 60%, respectively. Excess EO promotes the epoxy ring-opening reaction and also acts as a solvent. The product... 1 H NMR spectrum combined with MALDI-TOF spectrum and 13 The results of the C NMR spectroscopy also confirmed that the product has a strictly alternating sequence structure, and the specific structure of the product is shown below:

[0204] Tf represents trifluoromethanesulfonyl group; represent * indicates a connection or substitution position, and Tf indicates a trifluoromethanesulfonyl group, which indicates that the structures at both ends of the polymer are the same or similar.

[0205] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate is 16.6 kg / mol. The number-average molecular weight of the above product was determined to be 13.1 kg / mol by SEC (size exclusion chromatography), and the molecular weight distribution index was 1.07.

[0206] Example 5

[0207] The reaction formula involved in this embodiment is as follows:

[0208] In the formula, Ts represents p-toluenesulfonyl group.

[0209] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0210] In a nitrogen atmosphere, 1 mmol of BEDO and 2 mmol of... tBuP2 and 20 mL of toluene were added to a glass reactor; 100 mmol of N-p-toluenesulfonyl hexanecycloketone (TsVL) was then added, the glass reaction vessel was sealed, a magnetic stirrer was turned on, and the reaction was carried out at 100 °C for 48 h to obtain the initial product (colorless viscous liquid); the reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane at the same time, followed by the addition of methanol to precipitate the product. The solid was collected and placed in a vacuum oven at 50 °C for vacuum drying for 12 h to obtain the product (i.e., sulfonamide polymer).

[0211] Through testing and analysis, the conversion rate of TsVL in this embodiment was 93%, and the product... 1 H NMR spectrum combined with MALDI-TOF spectrum and 13 The C NMR spectroscopy results fully demonstrate that the product has a strictly alternating sequence structure and is a homopolymer of TsVL. The specific structure of the product is shown below:

[0212] Ts represents p-toluenesulfonyl group; represent * indicates a connection or substitution site, which means that the structures at both ends of the polymer are the same or similar.

[0213] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate was 23.6 kg / mol. The number-average molecular weight of the above product, determined by SEC (size exclusion chromatography), was 15.6 kg / mol, and the molecular weight distribution index was 1.10.

[0214] Example 6

[0215] The reaction formula involved in this embodiment is as follows:

[0216]

[0217] In the formula, Ts represents p-toluenesulfonyl group.

[0218] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0219] In a nitrogen atmosphere, 1 mmol of BEDO and 2 mmol of... t BuP2 and 20 mL of toluene were added to a glass reactor; 100 mmol of N-p-toluenesulfonylcaprolactam (TsCL) was then added, the glass reaction vessel was sealed, a magnetic stirrer was turned on, and the reaction was carried out at 100 °C for 48 h to obtain the initial product (colorless viscous liquid); the reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane, followed by the addition of methanol for precipitation. The solid was collected and placed in a vacuum oven at 50 °C for vacuum drying for 12 h to obtain the product (i.e., sulfonamide polymer).

[0220] Through testing and analysis, the conversion rate of N-p-toluenesulfonylcaprolactam (TsCL) in this example was 53%, and the product... 1 H NMR spectrum combined with matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) and carbon NMR spectrum ( 13 The CNMR test results fully demonstrate that the product has a strictly alternating sequence structure, and the specific structure of the product is shown below:

[0221] Ts represents p-toluenesulfonyl group. represent * indicates a connection or substitution site, which means that the structures at both ends of the polymer are the same or similar.

[0222] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate was 14.3 kg / mol. The number-average molecular weight of the product, determined by SEC (size exclusion chromatography), was 9.8 kg / mol, and the molecular weight distribution index was 1.17.

[0223] Example 7

[0224] The reaction formula involved in this embodiment is as follows:

[0225]

[0226] In the formula, Tf represents trifluoromethanesulfonyl group, and RT represents room temperature.

[0227] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0228] In a nitrogen atmosphere, 1 mmol of cis-butenediol (BEDO), 1 mmol of TEA, and 5 mL of cyclopentyl methyl ether were added to a glass reactor. Then, 60 mmol of N-trifluoromethanesulfonyl hexanecycloone (TfVL) and 80 mmol of trifluoropropylene oxide (TfPO) were added. The glass reaction vessel was sealed, and a magnetic stirrer was turned on. The reaction was carried out at room temperature for 32 h to obtain the initial product (a colorless viscous liquid). The reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane. Hexane was then added to precipitate the product. The solid was collected and dried in a vacuum oven at 50 °C for 12 h to obtain the final product (i.e., a sulfonamide polymer).

[0229] In this embodiment, SEC and 1 The H NMR test results are as follows: Figure 1 and Figure 2 As shown. The MALDI-TOF MS test results, obtained by sampling and measuring at 6 hours of reaction in this embodiment, are as follows. Figure 3 As shown.

