Efficient and simplified strategy to access novel polysulfamate materials: from laboratory research to industrial production

Abstract

The development of materials from laboratory research to industrial production is a complex, challenging, but significant process. Polysulfamates have not been industrially available to date because of the absence of efficient and economical synthetic methods. Herein, a comprehensive process for the development of novel polysulfamate (PSA) materials from laboratory research to industrial manufacture is reported. PSAs were prepared with high molecular weight and narrow polydispersity through nucleophilic polycondensation between aryl bisphenols and disulfamoyl difluorides in the presence of an inorganic base. The polymerization process was stable in moisture and air. The industrial production of PSAs was achieved on 100 kg scale with the assistance of a cooperative factory for the first time. The PSAs displayed excellent solvent tolerance, acid/base resistance, thermal stability, machinability and mechanical properties, which were promising for their application in the area of engineering plastics, as well as high-performance resins.

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Introduction

The sulfur(VI) fluoride exchange (SuFEx) reaction is an efficient and rapid method to synthesize functional molecules containing (poly)sulfates, (poly)sulfonates or sulfamates,^1,2 which has been widely applied in the fields of organic synthesis, materials science, pharmaceutical chemistry and bio-chemistry.^3–5 In materials chemistry, especially, polysulfates and polysulfonates with excellent properties have been successfully synthesized through the SuFEx reaction.⁶ Additionally, this new click reaction has also been instrumental in the formation of S(VI)–N bonds,⁷ resulting in the construction of sulfonamides, sulfamates, and sulfamides.^8,9 Sulfamides are valuable motifs, which can be found in therapeutic applications^10,11 and the catalytic synthesis of pyrimidine systems,^12,13 as well as in polymer synthesis.^14,15 However, despite their good performance in bioactive compounds, sulfamates are comparatively underexplored because of the challenges posed by their synthesis. In particular, polysulfamate (PSA) materials have not been available to date because of the absence of an efficient and economical synthetic method. S. Mahapatra et al. reported an advanced process to synthesize nitrogenous sulfur(VI) compounds.¹⁶ Compared to traditional synthetic protocols, S(VI) fluorides were activated by calcium triflimide and DABCO for SuFEx with amines (Fig. 1a1). However, the stoichiometric utilization of Ca(NTf₂)₂ and DABCO sets up a barrier against the large-scale synthesis of PSAs.

Fig. 1 Reaction of sulfonyl fluorides and nucleophilic reagents.

With the progress of science and technology, the modification of existing materials or the development of new materials are of great significance.^17,18 We previously reported a nucleophilic process to construct sulfate bonds through the reaction of aryl phenols and aryl fluorosulfates (Fig. 1a2).¹⁹ Polysulfates are promising engineering polymers due to their excellent mechanical and chemical properties.^19–21 Thus, we hypothesized that the reaction between aryl phenols and R₂N–SO₂F in the presence of an inorganic base (IOB) could be applicable to the synthesis of sulfamates. We proposed that polymers bearing a sulfamate bond instead of a sulfate bond may lead to a PSA with the properties of tenacity, machinability and mechanical performance.

Materials science plays an indispensable role in the progress of science, transmission of civilization and the development of human society.^22–24 The purpose of laboratory research is to provide primary products and technical services for industrial production. Generally, the development of materials from laboratory research to industrial production and commercial applications is a complex, challenging and protracted process.²⁵ For example, polycarbonates (PCs) were first prepared by Einhorn in 1898, but the widely used PC produced from bisphenol A (BPA) was prepared in 1941.²⁶ The polymerization of vinyl chloride in sealed tubes was reported in 1872, but commercial interest in poly(vinyl chloride) was revealed in 1928.²⁷ Polyethylene (PE) was produced from ethylene in 1936 by Fawcett, but all commercial PE was produced by high-pressure processes until the mid-1950s.²⁸ Therefore, substantial efforts should be made to achieve the scaled-up and industrial production of PSA, which is necessary to support their industrial application.

The goal of our research is to develop an efficient and cost-effective protocol to access polysulfamates with high molecular weight and low polydispersity index (PDI) both in laboratory research and industrial production. Herein, we report a simplified method to access sulfamates (Fig. 1b1) and polysulfamates (Fig. 1b2) efficiently through the reaction between aliphatic sulfonyl fluorides and aryl phenols in the presence of IOBs. We also evaluated the physical and chemical properties of the polysulfamates. This study aims to bridge the gaps between laboratory research, industrial production, and practical applications of PSAs.

