Aryldithiolane monomers and polydisulfides containing same and methods of making same

Abstract

The application discloses an aryl-containing dithiolcyclopentane monomer and a polydisulfide and a preparation method thereof. The aryl group is introduced into the 4th position of a 1,2-dithiolcyclopentane monomer for the first time, the introduction of the aryl group expands the monomer library of the polydisulfide, the monomer has high polymerization activity, and the obtained polymer has more excellent thermal stability, mechanical and optical properties, and degradability compared with a polydisulfide prepared from a traditional thioctic acid derivative. The light-cured resin prepared from the aryl-containing dithiolcyclopentane monomer and a crosslinking reagent has excellent mechanical properties and higher strength than similar light-cured resins based on disulfides. Moreover, the aryl-containing dithiolcyclopentane monomer is prepared from an allyl benzene derivative as a reaction raw material, and in particular, an allyl phenyl ether substrate is a natural product of piperonyl and estragole and derivatives thereof, the raw material is green, low-toxic and low-cost.

Description

Technical Field

[0001] This invention relates to the fields of monomer synthesis and polymer synthesis technology, specifically to aryl dithiocyclopentane monomers and their synthesis methods, methods for preparing aryl side-chain polydisulfides by ring-opening polymerization, and methods for efficiently degrading polymers into monomers. Background Technology

[0002] Sulfur-containing polymers are a class of polymers with special functions. Due to the unique physical and chemical properties of the sulfur element they contain, sulfur-containing polymers exhibit good thermal stability, optical properties, and corrosion resistance. Sulfur-containing polymers can be broadly classified into two types: those containing carbon-sulfur double bonds and those containing carbon-sulfur single bonds. The former, represented by thioesters, slowly decomposes and releases hydrogen sulfide over long-term use. The latter, represented by thioethers and polydisulfides, are less prone to decomposition and therefore have broader application prospects. Among them, polydisulfides, due to the additional dynamic nature of their S–S bonds, have potential application value in biodegradable polymers, biomedical materials, battery materials, and reprocessable materials, and are developing rapidly. However, due to the dynamic nature of their skeleton, their mechanical and thermal properties are relatively low, and improving stability may lead to a decrease in degradability.

[0003] Currently, ring-opening polymerization of 1,2-dithiocyclopentane is the main method for preparing polydisulfides. However, the types and properties of monomers available for ring-opening polymerization are limited, mainly lipoic acid and asparagic acid and their derivatives. Furthermore, the industrial preparation of 1,2-dithiocyclopentane involves three independent synthetic steps, which presents problems such as complex synthetic routes, high purification difficulty, low yield, and susceptibility to supply fluctuations in the international market. Summary of the Invention

[0004] This invention provides a novel method for preparing 1,2-dithiocyclopentane monomers from inexpensive bulk chemicals. This monomer contains aryl side chains and exhibits high polymerization activity. The resulting polymer demonstrates superior thermal stability, mechanical and optical properties, and biodegradability compared to polydisulfides prepared from traditional lipoic acid derivatives. This overcomes the problems of poor performance, complex synthesis, and the incompatibility between stability and biodegradability found in traditional polydisulfides.

[0005] The present invention achieves the above-mentioned technical objectives through the following technical solutions.

[0006] In a first aspect of the present invention, a 4-aryl-1,2-dithiocyclopentane monomer is provided, the general structural formula of which is shown in formula (I):

[0007]

[0008] Wherein, R can be a mono- or poly-substituted benzene ring, and R can be hydrogen, alkyl, aryl, alkoxy, aryloxy, benzyloxy, siloxy, halogen, etc. The alkyl group is preferably a C1-C12 alkyl group, which can be a straight-chain or branched alkyl group, or a cycloalkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, etc.; the aryl group is preferably a C6-C12 aryl or substituted aryl group, such as phenyl, naphthyl, substituted phenyl, substituted naphthyl, etc.; the alkoxy group is preferably a C1-C12 alkoxy group, and the alkyl group on the oxygen atom can be a straight-chain or branched alkyl group, or a cycloalkyl group, such as methoxy, ethyl... The aryloxy group includes hydroxyl groups such as n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and cyclohexyloxy. The aryloxy group is preferably a C6-C12 aryloxy or substituted aryloxy group, such as phenoxy, naphthoxy, substituted phenoxy, or substituted naphthoxy. The siloxy group is preferably a trialkylsiloxy group, where the three alkyl substituents on the silicon atom are the same or different, preferably C1-C6 alkyl substituents, such as trimethylsiloxy or tert-butyldimethylsiloxy. The halogen includes fluorine, chlorine, bromine, and iodine. The substituents on the substituted aryl and substituted aryloxy groups are preferably C1-C6 alkyl groups.

