Nitrogen disubstituted polyurethane and preparation method thereof

Abstract

The invention discloses nitrogen disubstituted polyurethane and a preparation method thereof. The preparation method of the nitrogen disubstituted polysulfamate as shown in the formula I comprises the following step: in a sulfone solvent, in the presence of HMDS (hexamethyldisilazane) and phenate, performing substitution reaction on a nitrogen disubstituted compound as shown in a formula II and a bisphenol compound as shown in a formula III to obtain the nitrogen disubstituted polysulfamate as shown in the formula I. The invention further discloses a preparation method of the nitrogen disubstituted polysulfamate as shown in the formula I. The molecular weight of the nitrogen-bis-substituted polysulfamic acid ester is high; the method for preparing N-bis-substituted polysulfamate from phenate has the advantages of higher yield, fewer additives, suitability for raw materials of various structure types, and simple reaction post-treatment. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a nitrogen disubstituted polyaminosulfonate and a preparation method thereof. Background Art

[0002] Polysulfates and polysulfonates have very superior mechanical properties and can be used as engineering plastics, with broad application prospects and potential in the field of materials. Traditional sulfur (VI) polymers rely on the reaction between sulfonyl chloride and nucleophiles, but the reaction selectivity of chlorinated sulfur (VI) itself is not high, which limits the use of polymerization methods.

[0003] In 2014, the Sharpless group used DBU or BEMP as a catalyst, silicon-protected phenol and phenol fluorosulfate as raw materials (SuFEx), and successfully synthesized new polysulfonates and polysulfates (Jiajia Dong, KB Sharpless, et al, Angew. Chem. Int. Ed. 2014, 53, 9466-9470). In 2017, the Sharpless group also found that the use of anionic fluoride salts [HF 2- ](Bifluoride anion) can synthesize polysulfate with low dosage and high catalytic efficiency (Bing Gao, KB Sharpless. et al. Nature Chemistry, 2017, 9, 1083–1088).

[0004] In 2020, Dong Jiajia et al. published a patent (CN111318303A) using phenol salts as hexavalent sulfur-fluorine exchange reaction catalysts. The phenol salts can also catalyze the polymerization of polysulfates and polysulfonates. Compared with previous catalysts, they are cheaper and have higher catalytic efficiency. In 2022, Moses et al. reported (Angew. Chem. Int. Ed. 2022, 61) the efficient reaction of hexamethyldisilazane with phenol in one pot and hexavalent sulfur-fluorine bonds. This method does not require the preparation of silicon-protected phenols in advance, and can achieve hexavalent sulfur-fluorine exchange reactions on unstable silicon-protected nucleophilic functional group substrates.

[0005] However, none of the above literatures has solved the synthesis of nitrogen disubstituted polyaminosulfonates. The monomer reactivity of nitrogen disubstituted fluorosulfonamide is poor. In 2014, the Sharpless research group (Jiajia Dong, KB Sharpless, et al, Angew. Chem. 2014, 126, 9584–9603) reported that sulfur-fluorine exchange reaction with active cyclic secondary amine can only be carried out in a two-phase solvent system of acetonitrile and water with magnesium oxide as a base and heated under reflux.

[0006] In 2020, Chen Jinwei et al. mentioned in their patent (CN111072966A) that similar piperazine polysulfamide resins can be obtained by using common bases and bis(fluorosulfonylpiperazine) as raw materials. However, this method uses a large amount of base, produces a large amount of sodium fluoride salt as a by-product, and the molecular weight of the polymer obtained by the reaction is small, the actual yield is not high, and there are only piperazine derivatives at the amino end of the reaction, which has little actual production application value. Moreover, the inventor repeated this reaction and no solid precipitated.

[0007] Therefore, as a new polymer with a new connection method, how to stably and efficiently synthesize such polymers with diverse composition structures needs to be solved urgently, thereby providing the material premise for studying the properties of such polymers and expanding the research space of material materials. Summary of the invention

[0008] The technical problem to be solved by the present invention is to overcome the problem that the existing preparation methods of nitrogen disubstituted polyaminosulfonates are limited in variety, thereby providing a nitrogen disubstituted polyaminosulfonate and a preparation method thereof. The number average molecular weight and weight average molecular weight of the nitrogen disubstituted polyaminosulfonate of the present invention are both greater than 50,000; the method of preparing the nitrogen disubstituted polyaminosulfonate from phenol salt of the present invention has a high yield, uses less additives, is applicable to raw materials of various structural types, and has simple post-reaction treatment.

[0009] The present invention solves the above technical problems through the following technical solutions.

[0010] The present invention provides a nitrogen disubstituted polyaminosulfonate as shown in formula I,

[0011]

[0012] Among them, X is or -O-;

[0013] R 1 and R 1’ is independently unsubstituted or substituted with one or more halogens. 1 -C 4 alkyl;

[0014] Or, R 1 , R 1’ The carbon atom to which it is attached is unsubstituted or replaced by one or more R 1-1 Substituted C 3 -C 20 Cycloalkyl; each R 1-1 Independently for C 1 -C 4 Alkyl or halogen;

[0015] L is or "-by R 2Substituted imino-C 1 -C 4 Alkylene-R 2 substituted imino-";

[0016] Each p is independently 0, 1 or 2;

[0017] L 1 For a single key or

[0018] Each R 2 Independently for C 1 -C 4 alkyl;

[0019] n is 10 to 1000;

[0020] When L is When each p is 1, the number average molecular weight Mn of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is PS 80000~200000Da;

[0021] Or, when L is When each p is 1, the weight average molecular weight Mw of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is PS It is 85000~300000Da.

[0022] In one embodiment, in the nitrogen disubstituted polyaminosulfonate as shown in Formula I, some of the groups are defined as follows, and the remaining groups are defined as described in any other embodiment (hereinafter referred to as "one embodiment"),

[0023] When "R 1 and R 1’ is independently unsubstituted or substituted with one or more halogens. 1 -C 4 When "alkyl", the C 1 -C 4 Alkyl is methyl, ethyl, n-propyl or isopropyl, for example methyl.

[0024] In one scenario, when “R 1 and R 1’ is independently unsubstituted or substituted with one or more halogens. 1 -C 4 When the halogen is independently fluorine,

[0025] In one scenario, when “R 1 , R 1’ The carbon atom to which it is attached is unsubstituted or replaced by one or more R 1-1 Substituted C 3 -C20 When "cycloalkyl", the C 3 -C 20 Cycloalkyl is a monocyclic cycloalkyl, C 3 -C 20 Spirocyclic cycloalkyl, C 3 -C 20 Condensed ring cycloalkyl or C 3 -C 20 Bridged ring cycloalkyl.

[0026] The C 3 -C 20 The monocyclic cycloalkyl group may be C 3 -C 6 Monocyclic cycloalkyl, preferably C 3 -C 6 Saturated monocyclic cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, also for example cyclohexyl.

[0027] The C 3 -C 20 The fused ring cycloalkyl may be C 11 -C 20 Condensed ring cycloalkyl, preferably C 11 -C 20 Unsaturated fused ring cycloalkyl, more preferably C 13 Unsaturated fused ring cycloalkyl, such as

[0028] In one scheme, when L is “-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 When the imino group is substituted, the C 1 -C 4 Alkylene is methylene, ethylene, propylene or butylene, for example ethylene.

[0029] In one scheme, when L is “-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 When the R 2 is independently methyl, ethyl, n-propyl or isopropyl, for example methyl.

[0030] In one embodiment, each p is independently 1.