Results and discussion

Nucleophilic construction of a sulfamate bond

We began our study by treating pyrrolidine-1-sulfonyl fluoride (1a) with 4-(2-phenylpropan-2-yl) phenol (2a) in the presence of K₂CO₃ in N,N-dimethylformamide (DMF). (For details of the screening of conditions, see ESI section 2.1.†)¹⁹ To our delight, the corresponding sulfamates could be obtained in excellent yields when the reaction was conducted at 135 °C. Fig. 2 shows the substrate scope of this nucleophilic sulfamate bond-construction reaction. Various aliphatic sulfonyl fluorides can react with aryl phenols, affording the desired sulfamates in excellent yields. Among them, piperidine-1-sulfonyl fluoride displayed higher reactivity with aryl phenols than pyrrolidine-1-sulfonyl fluoride under the reaction conditions (Fig. 2). These results inspired us to try polycondensation between disulfamoyl difluorides and aryl diphenols.

Fig. 2 Substrate scope of the nucleophilic construction of the sulfamate bond.

Laboratory research into PSAs

Laboratory synthesis of PSAs. In general, the nucleophilic substitution reaction between aryl fluorosulfates and aliphatic amines (see ESI section 3.1† for details)⁷ or the reaction between aryl bisphenols and alkylsulfamoyl fluorides could afford the desired PSAs (Fig. 1). However, our condition screening experiments showed that the reaction between aryl bisphenols and alkylsulfamoyl fluorides was the preferred one to obtain a PSA with a higher M_n and narrow PDI. Screening of the conditions for polycondensation (Table 1) was evaluated on the basis of previous work,¹⁹ using A1 and B1 as model monomers. When the polycondensation was conducted at 25 °C in the presence of Na₂CO₃ for 6 h in DMF, no desired polymer was observed (Table 1, entry 1). Then, we increased the reaction temperature to 80 °C and after 6 h, both Na₂CO₃ and K₂CO₃ promoted the polycondensation and gave the polysulfamate P1 with M^PS_n = 1.26 kDa (PDI = 1.80) and M^PS_n = 1.48 kDa (PDI = 1.93), respectively (Table 1, entries 2 and 3). These results indicated that the polycondensation reaction between A1 and B1 could be promoted by K₂CO₃ or Na₂CO₃. The M^PS_n of P1 was dramatically improved to 61.49 kDa (PDI = 1.59) with quantitative yield, by increasing the reaction temperature to 135 °C in the presence of Na₂CO₃ (Table 1, entry 4), while K₂CO₃ exhibited better promotion performance for this reaction (Table 1, entry 5). Reducing the reaction concentration or the amount of base could result in P1 with lower M^PS_n (Table 1, entries 6 and 7). Polycondensation carried out at 150 °C did not show superior results compared with that at 135 °C, producing P1 with lower M^PS_n (42.17–60.72 kDa vs. 77.84 kDa) and relatively unchanged PDI (Table 1, entries 8–11). This might be because of decomposition of the solvent at high temperature. Then we tried sulfolane and NMP, and the results indicated that sulfolane was the best choice when the reaction was carried out at 150 °C, giving P1 with high molecular weight (M^PS_n = 105.10 kDa) and narrow PDI (1.58) in quantitative yield (Table 1, entry 12). When the reaction was conducted in N-methylpyrrolidone (NMP), no better result was obtained (Table 1, entry 13). Neither did the employment of K₃PO₄ or Na₃PO₄ show superior results (Table 1, entries 14 and 15). Alkaline-earth metal carbonates, such as MgCO₃, CaCO₃ or BaCO₃, could not promote the reaction (Table 1, entry 16). We did not investigate a higher reaction temperature because attacks by the base on R₂N–SO₂F, decomposition of the solvent and oxidation of aryl phenol at high temperature had negative effects on polycondensation. We have now obtained the optimal conditions (Table 1, entry 12) for this polycondensation reaction to synthesize PSAs.