[0009] R includes, but is not limited to, the following structures:

[0010]

[0011] In a second aspect of the present invention, a method for synthesizing the above-mentioned 4-aryl-1,2-dithiocyclopentane monomer is provided, comprising the following steps:

[0012]

[0013] Step a: Dissolve the allylbenzene derivative in an organic solvent, and add Br at room temperature. + reagents, Br – The reagents and additives are stirred for a period of time (e.g., 2–16 h), the insoluble matter is removed by filtration, and the solvent is evaporated to obtain a mixture of intermediates 1,3-dibromide and 1,2-dibromide, which is used directly in step b.

[0014] Step b: Dissolve the mixture of 1,3-dibromide and 1,2-dibromide in dimethyl sulfoxide, add potassium thioacetate and stir at room temperature for a period of time, such as 2 hours. Then add alkali and alcohol, and reflux and stir at a certain temperature for a period of time (such as 16 hours). After the reaction, cool to room temperature and purify the product: add water, extract with ethyl acetate, and rotary evaporate to obtain the crude product. Finally, obtain the 4-aryl-substituted 1,2-dithiocyclopentane monomer by column chromatography or vacuum distillation.

[0015] In step a above, the organic solvent may be selected from one or more of 1,2-dichloroethane, dichloromethane, tetrahydrofuran, toluene, and acetone; the concentration of the substrate (allylbenzene derivative) may be 0.1–2.0 M; the Br + The reagent may be selected from one or more of N-bromosuccinimide, N-bromophthalimide, and dibromohydantoin; the Br – The reagent can be selected from bromides such as zinc bromide, lithium bromide, potassium bromide, sodium bromide, magnesium bromide, copper bromide, iron bromide, and tetrabutylammonium bromide, preferably one or more of them; the additive can be selected from strong organic acids such as trifluoroacetic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid, or 1,3-diphenylurea, 1,3-diphenylthiourea, and 1,3-(3',5'-bistrifluoromethyl)phenylthiourea.

[0016] In step b above, the alkali can be one or more of lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; the alcohol can be one or more of methanol, ethanol, and propanol; the temperature can be between 80 and 100°C; and the concentration of the substrate (a mixture of 1,3-dibromide and 1,2-dibromide) can be 0.1–2.0 M.

[0017] In some embodiments of the present invention, methods for synthesizing 4-allylphenyl ether from 4-allylphenol (piperol) are provided, with different methods provided for substituents R containing different orders of carbon atoms, including:

[0018]

[0019] Method A: Alkylation using a haloalkane. Dissolve 4-allylphenol in an organic solvent, then add a primary haloalkane R′X and a base. Reflux the reaction mixture for 6–12 h. Cool the reaction to room temperature, add water, extract with ethyl acetate, and rotary evaporate to obtain the crude product. Finally, obtain 4-allylphenyl ether by column chromatography or vacuum distillation.

[0020] Method B: Alkylation using cycloolefins. 4-Allylphenol is dissolved in a cycloolefin, a catalyst is added, and the reaction mixture is refluxed for 1–5 h. The reaction is cooled to room temperature, water is added, and the mixture is extracted with ethyl acetate. The crude product is obtained by rotary evaporation and finally 4-allylphenyl ether is obtained by column chromatography or vacuum distillation.

[0021] Method C: Alkylation using dialkyl dicarbonate. 4-Allylphenol was dissolved in an organic solvent, and dialkyl dicarbonate and magnesium perchlorate were added. The reaction mixture was refluxed for 8–16 h. The reaction was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation, and finally, 4-allylphenyl ether was obtained by column chromatography or vacuum distillation.