[0031] In one scheme, L 1 for

[0032] In one embodiment, n is 50-500.

[0033] In one scenario, R 1 and R 1’ are independently methyl or -CF 3 .

[0034] In one scenario, R 1 , R 1’ and the carbon atom to which it is attached to form a cyclohexyl or

[0035] In one solution, X is

[0036] In one scheme, L is

[0037] In one embodiment, the nitrogen disubstituted polyaminosulfonate as shown in formula I is

[0038]

[0039] Preferably, n is 50-500.

[0040] In one embodiment, the number average molecular weight Mn of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is PS It is 50000-200000 Da, preferably 65000-200000 Da.

[0041] In one embodiment, the weight average molecular weight Mw of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is PS It is 50,000 to 300,000 Da, preferably 80,000 to 270,000 Da.

[0042] In a certain embodiment, the polydispersity index PDI of the nitrogen disubstituted polyaminosulfonate as shown in formula I is 1.0 to 2.0, preferably 1.0 to 1.4.

[0043] In one embodiment, the Tg (DSC) of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is 50 to 250°C, preferably 60 to 210°C.

[0044] In one embodiment, the Td (TGA) of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is 300-400°C, preferably 330-380°C.

[0045] The present invention also provides a method for preparing a nitrogen disubstituted polyaminosulfonate as shown in formula I, comprising the following steps: in a sulfone solvent, in the presence of HMDS and phenolate, a nitrogen disubstituted compound as shown in formula II and a bisphenol compound as shown in formula III undergo a substitution reaction to obtain a nitrogen disubstituted polyaminosulfonate as shown in formula I;

[0046]

[0047] The phenolate comprises a cation and an anion;

[0048] The cation is R 4-1 , R 4-2 , R 4-3 and R 4-4 Independently for C 1 -C 6 alkyl;

[0049] The anion is a monovalent anion of a monophenol and / or a monovalent anion of a polyphenol (a monovalent anion of a polyphenol means that a plurality of phenol molecules are linked by hydrogen bonds of phenolic hydroxyl groups to form an anion with a negative charge);

[0050] Wherein, X, L and n are as defined above.

[0051] In one embodiment, the R 4-1 , R 4-2 , R 4-3 and R 4-4 Independently for C 1 -C 4 Alkyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl or n-butyl.

[0052] In one embodiment, the phenol in the monophenol monovalent anion is unsubstituted or substituted with one or more R 5-1 Substituted phenol or naphthol; each R 5-1 are independently halogen or C 1 -C 6 alkyl.

[0053] R 5-1 In the above, the halogen can independently be fluorine or bromine.

[0054] R 5-1 In the C 1 -C 6 The alkyl group independently may be methyl, ethyl, n-propyl or isopropyl.

[0055] The R 5-1 Independently, it can be fluorine or bromine.

[0056] In one embodiment, the phenol in the polyphenol monovalent anion is unsubstituted or substituted with one or more R 5-2 Substituted phenol or naphthol; each R 5-2 are independently halogen or C 1 -C 6 alkyl.

[0057] R 5-2 In the above, the halogen can independently be fluorine or bromine.

[0058] R 5-2 In the C 1 -C 6 The alkyl group independently may be methyl, ethyl, n-propyl or isopropyl.

[0059] The R 5-2 Independently, it can be fluorine or bromine.

[0060] In one embodiment, the cation is In one embodiment, the monophenol monovalent anion is In one embodiment, the polyphenol monovalent anion is

[0061] In one embodiment, the anion is

[0062] In one embodiment, the phenolate is

[0063] In one embodiment, the nitrogen disubstituted compound as shown in formula II is

[0064] In one embodiment, the bisphenol compound as shown in formula III is

[0065] In one embodiment, the nitrogen disubstituted polyaminosulfonate as shown in formula I is

[0066]

[0067]

[0068] Preferably, n is 100-200.

[0069] In one embodiment, the sulfone solvent is a conventional sulfone solvent in the art, such as sulfolane.

[0070] In one embodiment, the molar ratio of the bisphenol compound as shown in Formula III to the nitrogen disubstituted compound as shown in Formula II is the conventional molar ratio for such reactions in the art, which may be (0.95-1.05):1, preferably (0.98-1.02):1, for example 1:1, 1.02:1, 1.01:1, 0.98:1, 0.99:1.

[0071] In one embodiment, the molar ratio of the phenol salt to the nitrogen disubstituted compound of formula II is 0.0001-0.05, preferably 0.0005-0.02, for example 0.0005, 0.001, 0.002, 0.005, 0.01, 0.02.

[0072] In one embodiment, the volume mass ratio of the HMDS to the nitrogen disubstituted compound shown in Formula II is (1.2-3.0) mL / g, preferably (1.4-2.7) mL / g, for example 1.43 mL / g, 1.77 mL / g, 2.52 mL / g, 2.53 mL / g, and 2.65 mL / g.

[0073] In a certain embodiment, the volume mass ratio of the sulfone solvent to the nitrogen disubstituted compound as shown in Formula II is (0.5-5) mL / g, preferably (1.0-4.2) mL / g, for example 1.1 mL / g, 1.2 mL / g, 1.58 mL / g, 1.6 mL / g, 2 mL / g, 2.48 mL / g, 4.08 mL / g.

[0074] In one embodiment, the temperature of the substitution reaction is 100°C to 130°C, preferably 110°C to 125°C, for example 110°C, 125°C.

[0075] In one embodiment, the substitution reaction time is 2 h to 8 h, for example 2 h, 8 h.

[0076] In a certain embodiment, the substitution reaction further includes post-treatment. The post-treatment may include the following steps: removing HMDS, recrystallizing, filtering, and drying. The recrystallization may include the following steps: adding an amide solvent to dissolve, and then adding an alcohol solvent. The amide solvent may be DMF. The alcohol solvent may be methanol. The dissolution may be dissolving under heating conditions.

[0077] In a preferred embodiment, when L is Each p is 1, X is R 1 and R 1’ is independently unsubstituted C 1 -C 4 When alkyl

[0078] The molar ratio of the bisphenol compound represented by formula III to the nitrogen disubstituted compound represented by formula II is 1.01:1;

[0079] and / or, the molar ratio of the phenolate to the nitrogen disubstituted compound of formula II is 0.001;

[0080] and / or, the volume mass ratio of the sulfone solvent to the nitrogen disubstituted compound of formula II is 2.48 mL / g;

[0081] And / or, the temperature of the substitution reaction is 125°C.

[0082] In a preferred embodiment, when L is Each p is 1, X is or -O-, R 1 and R 1’ is independently unsubstituted or substituted with one or more halogens. 1 -C 4 Alkyl, or R 1 , R 1’ The carbon atom to which it is attached is unsubstituted or replaced by one or more R 1-1 Substituted C 3 -C 20 When cycloalkyl

[0083] The molar ratio of the phenolate to the nitrogen disubstituted compound of formula II is 0.01;

[0084] And / or, the volume mass ratio of the sulfone solvent to the nitrogen disubstituted compound as shown in Formula II is 1.6 mL / g.

[0085] The present invention also provides a nitrogen disubstituted polyaminosulfonate as shown in Formula I,

[0086]

[0087] Wherein, X, L and n are as defined above;

[0088] The nitrogen disubstituted polyaminosulfonate as shown in formula I is prepared by the preparation method described above.

[0089] The present invention also provides a nitrogen disubstituted compound as shown in Formula II,

[0090]

[0091] Among them, L is or "-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 substituted imino-";

[0092] Each p is independently 0, 1 or 2;

[0093] L 1 For a single key or

[0094] Each R 2 Independently for C 1 -C 4 alkyl.