Table 1 Screening of conditions for the synthesis of P1^a

Entry	Base	Solvent	T/°C	M ^PSn/kDa	PDI
a The reaction was carried out with 2.5 mmol A1 (1.00 equiv.) and B1 (1.01 equiv.) in 5 mL of solvent in the presence of 2.2 equiv. of base for 6 h. b 10 mL of DMF was used. c 1.1 equiv. of base was used. d The reaction was carried out for 12 h. T, external temperature. M^PSn, number-average molecular weight with polystyrene as standard. PDI, polydispersity index.
1	Na2CO3	DMF	25	—	—
2	Na2CO3	Sulfolane	80	1.26	1.80
3	K2CO3	Sulfolane	80	1.48	1.93
4	Na2CO3	DMF	135	61.49	1.59
5	K2CO3	DMF	135	77.84	1.58
6^b	K2CO3	DMF	135	69.52	1.69
7^c	K2CO3	DMF	135	64.79	1.66
8	K2CO3	DMF	150	42.17	1.49
9^b	K2CO3	DMF	150	44.57	1.52
10^d	K2CO3	DMF	150	61.38	1.66
11^b^,^d	K2CO3	DMF	150	60.72	1.68
12	K 2 CO 3	Sulfolane	150	155.02	1.65
13	K2CO3	NMP	150	49.73	1.53
14	K3PO4	Sulfolane	150	76.83	1.68
15	Na3PO4	Sulfolane	150	65.32	1.72
16	CaCO3	Sulfolane	150	—	—

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With the optimal conditions in hand, we then examined monomers with various groups to verify the application scope of our process, and the results are shown in Table 2. Both aliphatic chains or rings of disulfamoyl difluorides could react with aryl diphenols bearing different groups to produce PSAs with M^PS_n ranging from 32 kDa to 167 kDa (for details, see ESI section 4.1†) and narrow PDI (1.34–1.71). Aryl diphenols with large steric hindrance could be applied to this method to afford the target polymers (P7, P8, P12, P13, P19, P20, P26 and P27). We found that the molecular weights of P13 and P27 were relatively low, whereas those of P8 and P20 were relatively high. The results suggested that steric hindrance is not the sole determining factor, and the polymer may also be influenced by the reactivity of the monomers and the polymerization process. In addition, polymerization involving B7 as the bisphenol partner may be unsuitable due to the presence of lactone under the conditions of a base and high temperature (P7, P12 and P26). Copolymerization of A1, B1 and B7 could also provide the polymer with high M_n and narrow PDI (P28).

Table 2 Synthesis of PSAs from diverse building blocks^a,b

PSA	Mon.	M ^PSn/kDa	PDI	PSA	Mon.	M ^PSn/kDa	PDI
a The reaction was carried out on 2.5 mmol scale in sulfolane (0.5 M) at 150 °C for 6 h in the presence of K2CO3 (2.2 equiv.). b For structures of the polymers, see ESI section 3.2.2.† c n A1  : nB1 : nB7 = 1 : 0.9 : 0.1; M^PSn, number-average molecular weight with polystyrene as standard; PDI, polydispersity index; Mon., monomers.
P1	A1 + B1	155	1.65	P15	A3 + B2	81	1.53
P2	A1 + B2	110	1.56	P16	A3 + B3	63	1.61
P3	A1 + B3	90	1.41	P17	A3 + B5	103	1.61
P4	A1 + B4	45	1.43	P18	A3 + B6	120	1.57
P5	A1 + B5	60	1.34	P19	A3 + B7	47	1.41
P6	A1 + B6	67	1.71	P20	A3 + B8	72	1.45
P7	A1 + B7	45	1.27	P21	A4 + B1	64	1.52
P8	A1 + B8	140	1.69	P22	A4 + B2	44	1.51
P9	A2 + B1	42	1.50	P23	A4 + B3	37	1.71
P10	A2 + B2	85	1.64	P24	A4 + B5	37	1.51
P11	A2 + B3	34	1.57	P25	A4 + B6	66	1.44
P12	A2 + B7	96	1.50	P26	A4 + B7	40	1.38
P13	A2 + B8	35	1.50	P27	A4 + B8	32	1.59
P14	A3 + B1	64	1.46	P28	A1 + B1 + B7	167	1.60

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Possible mechanism. A nucleophilic polycondensation process was proposed for the formation of PSA (taking the reaction of A1 and B1 as an example (Fig. 3b)), according to previous work^19,29 and the results of control experiments. (When IOBs were absent from the polycondensation reaction, the desired P1 could not be obtained (Fig. 3a).) First, K₂CO₃ reacted with aryl bisphenol A (B1) to form potassium 4,4′-(propane-2,2-diyl)diphenolate (BPA–K) at high temperature, with the generation of H₂O and CO₂. Then, the nucleophilic polycondensation reaction between BPA–K and A1 and chain propagation proceeded with prolonged reaction time, affording the desired polymer with the release of KF: in brief, polycondensation including a “salifying–nucleophilic attack–chain propagation” process. In addition, the by-products (water, CO₂ and KF) of our method are widely used industrial raw materials,³⁰ which lowers the production cost.