[0022] In method A above, the organic solvent can be selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, and acetonitrile; X in the primary haloalkane R′X can be selected from chlorine, bromine, or iodine, and R′ can be selected from C1-C12 straight-chain or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; the base can be one or more of carbonates such as potassium carbonate, sodium carbonate, and magnesium carbonate; and the substrate concentration can be 0.1–2.0 M.

[0023] In method B above, the cyclic olefin can be selected from C5 to C12 cyclic olefins, such as one or more of cyclohexene, cyclopentene, and cycloheptene; the catalyst is one of boron trifluoride, stannous dichloride, and ferric chloride; and the substrate concentration can be 0.1–2.0 M.

[0024] In method C above, the alkyl group of the dialkyl dicarbonate can be selected from tertiary alkyl groups of C4 to C12, such as one or more of tert-butyl, tert-pentyl, and tert-hexyl; the substrate concentration can be 0.1–2.0 M.

[0025] In a third aspect of the invention, a polydisulfide with a benzene ring-containing main chain prepared from the above-described 4-aryl-1,2-dithiocyclopentane monomer is provided, the general structural formula of which is shown in formula (II):

[0026]

[0027] Wherein, n is the degree of polymerization, preferably 15-400; the number-average molecular weight of the polydisulfide shown in formula (II) is greater than or equal to 3 kDa, preferably 3-80 kDa, and the molecular weight distribution is 1.0-2.0, preferably 1.48-1.80. R represents one or more substituents on the benzene ring, which can be hydrogen, alkyl, aryl, alkoxy, aryloxy, benzyloxy, siloxy, halogen, etc.

[0028] In a fourth aspect of the present invention, a method for synthesizing the polydisulfide shown in formula (II) above is provided, as follows:

[0029] The 4-aryl-1,2-dithiocyclopentane monomer shown in formula (I) was dissolved in an organic solvent, and an initiator and a base were added to carry out a ring-opening polymerization reaction. Finally, a quencher was added to obtain the polydisulfide shown in formula (II).

[0030] In the above ring-opening polymerization reaction, the organic solvent may be selected from one or more of chloroform, dichloromethane, tetrahydrofuran, and toluene; the initiator may be selected from one or more of benzyl mercaptan, dodecyl mercaptan, and p-methoxythiophenol; the base may be selected from one or more of tetramethylguanidine, tert-butylimino-tris(dimethylamino)phosphine, and tetrahydropyrrole; and the quencher may be selected from one or more of methyl acrylate, m-chlorophenyl isocyanate, and trifluoroacetic acid.

[0031] In the ring-opening polymerization reaction, the molar concentration of the 4-aryl-1,2-dithiocyclopentane monomer compound shown in formula (I) in the organic solvent is preferably 2.5 to 3.0 mol / L; the molar ratio of the 4-aryl-1,2-dithiocyclopentane monomer compound shown in formula (I) to the initiator, base and quencher is preferably 400:1:1:40 to 1000:1:1:40.

[0032] The above ring-opening polymerization reaction was carried out at a temperature of -78°C to room temperature, and the reaction time was 20 to 60 minutes.

[0033] In a fifth aspect of the present invention, a method for preparing a photocurable resin using the 4-aryl-1,2-dithiocyclopentane monomer shown in formula (I) above and a crosslinking agent is provided, as follows:

[0034] After mixing the 4-aryl-1,2-dithiocyclopentane monomer shown in formula (Ⅰ) with the crosslinking monomer, stir until completely mixed, pour into a polytetrafluoroethylene mold, evacuate, and irradiate with 365nm light until completely cured.

[0035] In the above photocuring reaction, the crosslinking agent can be selected from one or more of bis(dithiopentane) or poly(dithiopentane) compounds such as PEG4Lp2, IsoLp2 and GlyLp3.

[0036]

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] (1) This invention introduces phenyl into 1,2-dithiocyclopentane monomer for the first time. The introduction of phenyl expands the monomer library of polydisulfides and broadens their application prospects.

[0039] (2) The monomer preparation reaction conditions in this invention are mild, the operation is simple, and the product purification process is convenient, saving time and resource costs, and enabling large-scale preparation.