[0095] In one scheme, when L is “-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 When the imino group is substituted, the C 1 -C 4 Alkylene is methylene, ethylene, propylene or butylene, for example ethylene.

[0096] In one scheme, when L is “-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 When the R 2 is independently methyl, ethyl, n-propyl or isopropyl, for example methyl.

[0097] In one embodiment, each p is independently 1.

[0098] In one scheme, L 1 for

[0099] In one embodiment, the nitrogen disubstituted compound as shown in formula II is

[0100] In the present invention, the term "cycloalkyl" refers to a cyclic hydrocarbon group having a specified number of carbon atoms, which is monocyclic or polycyclic (e.g., fused ring, spiro ring or bridged ring), and which is saturated or unsaturated. Monocyclic cycloalkyl includes but is not limited to cyclopentyl, cyclohexyl, etc. Fused ring cycloalkyl includes but is not limited to

[0101] In the present invention, the term "phenol" refers to a compound in which a hydroxyl group is directly linked to a benzene ring or a condensed benzene ring, such as phenol or naphthol.

[0102] In the present invention, the term "polyphenol monovalent anion" refers to a plurality of phenol molecules linked by hydrogen bonds of phenolic hydroxyl groups to form an anion with a negative charge.

[0103] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0104] The reagents and raw materials used in the present invention are commercially available.

[0105] The positive and progressive effects of the present invention are: the present invention provides a nitrogen disubstituted polyaminosulfonate and a preparation method thereof. The number average molecular weight and weight average molecular weight of the nitrogen disubstituted polyaminosulfonate of the present invention are both greater than 50,000; the method of preparing the nitrogen disubstituted polyaminosulfonate from phenol salt of the present invention has a high yield, uses less additives, is applicable to raw materials of various structural types, and has simple post-reaction treatment. DETAILED DESCRIPTION

[0106] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0107] Experimental instruments:

[0108] 1 H NMR spectra were measured using an Agilent-400 (400 MHz) nuclear magnetic resonance spectrometer. 1 The internal standards for H NMR were TMS (δ 0.00), CDCl 3 (δ7.26), DMSO-d 6 (δ2.50) or DMF-d 7 (δ8.03,2.92,2.75).

[0109] 13 C NMR spectra were measured using a Bruker AM-400 (100.7 MHz) nuclear magnetic resonance spectrometer. 13 The internal standard for C NMR is CDCl 3 (δ77.16), DMSO-d 6 (δ39.52), CD 3 CN(δ1.32),(CD 3 ) 2 CO(δ29.84,206.26).

[0110] 19 F NMR spectra were measured using an Agilent-400 (376 MHz) nuclear magnetic resonance spectrometer. 19 The internal standard for F NMR is FCCl 3 (δ0.00), low field is positive.

[0111] HRMS spectra were measured using a Finnigan MAT 8430 mass spectrometer.

[0112] The melting point was measured using a Büchi M-565 melting point apparatus.

[0113] GPC uses a Waters 1515 plasma chromatograph pump, a 2707 autosampler, a 2414 differential detector, a column temperature of 35 / 60°C, a mobile phase of 0.05 M lithium bromide in DMF, a flow rate of 1 mL / min, a time of 40 minutes, and an injection volume of 20 μL. Molecular weights are referenced to polystyrene.

[0114] LC-MS (ESI) spectra were measured using a Waters ACQUITY UPLC H-Class system and an ACQUITY QDa mass spectrometer detector (eluent: 0.1% trifluoroacetic acid in water and acetonitrile). [Method: 7000 psi, flow rate = 0.6 ml / min, t = 0 min, 95% H 2 O; t = 0.10 min, 95% H 2 O; t = 1.20 min, 5% H 2 O; t = 2.00 min, 5% H 2 O; t = 2.50 min, 95% H 2 O. Total aquisition time = 2.50 min] The spectra shown in the examples are UV absorption chromatograms, and the corresponding mass spectra are not shown. The horizontal axis of the chromatogram is time (unit min), and the vertical axis is absorption intensity. The three digits in the upper right corner of the chromatogram are the selected UV wavelengths (unit min).

[0115] Thermogravimetric analysis (TGA) was measured using a Q500 thermogravimetric analyzer (TA) at a temperature increase rate of 10°C / min from 0 to 600°C. Differential scanning calorimetry (DSC) was measured using a DSC 2500 (TA) analyzer at a temperature increase rate of 10°C / min from -50 to 300°C. The sample amount used in both was about 5 mg, and the nitrogen flow rate was 50 ml / min.

[0116] The reagents used were purchased from Wuhan Yaoming Lanbo Chemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd. (Aladdin), TCI (Shanghai) Chemical Industry Development Co., Ltd. (TCI), Shanghai Macklin Biochemical Technology Co., Ltd. (Macklin), San Chemical Technology (Shanghai) Co., Ltd. (Energy Chemical), Alfa Aesar (China) Chemical Co., Ltd. (Alfa Aesar), Shanghai Titan Technology Co., Ltd. (adamas), Shanghai Shuya Pharmaceutical Technology Co., Ltd., Shanghai Bid Pharmaceutical Technology Co., Ltd., Shanghai Tianlian Chemical Technology Co., Ltd., Shanghai Xianding Biotechnology Co., Ltd., Shanghai Lingfeng Chemical Reagent Co., Ltd. and Shanghai Reagent Factory No. 3.

[0117] Solvents were purchased from Sinopharm Reagent Co., Ltd., Shanghai Macklin Biochemical Technology Co., Ltd. (Macklin), Shanghai Titan Technology Co., Ltd. (adamas), Shanghai Tianlian Chemical Technology Co., Ltd., Shanghai Dahe Chemicals Co., Ltd., and Shanghai Hebang Pharmaceutical Technology Co., Ltd.; after purchase, they were used directly without additional treatment.

[0118] RT. refers to room temperature (20℃~30℃); Polydispersity and PDI refer to polydispersity index; Mn PS Number average molecular weight, Mw PS Refers to weight average molecular weight, all based on polystyrene.

[0119] In the present invention, DMSO is dimethyl sulfoxide, DMF is N,N-dimethylformamide, NMP is N-methylpyrrolidone, DMAP is 4-dimethylaminopyridine, and HMDS is hexamethyldisilazane.

[0120] Example 1

[0121] Synthesis of Bisfluorosulfonylpiperazine (A-1)

[0122]

[0123] Piperazine (34.7 g, 0.4 mol), sodium carbonate powder (94.2 g, 0.88 mol) and DMAP (49.4 g, 0.4 mol) were weighed into a 1 L egg-shaped bottle, and 500 mL of acetonitrile was added and stirred to dissolve. After plugging the bottle, a water pump was used to pump the bottle to a negative pressure, and SO 2 F 2 The balloon (about 18L) was stirred at room temperature for 24h. After the reaction, the inorganic salt was removed by filtration, the filtrate was dried, the solid was washed with hydrochloric acid until the pH of the washing solution was <7, filtered and washed with distilled water (200mL) to obtain a white solid (crude product, 92.2g). The solid was heated to reflux with acetonitrile (250mL), cooled with a small amount of water to precipitate and recrystallize, and 75.0g of white solid was obtained, with a yield of 75%.

[0124] Melting point 247.1-248.0℃.

[0125] 1 H NMR (400 MHz, DMSO-d 6 )δ3.63(s,8H).

[0126] 13 C NMR (101 MHz, DMSO-d 6 )δ45.61.