[0230] After testing and analysis, and Figure 1 , Figure 2 and Figure 3 It can be seen that the conversion rates of N-trifluoromethanesulfonyl azithionone (TfVL) and trifluoropropylene oxide (TfPO) in this embodiment are 86% and 65%, respectively. 1 ¹H NMR results indicate that the polymerization reaction is initiated by BEDO, and no chemical shift signals were observed in the polyether and polyamide. Combined with MALDI-TOF MS results, this fully demonstrates that the product structure is well-defined and exhibits a strictly alternating sequence structure. The specific structure of the product is shown below:

[0231] Tf represents trifluoromethanesulfonyl group. represent * indicates a connection or substitution site, which suggests that the structures at both ends of the polymer are similar or identical.

[0232] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate is 17.8 kg / mol. The number-average molecular weight of the above product was determined to be 14.6 kg / mol by SEC (size exclusion chromatography), and the molecular weight distribution index was 1.11.

[0233] Example 8

[0234] The reaction formula involved in this embodiment is as follows:

[0235] In the formula, Tf represents trifluoromethanesulfonyl group, and RT represents room temperature.

[0236] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0237] In a nitrogen atmosphere, 1 mmol of pentaerythritol (PT), 0.2 mmol of DBU, a tetrahydrofuran solution containing 0.12 mmol of TEB (TEB concentration of 1 mol / L), and 2 mL of tetrahydrofuran were added to a glass reactor. Then, 20 mmol of N-trifluoromethanesulfonyl hexanecyclohexanone (TfVL) and 24 mmol of allyl glycidyl ether (AGE) were added. The glass reaction vessel was sealed, and a magnetic stirrer was turned on. The reaction was carried out at room temperature for 5 h to obtain the initial product (a colorless viscous liquid). The reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane. Methanol was then added to precipitate the product. The solid was collected and dried in a vacuum oven at 50 °C for 12 h to obtain the final product (i.e., a sulfonamide polymer).

[0238] Through testing and analysis, the conversion rate of N-trifluoromethanesulfonyl azithionone (TfVL) in this embodiment was 100%, and the product... 1H NMR spectrum combined with matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) and carbon NMR spectrum ( 13 The CNMR test results fully demonstrate that the product has a strictly alternating sequence structure, and the specific structure of the product is shown below:

[0239] Tf represents trifluoromethanesulfonyl group. represent * indicates a connection or substitution position, which means that multiple substituents in the polymer have similar or identical repeating unit structures.

[0240] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate is 7.0 kg / mol. The number-average molecular weight of the above product, determined by SEC (size exclusion chromatography), is 4.6 kg / mol, and the molecular weight distribution index is 1.08.

[0241] Example 9

[0242] The reaction formula involved in this embodiment is as follows:

[0243]

[0244] In the formula, Tf represents trifluoromethanesulfonyl group, and RT represents room temperature.

[0245] This embodiment provides a method for preparing sulfonamide polymers, which differs from Example 8 only in the amount of triethylboron (TEB). The method specifically includes the following steps:

[0246] In a nitrogen atmosphere, 1 mmol of PT, 0.2 mmol of DBU, a tetrahydrofuran solution containing 0.02 mmol of TEB (concentration 1 mol / L), and 2 mL of tetrahydrofuran were added to a glass reactor. Then, 20 mmol of TfVL and 24 mmol of AGE were added. The glass reaction vessel was sealed, and a magnetic stirrer was turned on. The reaction was carried out at room temperature for 6 h to obtain a primary product (a colorless viscous liquid). The reaction was terminated by adding acetic acid, and the primary product was diluted with dichloromethane. Methanol was then added to precipitate the product. The solid was collected and dried in a vacuum oven at 50 °C for 12 h to obtain the final product (i.e., a sulfonamide polymer).

[0247] Through testing and analysis, the conversion rate of TfVL in this embodiment reached 100%. The product... 1 H NMR spectrum combined with matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) and carbon NMR spectrum ( 13 The C NMR test results fully demonstrate that the product has a strictly alternating sequence structure, and the specific structure of the product is shown below:

[0248] Tf represents trifluoromethanesulfonyl group. represent * indicates a connection or substitution position, which means that multiple substituents in the polymer have similar or identical repeating unit structures.

[0249] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate is 7.0 kg / mol. The number-average molecular weight of the above product, determined by SEC (size exclusion chromatography), is 4.7 kg / mol, and the molecular weight distribution index is 1.08.