[0040] (3) The polydisulfide in this invention has a thermal stability of up to 219°C, a glass transition temperature of up to 40.3°C, a refractive index of up to 1.65, and an Abbe number of up to 41.6 due to the influence of the side chain phenyl group; moreover, it has good depolymerization performance and is easy to recycle.

[0041] (4) The crosslinked material prepared in this invention has excellent mechanical properties, with a maximum tensile strength of up to 40 MPa and a maximum Young's modulus of up to 0.9 GPa, which is higher than that of similar photocurable resins based on disulfides.

[0042] (5) The present invention uses allylbenzene derivatives as reaction raw materials, especially allylbenzene ether substrates, which are natural products such as piperine and artemisia argyi and their derivatives. The raw materials are green, low in toxicity and low in cost. Attached Figure Description

[0043] Figure 1 The general structural formula of the 4-aryl-1,2-dithiocyclopentane monomer of the present invention is shown below.

[0044] Figure 2 The above is the 1H NMR spectrum of monomer M1 in Example 8 of this invention;

[0045] Figure 3 The carbon NMR spectrum of monomer M1 in Example 8 of this invention;

[0046] Figure 4 The 1H NMR spectrum of the P(M1) polymer in Example 17 of this invention;

[0047] Figure 5 The results of thermogravimetric analysis (TGA) of the polymers in Examples 17–24 of this invention are shown.

[0048] Figure 6 The results of differential scanning calorimetry (DSC) tests on the polymers in Examples 17–24 of this invention are shown.

[0049] Figure 7 The refractive index test results of the polymers in Examples 17–24 of this invention are shown below.

[0050] Figure 8 The stress-strain test results (a) of the M1-IsoLp2 monomer crosslinker in Example 25 of the present invention and the comparison (b) of its ultimate tensile strength (UTS) and Young's modulus (E) with other crosslinked polydisulfides;

[0051] Figure 9 The above are the 1H NMR spectra of the P(M1) polymer before and after depolymerization in Example 26 of this invention;

[0052] Figure 10 This is a depolymerization kinetic diagram of P(M1) polymer in Example 26 of the present invention, wherein (a) shows the change in conversion rate during the depolymerization of P(M1); (b) shows the change in molecular weight and its distribution during the depolymerization of P(M1), and the inset shows the change in gel size exclusion chromatography curve during the depolymerization of P(M1). Detailed Implementation

[0053] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0054] Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art; unless otherwise specified, the reagents used in the embodiments are all commercially available.

[0055] Example 1

[0056]

[0057] 4-Allylphenol (134.2 mg, 1.0 mmol, 1.0 equiv.) was added to a 5 mL round-bottom flask and dissolved in acetonitrile (2.0 mL). Then, bromoethane (109.0 mg, 1.0 mmol, 1.0 equiv.) and potassium carbonate (138.2 mg, 1.0 mmol, 1.0 equiv.) were added. The reaction was stirred at 80 °C for 12 h. After the reaction was complete, insoluble matter was removed by filtration, and the yield was determined to be 63% by GC-MS.

[0058] Example 2

[0059]

[0060] 4-Allylphenol (134.2 mg, 1.0 mmol, 1.0 equiv.) was added to a 5 mL round-bottom flask and dissolved in acetonitrile (2.0 mL). Then, bromopropane (123.0 mg, 1.0 mmol, 1.0 equiv.) and potassium carbonate (138.2 mg, 1.0 mmol, 1.0 equiv.) were added. The reaction was stirred at 80 °C for 12 h. After the reaction was complete, insoluble matter was removed by filtration, and the yield was determined to be 62% by GC-MS.

[0061] Example 3

[0062]

[0063] 4-Allylphenol (134.2 mg, 1.0 mmol, 1.0 equiv.) was added to a 5 mL round-bottom flask and dissolved in acetonitrile (2.0 mL). Then, bromobutane (137.0 mg, 1.0 mmol, 1.0 equiv.) and potassium carbonate (138.2 mg, 1.0 mmol, 1.0 equiv.) were added. The reaction was stirred at 80 °C for 12 h. After the reaction was complete, insoluble matter was removed by filtration, and the yield was determined to be 72% by GC-MS.