[0127] 19 F NMR (376MHz, Chloroform-d) δ41.36.

[0128] Example 2

[0129] Synthesis of Bis-4-Fluorosulfonylpiperazine Urea (A-2)

[0130]

[0131] Weigh N-boc-piperazine (58.7 g, 315 mmol) and triethylamine (43.2 g, 427 mmol) in a 1L egg-shaped bottle and dissolve in 200 mL of dichloromethane. Take triphosgene (14.8 g, 50 mmol) and dissolve in 100 mL of dichloromethane. Stir and add dropwise to the 1L reaction bottle under ice bath. After the addition, return to room temperature for reaction. After 22 hours, add water (400 mL) to quench the extraction. The aqueous phase is back-extracted once with dichloromethane (50 mL). After combining the organic phases, wash with 1M dilute hydrochloric acid until acidic, wash with saturated sodium bicarbonate solution (250 mL), saturated brine (250 mL), dry with anhydrous sodium sulfate, spin dry and put into the next step.

[0132] Add methanol (100 mL) to a 1L egg-shaped bottle, and add hydrochloric acid methanol solution (150 mL of concentrated hydrochloric acid, 100 mL of methanol) dropwise under an ice bath. Return to room temperature and react for 4 h. Dried out the solvent to obtain a crude product.

[0133] In a 1L egg-shaped bottle, weigh the crude product from the previous step, triethylamine (104.5mL, 750mmol) and DMAP (18.4g, 150mmol) and dissolve them in acetonitrile (200mL). After plugging the bottle with a stopper, pump it to negative pressure with a water pump and insert SO 2 F 2 The balloon (about 6L) was stirred at room temperature for reaction. After the balloon no longer became smaller, the acetonitrile was removed by rotation, and extracted with ethyl acetate (300mL) and water (300mL). The aqueous phase was back-extracted with ethyl acetate twice (100mL×2), 1M dilute hydrochloric acid (300mL), saturated brine (300mL×2), dried over anhydrous sodium sulfate, and the solvent was spin-dried to obtain a light yellow crude product. The crude product was heated to reflux with acetonitrile (100mL), and a small amount of water (5mL) was added to cool and precipitate and recrystallized to obtain 16.8g of a white solid with a total yield of 31%.

[0134] Melting point 163.8-164.9℃.

[0135] 1 H NMR (400MHz, Chloroform-d) δ 3.46 (d, J = 5.2 Hz, 8H), 3.43 (d, J = 5.4 Hz, 8H).

[0136] 13 C NMR (101MHz, Chloroform-d) δ 162.66, 46.56, 45.77.

[0137] 19 F NMR (376MHz, Chloroform-d) δ38.88.

[0138] Example 3

[0139] Synthesis of N,N'-difluorosulfonyl-N,N'-dimethylethylenediamine (A-3)

[0140]

[0141] In a 500 mL egg-shaped bottle, weigh N,N'-dimethylethylenediamine (8.8 g, 100 mmol), sodium carbonate powder (23.3 g, 220 mmol) and DMAP (12.2 g, 100 mmol), add 100 mL of acetonitrile and stir to dissolve. After plugging the bottle, pump it with a water pump until the bottle is under negative pressure, and insert SO 2 F 2 The reaction was stirred at room temperature with a balloon (about 6 L). After the disappearance of the raw material monitored by LC-MS, the solvent was dried, extracted with ethyl acetate (250 mL) and water (250 mL), washed with 1M dilute hydrochloric acid (200 mL) and saturated brine (300 mL), dried over anhydrous sodium sulfate, and dried to obtain 15.2 g of a crude product as a pale yellow solid. The crude product was heated with ethyl acetate for recrystallization, cooled, washed and filtered with petroleum ether, and 6.86 g of a white solid was obtained, with a total yield of 27%.

[0142] Melting point 87.4-88.5℃.

[0143] 1 H NMR (400 MHz, Acetonitrile-d 3 )δ3.58(s,4H),3.05(d,J=1.9Hz,6H).

[0144] 13 C NMR (101 MHz, Acetonitrile-d 3 )δ49.23,36.80.

[0145] 19 F NMR (376 MHz, Acetonitrile-d 3 )δ42.80.

[0146] Example 4

[0147] Synthesis of Catalyst Diphenol Tetrabutylammonium Phenolate (C)

[0148]

[0149] Tetrabutylammonium hydroxide solution (25.9 g, 40 mmol) was weighed into a 250 mL egg-shaped bottle, and molten phenol (11.3 g, 120 mmol) was added dropwise under stirring to precipitate a white solid, which was filtered, washed with distilled water, and dried in vacuo at 45°C to obtain 17.6 g of a white solid with a yield of 84%.

[0150] Melting point 67.7-68.6℃.

[0151] 1 H NMR (400 MHz, DMSO-d 6 )δ7.05–6.93(m,6H),6.65–6.57(m,6H),6.46(tt,J=7.2,1.3Hz,3H),3.22–3.0 7(m,8H),1.65–1.48(m,8H),1.29(hept,J=7.5Hz,8H),0.93(t,J=7.3Hz,12H).

[0152] 13 C NMR (101 MHz, DMSO-d 6 )δ162.32,128.85,116.49,114.88,57.50,23.05,19.17,13.44.

[0153] Phenol salt C-2 was prepared by the method described in Example 23 of patent CN111318303A.

[0154] Phenol salt C-3 was prepared by the method described in Example 18 of patent CN111318303A.

[0155] Phenol salt C-4 was prepared by the method described in Example 17 of patent CN111318303A.

[0156] Example 5

[0157] We first studied a group of reactions with the best substrate availability to explore the optimal conditions for this polymerization reaction.

[0158] Condition screening using the reaction of bis(fluorosulfonylpiperazine) (A-1) and bisphenol A (B-1) as an example

[0159]

[0160] A-1 (1.2512 g, 5.0 mmol) and bisphenol A (1.1414 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, and sulfolane and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 110°C or 125°C for 5 to 10 min to dissolve, and the catalyst C sulfolane solution (0.05 M) was added, and the heating reaction was continued. After the reaction, HMDS was pumped out with an oil pump, and DMF (2 to 5 mL) was added and heated at 140°C for 20 to 30 min to dissolve, and 200 mL of methanol was poured in while hot, stirred and precipitated, filtered, and vacuum dried.

[0161] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC. The reaction results of different catalyst dosages, different temperatures, different heating times and different sulfolane dosages are shown in Table 1.

[0162] Table 1 Screening of optimal conditions for polymerization reaction

[0163]

[0164] According to the screening results, the minimum amount of catalyst can be reduced to 0.5‰, preferably 1‰; the reaction temperature is raised to 125℃ without exceeding the boiling point of HMDS, which is the best; the polymer molecular weight is generally good when the heating time is 8h; the solvent volume is best when it is 3.1mL. Therefore, for the above substrates, No. 6 and 9 are the optimal reaction conditions.

[0165] Example 6

[0166] Screening of reaction feed ratios using the reaction of bis(fluorosulfonylpiperazine) (A-1) and bisphenol A (B-1) as an example

[0167]

[0168] A-1 and bisphenol A (BPA) were weighed into a 50 mL egg-shaped bottle, sulfolane (3.0 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5 to 10 minutes to dissolve, and the catalyst C sulfolane solution (0.05 M, 100 μL) was added, and the heating reaction was continued for 8 hours. After the reaction, HMDS was pumped out with an oil pump, and DMF (2 to 5 mL) was added and heated at 140°C for 20 to 30 minutes to dissolve, and 200 mL of methanol was poured in while hot, stirred and precipitated, filtered, and vacuum dried.