Fig. 3 Mechanistic study.

Scale-up synthesis of P1. To meet the requirements of industrial manufacture, scaled-up polymerization was investigated (taking the synthesis of P1 as an example), and the 100 g-scale experiment showed that P1 with high M_n (148 kDa) and narrow PDI (1.82) was obtained in 97% yield (for details, see ESI section 3.3†). From the results, we found that our protocol was very promising for the industrial production of PSAs. As a next step, we may focus on the industrial production and commercial applications of PSAs.

Characterizations of PSAs. To further investigate their engineering applications, the thermal, mechanical and chemical properties of the PSAs were measured. In line with the T_g values (ranging from 102.2 °C to 234.8 °C) of the PSAs (for details, see ESI section 4.2†), the polymers were amorphous, as we identified no crystalline melting or crystallization peaks (for details, see ESI section 7.3†).³¹ The PSAs exhibited excellent thermal stability, according to TG analysis: a weight loss of 5% occurred at 290–350 °C (Fig. S2†). The T_g and T_d of the polymers with flexible blocks were lower than those of the polymers with rigid blocks (for example: P2, P3vs. P1; P14vs. P1 and P1vs. P7, P8). The stability experiments of P1 showed that, even when P1 was soaked in strong acid (conc. HNO₃ and HCl) or NaOH solution (40%) for 7 days, the shape and mechanical properties of the polymer were maintained. These results indicate that PSA materials are promising high-performance acid/alkali-resistant polymers. The polymers also had the property of solvent resistance (for details and other properties of P1, see ESI section 4.4†).

Table 3 shows the mechanical properties of the polymers. P1, P9, and P21 exhibit high mechanical strength, with tensile strengths of 75 MPa, 77 MPa, and 71 MPa, respectively. The tensile and flexural strengths of PSAs with flexible blocks (P14) were lower than those of polymers with rigid blocks (for details of the testing of mechanical properties, see ESI section 4.3†). Compared to polycarbonate,¹⁹ polysulfone,¹⁹ and polyamide 6, the newly synthesized polysulfamates exhibit high strength and modulus, demonstrating their potential applications as engineering materials.

Table 3 Mechanical properties of the polymers^a,b

Polymer	Tensile strength (MPa)	Elastic modulus (MPa)	Flexural strength (MPa)	Flexural modulus (MPa)
a PC (polycarbonate), PSU (polysulfone) and PA 6 (polyamide 6) were applied as contrasting polymers. b P1 with M^PSn = 155 kDa, P9 with M^PSn = 42 kDa, P14 with M^PSn = 64 kDa and P21 with M^PSn = 64 kDa were applied.
P1	75	3500	94	3531
P9	77	3600	98	3560
P14	55	2300	75	2500
P21	71	3500	91	3500
PC	60	2500	79	2500
PSU	68	2600	88	2600
PA 6	60	2300	65	2340

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Industrial production and applications of PSAs

Industrial production of P1. Industrial production is the key issue for the commercial application of materials. In our lab research, the 1000-gram-scale synthesis of P1 was undertaken, which laid the foundation for further large-scale production. With the cooperation of Inner Mongolia Tuwei New Material Technology Co., Ltd, the conditions for the scaled-up production of P1 were optimized and hundreds of kilograms of P1 with high M_n (158 kDa) and narrow PDI (1.63) were successfully produced. After postprocessing, including granulating, washing, removal of salts, solvent recovery and drying, the material was used in the next application step without other modification.

We evaluated the mechanical properties of industrial P1 products (M^PS_n = 110 kDa, PDI = 1.61) and found that their mechanical strength was comparable at both the 1000 g and 100 kg production scales. This finding indicates that the mechanical properties of the polymer remain stable during large-scale industrial production (for details, see ESI section 5†).