[0064] Example 4

[0065]

[0066] 4-Allylphenol (134.2 mg, 1.0 mmol, 1.0 equiv.) was added to a 5 mL round-bottom flask and dissolved in acetonitrile (2.0 mL). Then, bromopentane (151.0 mg, 1.0 mmol, 1.0 equiv.) and potassium carbonate (138.2 mg, 1.0 mmol, 1.0 equiv.) were added. The reaction was stirred at 80 °C for 12 h. After the reaction was complete, insoluble matter was removed by filtration, and the yield was determined to be 78% by GC-MS.

[0067] Example 5

[0068]

[0069] 4-Allylphenol (134.2 mg, 1.0 mmol, 1.0 equiv.) was added to a 5 mL round-bottom flask and dissolved in acetonitrile (2.0 mL). Then, hexane (165.1 mg, 1.0 mmol, 1.0 equiv.) and potassium carbonate (138.2 mg, 1.0 mmol, 1.0 equiv.) were added. The reaction was stirred at 80 °C for 12 h. After the reaction was complete, insoluble matter was removed by filtration, and the yield was determined to be 58% by GC-MS.

[0070] Example 6

[0071]

[0072] 4-Allylphenol (134.2 mg, 1.0 mmol, 1.0 equiv.) was dissolved in cyclohexene (1.0 mL) in a 5 mL round-bottom flask, followed by boron trifluoride diethyl ether (71.0 mg, 0.5 mmol, 0.5 equiv.). The reaction was stirred at 85 °C for 22 h. After the reaction was complete, water was added, and the mixture was extracted with ethyl acetate. The yield was determined to be 42% by GC-MS.

[0073] Example 7

[0074]

[0075] 4-Allylphenol (134.2 mg, 1.0 mmol, 1.0 equiv.) was dissolved in dichloromethane (1.0 mL) in a 5 mL round-bottom flask, followed by di-tert-butyl dicarbonate (502.0 mg, 2.3 mmol, 2.3 equiv.) and magnesium perchlorate (22.3 mg, 0.1 mmol, 0.1 equiv.). The reaction was stirred at 50 °C for 19 h. After the reaction was complete, water was added, and the mixture was extracted with ethyl acetate. The yield was determined to be 68% by GC-MS.

[0076] Example 8

[0077]

[0078] In a 50 mL round-bottom flask, 1.48 g of allyl anisole (10.0 mmol, 1.0 equiv.) was dissolved in 20 mL of 1,2-dichloroethane. Zinc bromide (2.25 g, 10.0 mmol, 1.0 equiv.) and N-bromosuccinimide (2.14 g, 12.0 mmol, 1.2 equiv.) were then added. The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (3.43 g, 30.0 mmol, 3.0 equiv.) and dimethyl sulfoxide (50 mL) were then added to the reaction flask. The mixture was stirred at room temperature for 2 h, and then potassium carbonate (276.4 mg, 2.0 mmol, 0.2 eq.) and methanol (50 mL) were added. The mixture was refluxed at 80 °C and stirred for 16 h. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation and separated by column chromatography to yield monomer M1 (1.01 g, 4.76 mmol, 48%). The dried polymer was then analyzed by nuclear magnetic resonance. 1 H NMR spectrum and 13 C NMR such as Figure 2 and Figure 3 As shown. 1 H NMR (400MHz, CDCl3) δ = 7.23 (d, J = 8.7Hz, 2H), 6.87 (d, J = 8.7Hz, 2H), 3.80 (s, 3H), 3.63(d,J=7.4Hz,1H), 3.48(dd,J=11.2,7.0Hz,2H), 3.18(dd,J=11.2,7.9Hz,2H). 13 C NMR (101MHz, CDCl3) δ = 158.82, 133.33, 128.31, 114.24, 55.34, 52.53, 45.86.