[0169] 10 mg of the product solid was dissolved in 1 mL DMF (0.05 M LiBr) and analyzed by GPC. The reaction was verified for different substrate feed ratios, and considering the instability of substrate phenol in air, we also conducted an argon protection experiment. The experimental results are shown in Table 2.

[0170] Table 2 Screening of polymerization reaction feed ratio

[0171]

[0172] Note: # Use argon protection

[0173] Based on the above results, we found that for the substrate group of A-1 and BPA, a 1% excess of phenol can effectively increase the polymer molecular weight (numbers 4 and 6 in Table 2), and the reaction effects of the closed system with argon protection and without argon protection are similar.

[0174] Example 7

[0175] Synthesis of Polyaminosulfonates from Bis(Fluorosulfonyl)piperazine (A-1) and Different Bisphenols

[0176]

[0177] A-1 (1.2512 g, 5.0 mmol) and phenol B (5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.8 mL) and HMDS (3.15 mL) were added with a pipette, the closed system was heated under reflux at 125°C for 5-10 min to dissolve, catalyst C sulfolane solution (0.25 M, 200 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, 200 mL of methanol was poured in while hot, stirred and precipitated, filtered, and vacuum dried.

[0178] 10 mg of the product solid was dissolved in 1 mL DMF (0.05 M LiBr) and analyzed by GPC. Due to the large difference in the reactivity of bisphenol, different from the previous A-1 and B-1 reactions, after attempts (No. 1, 2), the amount of catalyst for substrate expansion was increased from 1‰eq. to 1%eq., and the solvent sulfolane was reduced to 2.0 mL. Some products were difficult to dissolve in DMF and could not be analyzed by GPC. Table 3 shows the experimental results of the synthesis of each polymer.

[0179] Table 3 Synthesis of bis(fluorosulfonyl)piperazine and different bisphenol polymers

[0180]

[0181]

[0182] Note: # Sulfolane 3.1 mL, catalyst dosage 1‰ eq; * Catalyst dosage 2% eq.

[0183] The remaining compounds were synthesized as follows:

[0184] Example 8

[0185] Bis-4-fluorosulfonylpiperazine urea (A-2) and bisphenol A (B-1)

[0186]

[0187] A-2 (0.906 g, 2.5 mmol) and phenol B-1 (0.570 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (1.6 mL) were added using a pipette, the closed system was heated under reflux at 125°C for 5-10 min, catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was removed by an oil pump, and DMF (2-5 mL) was added.

[0188] Heat at 140°C to dissolve for 20-30 min, pour in 100 mL of methanol while hot, stir to precipitate, filter, and vacuum dry to obtain 1.367 g of white solid, with a yield of 99%.

[0189] Tg(DSC)=142.2℃

[0190] Td(TGA)=355.6℃

[0191] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0192] The indicators are as follows:

[0193] Mn PS =95890Da

[0194] M PS =117738Da

[0195] PDI (Mw / Mn) = 1.23.

[0196] Degree of polymerization: 174.

[0197] Example 9

[0198] Bis-4-fluorosulfonylpiperazine urea (A-2) and bisphenol Z (B-6)

[0199]

[0200] A-2 (0.907 g, 2.5 mmol) and phenol B-6 (0.671 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (1.6 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 100 mL of methanol was poured in while hot to stir and precipitate, filtered, and vacuum dried. 1.420 g of white solid was obtained, with a yield of 96%.

[0201] Tg(DSC)=151.7℃

[0202] Td(TGA)=357.3℃

[0203] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC. The indicators are as follows:

[0204] Mn PS =65452Da

[0205] M PS =86292Da

[0206] PDI (Mw / Mn) = 1.32.

[0207] Degree of polymerization: 111.

[0208] Example 10

[0209] Bis-4-fluorosulfonylpiperazine urea (A-2) and bisphenol fluorene (B-7)

[0210]

[0211] A-2 (0.906 g, 2.5 mmol) and phenol B-7 (0.876 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (2.4 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 100 mL of methanol was poured in while hot to stir and precipitate, filtered, and vacuum dried. 1.63 g of white solid was obtained, with a yield of 97%.

[0212] Tg(DSC)=202.4℃

[0213] Td(TGA)=359.7℃

[0214] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0215] The indicators are as follows:

[0216] Mn PS =66035Da

[0217] M PS =87403Da

[0218] PDI (Mw / Mn) = 1.32.

[0219] Degree of polymerization: 98.

[0220] Embodiment 11

[0221] Bis-4-fluorosulfonylpiperazine urea (A-2) and 4,4'-dihydroxydiphenyl ether (B-10)

[0222]

[0223] A-2 (0.907 g, 2.5 mmol) and phenol B-10 (0.505 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (1.6 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 100 mL of methanol was poured in while hot to stir and precipitate, filtered, and dried in vacuo. 1.428 g of white solid was obtained, and the yield was >99%.

[0224] Tg(DSC)=124.0℃

[0225] Td(TGA)=341.9℃

[0226] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0227] The indicators are as follows:

[0228] Mn PS =90070Da

[0229] M PS =118425Da

[0230] PDI (Mw / Mn) = 1.31.

[0231] Degree of polymerization: 172.

[0232] Example 12

[0233] N,N'-difluorosulfonyl-N,N'-dimethylethylenediamine (A-3) and bisphenol A (B-1)

[0234]

[0235] A-3 (0.63 g, 2.5 mmol) and phenol B-1 (0.571 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (1.6 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 100 mL of methanol was poured in while hot to stir and precipitate, filtered, and dried in vacuo. 1.188 g of white solid was obtained, and the yield was >99%.

[0236] Tg(DSC)=67.2℃

[0237] Td(TGA)=350.4℃

[0238] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0239] The indicators are as follows:

[0240] Mn PS =88587Da

[0241] M PS =110348Da

[0242] PDI (Mw / Mn) = 1.24.

[0243] Degree of polymerization: 201.

[0244] Embodiment 13

[0245] N,N'-difluorosulfonyl-N,N'-dimethylethylenediamine (A-3) and hexafluorobisphenol A (B-2)

[0246]

[0247] A-3 (0.63 g, 2.5 mmol) and phenol B-2 (0.842 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (1.6 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 100 mL of methanol was poured in while hot to stir and precipitate, filtered, and dried in vacuo. 1.286 g of white solid was obtained, with a yield of 94%.

[0248] Tg(DSC)=86.1℃

[0249] Td(TGA)=372.8℃

[0250] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0251] The indicators are as follows:

[0252] Mn PS =105470Da

[0253] M PS =133506Da

[0254] PDI (Mw / Mn) = 1.26.

[0255] Degree of polymerization: 192.

[0256] Embodiment 14

[0257] N,N'-difluorosulfonyl-N,N'-dimethylethylenediamine (A-3) and bisphenol Z (B-6)

[0258]

[0259] A-3 (0.632 g, 2.5 mmol) and phenol B-6 (0.671 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (1.6 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 100 mL of methanol was poured in while hot to stir and precipitate, filtered, and dried in vacuo. 1.235 g of white solid was obtained, and the yield was >99%.

[0260] Tg(DSC)=83.9℃

[0261] Td(TGA)=350.2℃

[0262] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0263] The indicators are as follows:

[0264] Mn PS =94857Da

[0265] M PS =118102Da

[0266] PDI (Mw / Mn) = 1.24.

[0267] Degree of polymerization: 197.