Processing of PSAs. Machinability is important for engineering materials;³² thus, the machinability of PSAs should be evaluated for investigation of their further application. Four PSAs with different structures (P1, P9, P14, and P21) were selected to assess the processability of PSA. As shown in Fig. 4, PSA polymers can be processed to yield industrial resin raw materials. PSA resin is amber coloured and transparent (Fig. 4a), and the film exhibits good transparency (Fig. 4b). This further indicates that all four polymers possess amorphous structures, in agreement with the DSC results.³³

Fig. 4 Machinability and applications of PSAs. (a) PSA resins, (b) PSA films and (c) processed products using P1.

Applications of PSAs. Due to their excellent mechanical properties, chemical resistance, and thermal stability, PSA materials have broad application potential in various fields, such as automotive plastic parts and acid/alkali-resistant containers.³⁴Fig. 4c shows application products of P1. For example, wafer cassettes are commonly used in acid/base processes within the semiconductor etching industry to carry and transport wafers.³⁵ After being used for 30 days, there were no changes in performance of the wafer cassette prepared using P1, which indicated that PSA materials could be applied under acid- and alkali-resistant conditions.

Conclusions

We have developed an efficient method to construct a sulfamate bond. By applying this method, PSA materials were successfully produced both in the laboratory and in a chemical factory. PSAs possess the properties of lower production costs, higher T_g and mechanical strength than PSEs. This research on PSA from laboratory synthesis to industrial production is a successful example of the combination of study, research and production. Our work would make significant contributions to the development of sulfonic materials, as well as materials science. Research into the application of PSAs is underway in our lab and the cooperative enterprises.

Experimental

General procedure for laboratory synthesis of PSA

Aryl phenols (2.50 mmol, 1.0 equiv.) and alkylsulfamoyl fluorides (2.55 mol, 1.02 equiv.) were combined in a 25 mL glass vial equipped with a magnetic stir bar. Sulfolane (5.0 mL) was added, and the vial was placed into a pre-heated 150 °C oil bath with stirring. After 2 min, commercially available anhydrous K₂CO₃ (2.2 equiv.) was added in one portion. The reaction was run for 6 h, during which the reaction mixture turned highly viscous and moisture appeared. At the end of the reaction, it was allowed to cool to 70 °C and the mixture was slowly poured into 50 mL of cold water under vigorous stirring. Polymers precipitated as white fiber or powder once the sulfolane solution touched the water. The polymers were collected via filtration and then refluxed in water for 1 h to remove the salts and sulfolane. Finally, the polymers were dried at 40 °C for 12 h in vacuo. The molecular weight and polymer distribution were determined on GPC. The thermal properties were determined by DSC and TGA analysis.

Industrial production of P1

The 100 kg-scale P1 was produced in Inner Mongolia Tuwei New Material Technology Co., Ltd. Generally, under N₂ atmosphere, A1 (70.78 kg) and BPA (64 kg) were dissolved in sulfolane (450 kg) in a 1000 L steel reactor. K₂CO₃ (85.23 kg) was added (within 30 min) to the reaction mixture when the temperature was raised to 170 °C. The moisture was removed by N₂ and collected by condensing. After reaction, the crude product P1 was post-processed, including granulating, washing, removal of salts, solvent recovery and drying. The obtained P1 was used without other modification or processing.

Author contributions

Z. W. and J. X. conceived the experiments and led the project. M. X., L. P., C. J., Z. Z., W. X. and Z. Y. performed most experiments. Z. W. and M. X. wrote the manuscript.

Data availability

All relevant data are available from the corresponding author upon reasonable request. The authors declare that all data generated or analyzed during this study are included in this article and its ESI.†

Conflicts of interest

The authors have filed a patent application (CN111072966B), on materials reported in this manuscript and are working to commercialize advanced PSAs.

Acknowledgements

We appreciate the financial support from the National Natural Science Foundation of China (No. 91853106), Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery (No. 2023B1212060022), Guangdong Provincial Key Laboratory of Construction Foundation. Shenzhen Science and Technology Program (No. JSGG20200225153121723), and the Department of Education of Guangdong Province, China (No. 2020KQNCX016), and Fundamental Research Funds for the Central Universities, Sun Yat-Sen University (No. 23ptpy40). We also wish to thank Inner Mongolia Tuwei New Material Technology Co., Ltd for its support.

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Footnotes

† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4py01383b

‡ These authors contributed equally to this work.

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