[0079] Example 9

[0080]

[0081] In a 1000 mL round-bottom flask, allyl phenyl tert-butyl ether (100 g, 675 mmol, 1.0 equiv.) was added and dissolved in 1,2-dichloroethane (675 mL). Zinc bromide (152 g, 675 mmol, 1.0 equiv.) and N-bromosuccinimide (144 g, 809 mmol, 1.2 equiv.) were then added. The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (231 g, 2024 mmol, 3.0 equiv.) and dimethyl sulfoxide (300 mL) were then added to the reaction flask. The mixture was stirred at room temperature for 2 h, followed by the addition of potassium carbonate (46 g, 337 mmol, 0.5 eq.) and methanol (400 mL). The mixture was then refluxed at 80 °C and stirred for 16 h. The reaction was cooled to room temperature, saturated ammonium chloride aqueous solution was added, and the product was extracted with ethyl acetate. The crude product was obtained by rotary evaporation, and the fraction collected at 140-150℃ (0.5 Torr) was obtained by vacuum distillation to give monomer M1 (284.4 mg, 1.12 mmol, 38%).

[0082] Example 10

[0083]

[0084] In a 50 mL round-bottom flask, allyl phenethyl ether (1.23 g, 7.58 mmol, 1.0 equiv.) was dissolved in 1,2-dichloroethane (15 mL), followed by zinc bromide (1.71 g, 7.58 mmol, 1.0 equiv.) and N-bromosuccinimide (1.62 g, 9.10 mmol, 1.2 equiv.). The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (2.60 g, 22.7 mmol, 3.0 equiv.) and dimethyl sulfoxide (40 mL) were then added to the reaction flask, and the mixture was stirred at room temperature for 2 h. Potassium carbonate (523.8 mg, 3.79 mmol, 0.5 eq.) and methanol (40 mL) were then added, and the mixture was refluxed at 80 °C for 16 h. The reaction was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation and separated by column chromatography to obtain monomer M2 (916.8 mg, 4.05 mmol, 53%). 1 H NMR (400MHz, CDCl3) δ=7.24–7.18(m,2H),6.89–6.83(m,2H),4.02(q,J=7.0Hz,2H),3.63(p,J= 7.6Hz, 1H), 3.48 (dd, J=11.1, 7.0Hz, 2H), 3.18 (dd, J=11.2, 8.0Hz, 2H), 1.41 (t, J=7.0Hz, 3H).

[0085] Example 11

[0086]

[0087] In a 50 mL round-bottom flask, allyl phenyl propyl ether (1.59 g, 9.0 mmol, 1.0 equiv.) was dissolved in 1,2-dichloroethane (18 mL), followed by zinc bromide (2.03 g, 9.0 mmol, 1.0 equiv.) and N-bromosuccinimide (1.92 g, 10.8 mmol, 1.2 equiv.). The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (3.08 g, 27.0 mmol, 3.0 equiv.) and dimethyl sulfoxide (45 mL) were then added to the reaction flask, and the mixture was stirred at room temperature for 2 h. Potassium carbonate (621 mg, 4.5 mmol, 0.5 eq.) and methanol (45 mL) were then added, and the mixture was refluxed at 80 °C for 16 h. The reaction was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation and separated by column chromatography to obtain monomer M3 (1.05 g, 4.37 mmol, 48%). 1 H NMR (400MHz, CDCl3) δ=7.30–7.23(m,2H),6.96–6.89(m,2H),3.96(t,J=6.5Hz,2H),3.69(p,J=7.5Hz,1H) ,3.54(dd,J=11.2,7.0Hz,2H), 3.23(dd,J=11.2,8.0Hz,2H), 1.86(h,J=7.1Hz,2H), 1.09(t,J=7.4Hz,3H).

[0088] Example 12

[0089]