[0268] Embodiment 15

[0269] N,N'-difluorosulfonyl-N,N'-dimethylethylenediamine (A-3) and bisphenol fluorene (B-7)

[0270]

[0271] A-3 (0.631 g, 2.5 mmol) and phenol B-7 (0.876 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (1.6 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 100 mL of methanol was poured in while hot to stir and precipitate, filtered, and vacuum dried. 1.511 g of white solid was obtained, and the yield was >99%.

[0272] Tg(DSC)=137.0℃

[0273] Td(TGA)=352.8℃

[0274] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0275] The indicators are as follows:

[0276] Mn PS =96382Da

[0277] M PS =120225Da

[0278] PDI (Mw / Mn) = 1.25.

[0279] Degree of polymerization: 171.

[0280] Example 16

[0281] N,N'-difluorosulfonyl-N,N'-dimethylethylenediamine (A-3) and 4,4'-dihydroxydiphenyl ether (B-10)

[0282]

[0283] A-3 (0.631 g, 2.5 mmol) and phenol B-10 (0.505 g, 2.5 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (0.9 mL) and HMDS (1.6 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.25 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 100 mL of methanol was poured in while hot to stir and precipitate, filtered, and vacuum dried. 1.01 g of white solid was obtained, with a yield of 97%.

[0284] Tg(DSC)=62.0℃

[0285] Td(TGA)=331.8℃

[0286] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0287] The indicators are as follows:

[0288] Mn PS =118567Da

[0289] M PS =150812Da

[0290] PDI (Mw / Mn) = 1.27.

[0291] Degree of polymerization: 286.

[0292] The analysis results of the above synthesized polymers with different structures are summarized as follows:

[0293]

[0294] Embodiment 17

[0295]

[0296] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.8 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C-2 sulfolane solution (0.25 M, 200 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, filtered, and vacuum dried. 2.11 g of white solid was obtained, with a yield of 96%.

[0297] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0298] The indicators are as follows:

[0299] Mn PS =53910Da

[0300] M PS =72855Da

[0301] PDI (Mw / Mn) = 1.35.

[0302] Degree of polymerization: 123.

[0303] Embodiment 18

[0304]

[0305] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.8 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5 to 10 min to dissolve, and the catalyst C-3 sulfolane solution (0.25 M, 200 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2 to 5 mL) was added and heated at 140°C for 20 to 30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, filtered, and dried in vacuo. 2.19 g of white solid was obtained, and the yield was >99%.

[0306] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0307] The indicators are as follows:

[0308] Mn PS =109660Da

[0309] M PS=137846Da

[0310] PDI (Mw / Mn) = 1.26.

[0311] Degree of polymerization: 250.

[0312] Embodiment 19

[0313]

[0314] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.8 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C-4 sulfolane solution (0.25 M, 200 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, filtered, and vacuum dried. 2.06 g of white solid was obtained, with a yield of 94%.

[0315] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0316] The indicators are as follows:

[0317] Mn PS =44746Da

[0318] M PS =60939Da

[0319] PDI (Mw / Mn) = 1.36.

[0320] Degree of polymerization: 102.

[0321] Embodiment 20

[0322]

[0323] In a 200 mL eggplant-shaped bottle, a methanol solution of tetrabutylammonium hydroxide (40% wt, 12.98 g, 20 mmol) was weighed, and a corresponding amount of 4-fluorophenol (4.49 g, 40 mmol) was weighed. A small amount of methanol was added and stirred at room temperature to dissolve. After reacting for 1 h, the methanol was spin-dried and toluene was used to remove water 3 times. The product was dried under vacuum to obtain 8.8 g of a solid product with a yield of 95%.

[0324] 1 H NMR (400 MHz, DMSO-d 6)δ6.70(t,J=9.0Hz,4H),6.41(dd,J=9.0,4.8Hz,4H),3.24–3.03(m,8H),1.55 (td,J=12.0,10.3,6.1Hz,8H),1.30(h,J=7.3Hz,8H),0.93(t,J=7.3Hz,12H).

[0325] 13 C NMR (101 MHz, DMSO-d 6 ) δ161.55, δ152.24 (d, J = 226.1Hz), 116.68 (d, J = 7.6Hz), 114.58 (d, J = 21.4Hz), 57.52, 23.06, 19.17, 13.43.

[0326] 19 F NMR (376 MHz, DMSO-d 6 )δ-131.46.

[0327] Embodiment 21

[0328]

[0329] In a 50 mL eggplant-shaped bottle, a methanol solution of tetrabutylammonium hydroxide (40% wt, 6.51 g, 10 mmol) was weighed, and a corresponding amount of 2-bromophenol (3.47 g, 20 mmol) was weighed. A small amount of methanol was added and stirred at room temperature to dissolve. After reacting for 22 h, the methanol was spin-dried and toluene was used to remove water three times. The product was dried under vacuum to obtain 5.82 g of a solid product with a yield of 99%.

[0330] 1 H NMR (400 MHz, DMSO-d 6 )δ7.26(dd,J=7.8,1.7Hz,2H),6.92(ddd,J=8.6,7.1,1.8Hz,2H),6.71(dd,J=8.1,1.6Hz,2H),6.26(td,J=7.5,1 .6Hz,2H),3.28–3.04(m,8H),1.55(td,J=12.0,10.1,6.0Hz,8H),1.30(h,J=7.4Hz,8H),0.93(t,J=7.3Hz,12H).

[0331] 13 C NMR (101 MHz, DMSO-d 6 )δ161.00,131.85,128.02,117.97,114.10,112.22,57.51,23.04,19.18,13.46.

[0332] Embodiment 22

[0333]

[0334] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.8 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C-5 sulfolane solution (0.25 M, 200 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (5-10 mL) was added and heated at 140°C for 20-30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, filtered, and dried in vacuo. 2.18 g of white solid was obtained, with a yield of 99%.

[0335] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0336] The indicators are as follows:

[0337] Mn PS =131248Da

[0338] M PS =168316Da

[0339] PDI (Mw / Mn) = 1.28.

[0340] Degree of polymerization: 300.

[0341] Embodiment 23

[0342]

[0343] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.8 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C-6 sulfolane solution (0.25 M, 200 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (5-10 mL) was added and heated at 140°C for 20-30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, filtered, and dried in vacuo. 2.15 g of white solid was obtained, with a yield of 98%.

[0344] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0345] The indicators are as follows:

[0346] Mn PS =118515Da

[0347] M PS =147705Da

[0348] PDI (Mw / Mn) = 1.25.

[0349] Degree of polymerization: 270.

[0350] Comparative Example 1

[0351] Polymerization using DBU as catalyst

[0352]

[0353] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.8 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5 to 10 min to dissolve, and the catalyst DBU (153 mg, 1.0 mmol) was dissolved in sulfolane (0.2 mL) and then added, and the heating reaction was continued for 8 h. After the reaction, the HMDS was pumped out with an oil pump, and DMF (2 to 5 mL) was added and heated at 140°C for 20 to 30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, and no solid was precipitated.

[0354] Comparative Example 2

[0355] Polymerization using 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG) as catalyst

[0356]

[0357] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.8 mL) and HMDS (3.15 mL) were added with a pipette, the closed system was heated under reflux at 125°C for 5-10 min, the catalyst BTMG sulfolane solution (0.25 M, 200 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was removed by an oil pump, DMF (2-5 mL) was added, and the mixture was heated at 140°C for 20-30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, and no solid was precipitated.