[0250] Compared to Example 8, the reaction time required for complete conversion of TfVL increased, indicating that reducing the amount of TEB leads to a decrease in the copolymerization rate. In two-component catalysis, the effect of each catalytic component on one of the monomers is different. Although under normal circumstances, catalyst dosage and reactivity are positively correlated, in two-component catalytic systems, the influence of any catalyst component on the reactivity and selectivity of different monomers is difficult to predict.

[0251] Example 10

[0252] The reaction formula involved in this embodiment is as follows:

[0253]

[0254] In the formula, Tf represents trifluoromethanesulfonyl group, and RT represents room temperature.

[0255] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0256] In a nitrogen atmosphere, 1 mmol of BEDO, 0.2 mmol of TEA, a tetrahydrofuran solution containing 0.02 mmol of TEB (concentration 1 mol / L), and 2 mL of tetrahydrofuran were added to a glass reactor. Then, 20 mmol of TfVL and 24 mmol of propylene oxide (PO) were added. The glass reaction vessel was sealed, and a magnetic stirrer was turned on. The reaction was carried out at room temperature for 6 h to obtain a primary product (a colorless viscous liquid). The reaction was terminated by adding acetic acid, and the primary product was diluted with dichloromethane. Hexane was then added to precipitate the product. The solid was collected and dried in a vacuum oven at 50 °C for 12 h to obtain the final product (i.e., a sulfonamide polymer).

[0257] The SEC of the sulfonamide polymer in this embodiment, 1 The results of H NMR and MALDI-TOF MS tests are as follows: Figure 4 , Figure 5 and Figure 6 As shown.

[0258] Depend on Figure 4 , Figure 5 and Figure 6 It can be seen that the MALDI-TOF MS test results fully demonstrate that the product structure is clear. 1 ¹H NMR results indicate that the polymerization reaction was initiated by BEDO. The integral ratio of the hydrogen chemical shift signals attributed to TfVL and PO in the copolymer is approximately 4 / 3. Furthermore, no chemical shift signals were observed for polyether and polyamide, all confirming that the product is an alternating copolymer. Moreover, in this example, the TfVL conversion reached 100%, and the product exhibits a strictly alternating sequence structure. The specific structure of the product is shown below:

[0259] Tf represents trifluoromethanesulfonyl group. represent * indicates a connection or substitution site, which means that both ends of the polymer have similar or identical repeating unit structures.

[0260] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate is 5.9 kg / mol. The number-average molecular weight of the above product was determined to be 5.4 kg / mol by SEC (size exclusion chromatography), and the molecular weight distribution index was 1.08.

[0261] Example 11

[0262] The reaction formula involved in this embodiment is as follows:

[0263]

[0264] In the formula, Tf represents trifluoromethanesulfonyl group, and RT represents room temperature.

[0265] This embodiment provides a method for preparing sulfonamide polymers, which differs from Example 10 only in the amount of TEB used. The specific steps include:

[0266] In a nitrogen atmosphere, 1 mmol of BEDO, 0.2 mmol of TEA, a tetrahydrofuran solution containing 0.3 mmol of TEB (TEB concentration of 1 mol / L), and 2 mL of tetrahydrofuran were added to a glass reactor. Then, 20 mmol of TfVL and 24 mmol of PO were added. The glass reaction vessel was sealed, and a magnetic stirrer was turned on. The reaction was carried out at room temperature for 8 hours to obtain the initial product (a colorless viscous liquid). The reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane. Hexane was then added to precipitate the product. The solid was collected and dried in a vacuum oven at 50°C for 12 hours to obtain the final product (i.e., a sulfonamide polymer).

[0267] Through testing and analysis, the conversion rates of TfVL and PO in this embodiment were both 100%. The amount of TEB used in this embodiment was 15 times that in Example 10. Due to the activating effect of TEB on epoxy, the ring-opening activity of the epoxy was significantly improved, resulting in a random arrangement of alternating structural units and ether linkages in the copolymer product, with fewer continuous units. The product's... 1 1H NMR spectrum combined with matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF, e.g.) Figure 7 (as shown) and carbon NMR spectrum ( 13 The C NMR test results show that the specific structure of the product is as follows:

[0268] Tf represents trifluoromethanesulfonyl group. represent * indicates a connection or substitution site, which means that both ends of the polymer have similar or identical repeating unit structures.

[0269] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate is 6.1 kg / mol. The number-average molecular weight of the above product, determined by SEC (size exclusion chromatography), is 5.1 kg / mol, and the molecular weight distribution index is 1.09.

[0270] Example 12

[0271] The reaction formula involved in this embodiment is as follows:

[0272]

[0273] In the formula, Tf represents trifluoromethanesulfonyl group, and RT represents room temperature.