[0090] In a 50 mL round-bottom flask, allyl phenylbutyl ether (1.39 g, 7.3 mmol, 1.0 equiv.) was added and dissolved in 1,2-dichloroethane (15 mL). Zinc bromide (1.64 g, 7.3 mmol, 1.0 equiv.) and N-bromosuccinimide (1.56 g, 8.76 mmol, 1.2 equiv.) were then added. The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (2.50 g, 21.9 mmol, 3.0 equiv.) and dimethyl sulfoxide (40 mL) were then added to the reaction flask. The mixture was stirred at room temperature for 2 h, and then potassium carbonate (504 mg, 3.65 mmol, 0.5 eq.) and methanol (40 mL) were added. The mixture was refluxed at 80 °C and stirred for 16 h. The reaction was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation and separated by column chromatography to obtain monomer M4 (1.22 g, 4.78 mmol, 65%). 1 H NMR (400MHz, CDCl3) δ = 7.24–7.18 (m, 2H), 6.90– 6.81(m,2H),3.95(t,J=6.5Hz,2H),3.63(p,J=7.5Hz,1H),3.48(dd,J=11.2,7.0Hz,2H ),3.18(dd,J=11.2,8.0Hz,2H),1.82–1.70(m,2H),1.55–1.43(m,2H),0.97(t,J=7.4Hz,3H).

[0091] Example 13

[0092]

[0093] In a 50 mL round-bottom flask, allyl phenylpentyl ether (3.59 g, 17.6 mmol, 1.0 equiv.) was added and dissolved in 1,2-dichloroethane (40 mL). Zinc bromide (3.96 g, 17.6 mmol, 1.0 equiv.) and N-bromosuccinimide (3.75 g, 21.1 mmol, 1.2 equiv.) were then added. The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (6.02 g, 52.7 mmol, 3.0 equiv.) and dimethyl sulfoxide (100 mL) were then added to the reaction flask. The mixture was stirred at room temperature for 2 h, and then potassium carbonate (1.21 g, 8.79 mmol, 0.5 eq.) and methanol (100 mL) were added. The mixture was refluxed at 80 °C and stirred for 16 h. The reaction was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation and separated by column chromatography to obtain monomer M5 (2.17 g, 8.09 mmol, 46%). 1H NMR (400MHz, CDCl3) δ=7.24–7.18(m,2H),6.89–6.82(m,2H),3.94(t,J=6.6Hz,2H),3.68–3.59(m,1H),3.48(dd,J=1 1.2,7.0Hz,2H),3.18(dd,J=11.2,8.0Hz,2H),1.78(dq,J=8.0,6.5Hz,2H),1.50–1.31(m,4H),0.93(t,J=7.1Hz,3H).

[0094] Example 14

[0095]

[0096] In a 50 mL round-bottom flask, allyl phenylhexane (1.65 g, 7.58 mmol, 1.0 equiv.) was dissolved in 1,2-dichloroethane (17 mL), followed by zinc bromide (1.71 g, 7.58 mmol, 1.0 equiv.) and N-bromosuccinimide (1.62 g, 9.10 mmol, 1.2 equiv.). The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (2.60 g, 22.7 mmol, 3.0 equiv.) and dimethyl sulfoxide (40 mL) were then added to the reaction flask, and the mixture was stirred at room temperature for 2 h. Potassium carbonate (523 mg, 3.79 mmol, 0.5 eq.) and methanol (40 mL) were then added, and the mixture was refluxed at 80 °C for 16 h. The reaction was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation and separated by column chromatography to obtain monomer M6 (837.6 mg, 2.97 mmol, 39%). 1 H NMR (400MHz, CDCl3) δ=7.24–7.18(m,2H),6.89–6.83(m,2H),3.94(t,J=6.5Hz,2H),3.63(p,J=7.5Hz,1H),3.48(dd,J=11.2,7.0 Hz,2H),3.18(dd,J=11.2,8.0Hz,2H),1.77(p,J=6.7Hz,2H),1.51–1.40(m,2H),1.40–1.29(m,4H),0.90(td,J=5.8,3.2Hz,3H).

[0097] Example 15

[0098]