[0358] Comparative Example 3

[0359]

[0360] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, and DMF (3.0 mL) and HMDS (3.15 mL) were added with a pipette. The closed system was heated under reflux at 125°C for 5 to 10 min to dissolve, and a catalyst C sulfolane solution (0.05 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2 to 5 mL) was added and heated at 140°C for 20 to 30 min to dissolve. While hot, 200 mL of methanol was poured in, stirred and precipitated, filtered, and vacuum dried. 2.09 g of white solid was obtained, with a yield of 95%.

[0361] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0362] The indicators are as follows:

[0363] Mn PS =29335Da

[0364] M PS =37695Da

[0365] PDI (Mw / Mn) = 1.28.

[0366] Degree of polymerization: 67.

[0367] Comparative Example 4

[0368]

[0369] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, and NMP (3.0 mL) and HMDS (3.15 mL) were added with a pipette. The closed system was heated under reflux at 125°C for 5 to 10 min to dissolve, and a catalyst C sulfolane solution (0.05 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2 to 5 mL) was added and heated at 140°C for 20 to 30 min to dissolve. While hot, 200 mL of methanol was poured in, stirred and precipitated, filtered, and vacuum dried. 1.61 g of white solid was obtained, with a yield of 74%.

[0370] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0371] The indicators are as follows:

[0372] Mn PS =17577Da

[0373] M PS=19004Da

[0374] PDI (Mw / Mn) = 1.08.

[0375] Degree of polymerization: 40.

[0376] Comparative Example 5

[0377]

[0378] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (5.0 mL) was added with a pipette, sodium carbonate (2.65 g) and sodium hydroxide (1.0 g) were added, and the closed system was heated under reflux at 125°C for reaction. After the reaction, water was added to dilute and quench, 200 mL of ethanol was poured in and stirred, and the mixture was washed with water and filtered, and no solid was precipitated.

[0379] Comparative Example 6

[0380]

[0381] Piperazine (0.43 g, 5.0 mmol) and bisphenol A (1.96 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (2.5 mL) was added with a pipette, sodium carbonate (2.65 g) and sodium hydroxide (1.0 g) were added, and the closed system was heated under reflux at 125° C. After the reaction, water was added to dilute and quench, 200 mL of ethanol was poured in and stirred, and the mixture was washed and filtered with water, and no solid was precipitated.

[0382] Comparative Example 7

[0383] Polymerization using N-BETA-aminoethyl-GAMMA-aminopropylmethyldimethoxysilane (BEMP) as catalyst

[0384]

[0385] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (2.0 mL) and HMDS (3.15 mL) were added with a pipette, the closed system was heated under reflux at 125°C for 5-10 min, the catalyst BEMP n-hexane solution (1 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, DMF (2-5 mL) was added, and the mixture was heated and dissolved at 140°C for 20-30 min, 200 mL of methanol was poured in while hot, stirred, filtered, and dried under vacuum. 0.69 g of white solid was obtained, with a yield of 32%.

[0386] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0387] The indicators are as follows:

[0388] Mn PS =12982Da

[0389] M PS =13527Da

[0390] PDI (Mw / Mn) = 1.04.

[0391] Degree of polymerization: 30.

[0392] Comparative Example 8

[0393] Polymerization using tris(dimethylamino)sulfonium difluoride as catalyst

[0394]

[0395] A-1 (1.25 g, 5.0 mmol) and bisphenol A (1.14 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (1.9 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5 to 10 min to dissolve, and the catalyst tris(dimethylamino)sulfonium difluoride sulfolane solution (0.05 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was removed by an oil pump, and DMF (2 to 5 mL) was added and heated at 140°C for 20 to 30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, filtered, and dried in vacuo. 2.12 g of white solid was obtained, with a yield of 97%.

[0396] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0397] The indicators are as follows:

[0398] Mn PS =29472Da

[0399] M PS =35033Da

[0400] PDI (Mw / Mn) = 1.19.

[0401] Degree of polymerization: 67.

[0402] Comparative Example 9

[0403] Polymerization using di(tert-butyldimethylsilyl)bisphenol A as raw material

[0404]

[0405] A-1 (1.25 g, 5.0 mmol) and di(tert-butyldimethylsilyloxy)bisphenol A (2.28 g, 5.0 mmol) were weighed into a 50 mL egg-shaped bottle, sulfolane (3.0 mL) and HMDS (3.15 mL) were added with a pipette, and the closed system was heated under reflux at 125°C for 5-10 min to dissolve, and the catalyst C sulfolane solution (0.05 M, 100 μL) was added, and the heating reaction was continued for 8 h. After the reaction, HMDS was pumped out with an oil pump, and DMF (2-5 mL) was added and heated at 140°C for 20-30 min to dissolve, and 200 mL of methanol was poured in while hot and stirred, filtered, and dried in vacuo. 0.71 g of white solid was obtained, with a yield of 32%.

[0406] 10 mg of the product solid was dissolved in 1 mL of DMF (0.05 M LiBr) and analyzed by GPC.

[0407] No obvious polymer curve was observed, which could be considered as an oligomer.

Claims

1. A nitrogen disubstituted polyaminosulfonate as shown in formula I, in, X is or -O-; R 1 and R 1’ is independently unsubstituted or substituted with one or more halogens. 1 -C 4 alkyl; Or, R 1 , R 1’ The carbon atom to which it is attached is unsubstituted or replaced by one or more R 1-1 Substituted C 3 -C 20 Cycloalkyl; each R 1-1 Independently for C 1 -C 4 Alkyl or halogen; L is or "-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 substituted imino-"; Each p is independently 0, 1 or 2; L 1 For a single key or Each R 2 Independently for C 1 -C 4 alkyl; n is 10 to 1000; When L is When each p is 1, the number average molecular weight Mn of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is PS 80000~200000Da; Or, when L is When each p is 1, the weight average molecular weight Mw of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is PS It is 85000~300000Da.

2. The nitrogen disubstituted polyaminosulfonate as shown in formula I as claimed in claim 1, It is characterized in that The nitrogen disubstituted polyaminosulfonate as shown in formula I satisfies one or more of the following conditions: (1) When "R 1 and R 1’ is independently unsubstituted or substituted with one or more halogens. 1 -C 4 When "alkyl", the C 1 -C 4 Alkyl is methyl, ethyl, n-propyl or isopropyl, for example methyl; (2) When "R 1 and R 1’ is independently unsubstituted or substituted with one or more halogens. 1 -C 4 When "alkyl", the halogen is independently fluorine; (3) When "R 1 , R 1’ The carbon atom to which it is attached is unsubstituted or replaced by one or more R 1-1 Substituted C 3 -C 20 When "cycloalkyl", the C 3 -C 20 Cycloalkyl is a monocyclic cycloalkyl, C 3 -C 20 Spirocyclic cycloalkyl, C 3 -C 20 Condensed ring cycloalkyl or C 3 -C 20 bridged ring cycloalkyl; The C 3 -C 20 The monocyclic cycloalkyl group may be C 3 -C 6 Monocyclic cycloalkyl, preferably C 3 -C 6 saturated monocyclic cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, also for example cyclohexyl; The C 3 -C 20 The fused ring cycloalkyl may be C 11 -C 20 Condensed ring cycloalkyl, preferably C 11 -C 20 Unsaturated fused ring cycloalkyl, more preferably C 13 Unsaturated fused ring cycloalkyl, for example (4) When L is "-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 When the imino group is substituted, the C 1 -C 4 Alkylene is methylene, ethylene, propylene or butylene, for example ethylene; (5) When L is "-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 When the R 2 are independently methyl, ethyl, n-propyl or isopropyl, for example methyl; (6) Each p is independently 1; (7)L 1 for and (8)n is 50 to 500.