[0274] This embodiment provides a method for preparing sulfonamide polymers, including the following steps:

[0275] In a nitrogen atmosphere, 1 mmol of BEDO and 1 mmol of... t BuP1, a tetrahydrofuran solution containing 0.2 mmol of tri-n-butylboron (TBB) (TBB concentration 1 mol / L), and 10 mL of tetrahydrofuran were added to a glass reactor. Then, 100 mmol of TfBL and 150 mmol of PO were added. The glass reaction vessel was sealed, and a magnetic stirrer was turned on. The reaction was carried out at room temperature for 24 h to obtain the initial product (a colorless viscous liquid). The reaction was terminated by adding acetic acid, and the initial product was diluted with dichloromethane. Methanol was then added to precipitate the product. The solid was collected and dried in a vacuum oven at 50 °C for 12 h to obtain the final product (i.e., a sulfonamide polymer).

[0276] Through testing and analysis, the conversion rate of TfBL in this embodiment was 86%, and the product... 11H NMR spectroscopy, matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF), and carbon NMR spectroscopy (NMR spectroscopy) 13 The C NMR test results fully demonstrate that the product has a strictly alternating sequence structure, and the specific structure of the product is shown below:

[0277] Tf represents trifluoromethanesulfonyl group. represent * indicates a connection or substitution site, which suggests that the structures at both ends of the polymer are similar or identical.

[0278] Meanwhile, the theoretical number-average molecular weight calculated based on the feed ratio and conversion rate was 23.8 kg / mol. The number-average molecular weight of the above product was determined to be 18.1 kg / mol by SEC (size exclusion chromatography), and the molecular weight distribution index was 1.12.

[0279] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a sulfonamide polymer, characterized in that, Includes the following steps: A sulfonamide polymer is obtained by mixing a sulfonamide compound, an active hydrogen compound, and a catalyst and carrying out a polymerization reaction. or, A sulfonamide polymer is obtained by mixing sulfonamide compounds, epoxy compounds, active hydrogen compounds and a catalyst and carrying out a polymerization reaction. The molar ratio of the sulfonamide compound to the catalyst is 100:(0.01~5); the catalyst is selected from at least one of Lewis acids, Bronte acids, Lewis bases, and Bronte bases. The sulfonamide compound is selected from one of the following compounds: ； Where k and L are both integers, and the value of k ranges from 1 to 12, and the value of L ranges from 1 to 3; R is selected from one of phenyl, benzyl, C1-C5 alkyl para-substituted phenyl, nitrophenyl, CF3-substituted phenyl, heteroaryl, F-substituted C1-C5 alkyl, Br-substituted C1-C5 alkyl, and Cl-substituted C1-C5 alkyl.

2. The preparation method according to claim 1, characterized in that: The preparation method includes the following steps: A sulfonamide compound, an active hydrogen compound, and a catalyst are mixed and polymerized to obtain a sulfonamide polymer; wherein the molar ratio of the sulfonamide compound to the catalyst is 10:(0.1~0.5); and the catalyst is selected from at least one Lewis base or a Bronte base. or, A sulfonamide polymer is obtained by mixing sulfonamide compounds, epoxy compounds, active hydrogen compounds and a catalyst and carrying out a polymerization reaction. The molar ratio of the sulfonamide compound to the catalyst is 10:(0.01~0.5). The catalyst is selected from at least one of Lewis acids, Bronte acids, Lewis bases, and Bronte bases.

3. The method for preparing the sulfonamide polymer according to claim 1 or 2, characterized in that: The sulfonamide compound is selected from one of the following compounds: 。 4. The method for preparing the sulfonamide polymer according to claim 1 or 2, characterized in that: The epoxy compound is selected from at least one of ethylene oxide, linear alkyl ethylene oxide with 1 to 20 alkyl carbon atoms, styrene oxide, cyclohexane oxide, 4-vinylcyclohexane oxide, limonene oxide, linear alkyl glycidyl ether with 1 to 16 alkyl carbon atoms, tert-butyl glycidyl ether, epichlorohydrin, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, trifluoropropylene oxide, 3,4-epoxy-1-butene, glycidyl methacrylate, and glycidyl cinnamate.

5. The method for preparing the sulfonamide polymer according to claim 1 or 2, characterized in that: The active hydrogen compound contains at least one group selected from amino, imino, amide, imino, sulfonamide, sulfonylimino, hydroxyl, phenolic hydroxyl, mercapto, carboxyl, and thiocarboxyl.

6. The method for preparing the sulfonamide polymer according to claim 1 or 2, characterized in that: The reaction temperature is 15~120℃, and the reaction time is 3~90h.

7. The method for preparing the sulfonamide polymer according to claim 1 or 2, characterized in that: The catalyst includes at least one of the following compounds: 。 8. The method for preparing the sulfonamide polymer according to claim 1 or 2, characterized in that: The catalyst is selected from at least one of the following compounds: 。

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