3. The nitrogen disubstituted polyaminosulfonate as shown in formula I as claimed in claim 2, It is characterized in that The nitrogen disubstituted polyaminosulfonate as shown in formula I satisfies one or more of the following conditions: (1)X is (2) L is (3) The number average molecular weight Mn of the nitrogen disubstituted polyaminosulfonate as shown in Formula I PS 50000-200000Da, preferably 65000-200000Da; (4) The weight average molecular weight Mw of the nitrogen disubstituted polyaminosulfonate as shown in Formula I PS 50000-300000Da, preferably 80000-270000Da; (5) The polydispersity index (PDI) of the nitrogen disubstituted polyaminosulfonate as shown in formula I is 1.0 to 2.0, preferably 1.0 to 1.4; (6) The Tg of the nitrogen disubstituted polyaminosulfonate of formula I is 50 to 250° C., preferably 60 to 210° C.; and (7) The Td of the nitrogen disubstituted polyaminosulfonate as shown in Formula I is 300 to 400°C, preferably 330 to 380°C; Preferably, the nitrogen disubstituted polyaminosulfonate as shown in formula I is More preferably, n is 50-500.

4. A method for preparing a nitrogen disubstituted polyaminosulfonate as shown in formula I, It is characterized in that The method comprises the following steps: in a sulfone solvent, in the presence of HMDS and phenolate, a nitrogen disubstituted compound as shown in formula II and a bisphenol compound as shown in formula III are subjected to substitution reaction to obtain a nitrogen disubstituted polyaminosulfonate as shown in formula I; The phenolate comprises a cation and an anion; The cation is R 4-1 , R 4-2 , R 4-3 and R 4-4 Independently for C 1 -C 6 alkyl; The anions are monophenol monovalent anions and / or polyphenol monovalent anions; Wherein, the definitions of X, L and n are as described in any one of claims 1-3.

5. The method for preparing the nitrogen disubstituted polyaminosulfonate as shown in formula I as claimed in claim 4, It is characterized in that The preparation method meets one or more of the following conditions: (1) R 4-1 , R 4-2 , R 4-3 and R 4-4 Independently for C 1 -C 4 Alkyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl or n-butyl; (2) The phenol in the monophenol monovalent anion is unsubstituted or substituted with one or more R 5-1 Substituted phenol or naphthol; each R 5-1 are independently halogen or C 1 -C 6 alkyl; R 5-1 In the above, the halogen can be independently fluorine or bromine; R 5-1 In the C 1 -C 6 Alkyl groups independently may be methyl, ethyl, n-propyl or isopropyl; (3) The phenol in the polyphenol monovalent anion is unsubstituted or substituted with one or more R 5-2 Substituted phenol or naphthol; each R 5-2 are independently halogen or C 1 -C 6 alkyl; R 5-2 In the above, the halogen can be independently fluorine or bromine; R 5-2 In the C 1 -C 6 Alkyl groups independently may be methyl, ethyl, n-propyl or isopropyl; (4) The sulfone solvent is sulfolane; (5) The molar ratio of the bisphenol compound represented by Formula III to the nitrogen disubstituted compound represented by Formula II is a conventional molar ratio for such reactions in the art, which may be (0.95-1.05):1, preferably (0.98-1.02):1, for example, 1:1, 1.02:1, 1.01:1, 0.98:1, 0.99:1; (6) The molar ratio of the phenolate to the nitrogen disubstituted compound of formula II is 0.0001 to 0.05, preferably 0.0005 to 0.02, for example 0.0005, 0.001, 0.002, 0.005, 0.01, 0.02; (7) The volume mass ratio of the HMDS to the nitrogen disubstituted compound of formula II is (1.2-3.0) mL / g, preferably (1.4-2.7) mL / g, for example 1.43 mL / g, 1.77 mL / g, 2.52 mL / g, 2.53 mL / g, 2.65 mL / g; (8) The volume mass ratio of the sulfone solvent to the nitrogen disubstituted compound of Formula II is (0.5-5) mL / g, preferably (1.0-4.2) mL / g, for example, 1.1 mL / g, 1.2 mL / g, 1.58 mL / g, 1.6 mL / g, 2 mL / g, 2.48 mL / g, 4.08 mL / g; (9) The temperature of the substitution reaction is 100°C to 130°C, preferably 110°C to 125°C, for example 110°C, 125°C; (10) The time of the substitution reaction is 2 h to 8 h, for example 2 h, 8 h; (11) The substitution reaction further includes post-treatment; the post-treatment may include the following steps: removing HMDS, recrystallizing, filtering, and drying; the recrystallization may include the following steps: adding an amide solvent to dissolve, and then adding an alcohol solvent; the amide solvent may be DMF; the alcohol solvent may be methanol; the dissolution may be dissolved under heating conditions; (12) The nitrogen disubstituted compound as shown in formula II is (13) The bisphenol compound as shown in formula III is and (14) The nitrogen disubstituted polyaminosulfonate as shown in formula I is 6. The preparation method according to claim 5, It is characterized in that The preparation method meets one or more of the following conditions: (1) The cation is (2) R 5-1 are independently fluorine or bromine; (3) R 5-2 are independently fluorine or bromine; (4) The monophenol monovalent anion is (5) The polyphenol monovalent anion is Preferably, the phenate is 7. The preparation method according to claim 5, It is characterized in that The preparation method satisfies the following conditions (1) or (2): (1) When L is Each p is 1, X is R 1 and R 1’ is independently unsubstituted C 1 -C 4 When alkyl The molar ratio of the bisphenol compound represented by formula III to the nitrogen disubstituted compound represented by formula II is 1.01:1; and / or, the molar ratio of the phenolate to the nitrogen disubstituted compound of formula II is 0.001; and / or, the volume mass ratio of the sulfone solvent to the nitrogen disubstituted compound of formula II is 2.48 mL / g; And / or, the temperature of the substitution reaction is 125°C; (2) When L is Each p is 1, X is or -O-, R 1 and R 1’ is independently unsubstituted or substituted with one or more halogens. 1 -C 4 Alkyl, or R 1 , R 1’ The carbon atom to which it is attached is unsubstituted or replaced by one or more R 1-1 Substituted C 3 -C 20 When cycloalkyl The molar ratio of the phenolate to the nitrogen disubstituted compound as shown in Formula II is 0.01; And / or, the volume mass ratio of the sulfone solvent to the nitrogen disubstituted compound as shown in Formula II is 1.6 mL / g.

8. A nitrogen disubstituted polyaminosulfonate as shown in formula I, in, X, L and n are defined as in any one of claims 1 to 3; The nitrogen disubstituted polyaminosulfonate as shown in formula I is prepared by the preparation method described in any one of claims 4 to 7.

9. A nitrogen disubstituted compound as shown in formula II, in, L is or "-by R 2 Substituted imino-C 1 -C 4 Alkylene-R 2 substituted imino-"; Each p is independently 0, 1 or 2; L 1 For a single key or Each R 2 Independently for C 1 -C 4 alkyl.

10. The nitrogen disubstituted compound as shown in formula II as claimed in claim 9, It is characterized in that The nitrogen disubstituted compound as shown in formula II satisfies one or more of the following conditions: (1) C 1 -C 4 Alkylene is methylene, ethylene, propylene or butylene, for example ethylene; (2) R 2 are independently methyl, ethyl, n-propyl or isopropyl, for example methyl; (3) each p is independently 1; and (4)L 1 for Preferably, the nitrogen disubstituted compound as shown in formula II is

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