[0099] In a 50 mL round-bottom flask, allyl phenylcyclohexyl ether (2.53 g, 11.7 mmol, 1.0 equiv.) was added and dissolved in 1,2-dichloroethane (25 mL). Zinc bromide (2.63 g, 11.7 mmol, 1.0 equiv.) and N-bromosuccinimide (2.50 g, 14.0 mmol, 1.2 equiv.) were then added. The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (4.01 g, 35.1 mmol, 3.0 equiv.) and dimethyl sulfoxide (63 mL) were then added to the reaction flask. The mixture was stirred at room temperature for 2 h, and then potassium carbonate (1.62 g, 11.7 mmol, 1.0 eq.) and methanol (63 mL) were added. The mixture was refluxed at 80 °C and stirred for 16 h. The reaction was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation and separated by column chromatography to obtain monomer M6C (284.4 mg, 1.12 mmol, 38%). 1 H NMR (400MHz, CDCl3) δ=7.23–7.16(m,2H),6.89–6.83(m,2H),4.21(td,J=8.9,4.5Hz,1H),3.62(p,J=7.6Hz,1H),3.48(dd,J= 11.2,7.0Hz,2H),3.17(dd,J=11.2,8.0Hz,2H),2.02–1.92(m,2H),1.86–1.76(m,2H),1.63–1.44(m,3H),1.43–1.27(m,3H).

[0100] Example 16

[0101]

[0102] In a 50 mL round-bottom flask, allyl phenyl tert-butyl ether (565.1 mg, 3.0 mmol, 1.0 equiv.) was added and dissolved in 1,2-dichloroethane (6 mL). Zinc bromide (675.6 mg, 3.0 mmol, 1.0 equiv.) and N-bromosuccinimide (640.8 mg, 3.6 mmol, 1.2 equiv.) were then added. The reaction was stirred at room temperature for 16 h. After the reaction was complete, the insoluble matter was removed by filtration, and 1,2-dichloroethane was removed by rotary evaporation. Potassium thioacetate (1.02 g, 9.0 mmol, 3.0 equiv.) and dimethyl sulfoxide (15 mL) were then added to the reaction flask. The mixture was stirred at room temperature for 2 h, and then potassium carbonate (205.2 mg, 1.5 mmol, 0.5 eq.) and methanol (15 mL) were added. The mixture was refluxed at 80 °C and stirred for 16 h. The reaction was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The crude product was obtained by rotary evaporation and separated by column chromatography to obtain monomer M4T (284.4 mg, 1.12 mmol, 38%). 1 H NMR(400MHz, CDCl3)δ=7.21–7.16(m,2H),6.97–6.91(m,2H),3.68–3.59(m,1 H), 3.50 (dd, J=11.1, 7.0Hz, 2H), 3.19 (dd, J=11.3, 8.0Hz, 2H), 1.34 (s, 9H).

[0103] Example 17

[0104]

[0105] A chloroform solution (162 μL) containing 170.5 mg of monomer M1 (3.0 M) was added to a 2 mL reaction flask. An 8 μL solution of BnSH / TMG initiator (1:1 ratio) (0.25 M) was added at 0 °C. The reaction was stirred at 0 °C for 30 min, followed by the addition of methyl acrylate (7.3 μL) and shaking for 10 s. The resulting polymer was precipitated three times with acetone and dried in a vacuum oven (35 °C, 1 torr) to remove residual solvent, yielding the pure polymer P(M1).

[0106] The reaction solution obtained in this invention was subjected to 1H NMR spectroscopy, and the results showed that the monomer conversion rate was 77%. 1 HNMR spectrum as follows Figure 4 As shown.

[0107] This invention employs gel permeation chromatography (GPC) to analyze the molecular weight of polymers, using tetrahydrofuran as the mobile phase and polystyrene as the standard to construct a standard curve. The results show that the number-average molecular weight is M... n = 45.6 kDa, Dispersion

[0108] Example 18

[0109]

[0110] A chloroform solution (223 μL) containing 233.5 mg of monomer M2 was added to a 2 mL reaction flask, resulting in a concentration of 3.0 M. A 1:1 toluene solution (10.3 μL) of BnSH / TMG initiator (0.25 M) was added at 0 °C, and the reaction was stirred at 0 °C for 30 min. Then, methyl acrylate (9.3 μL) was added and the mixture was shaken for 10 s. The resulting polymer was precipitated three times with acetone and dried in a vacuum oven (35 °C, 1 torr) to remove residual solvent, yielding the pure polymer P(M2).

[0111] The present invention performs nuclear magnetic resonance hydrogen spectrum detection on the obtained reaction solution, and the results show that the monomer conversion rate is 85%.

[0112] This invention employs gel permeation chromatography (GPC) to analyze the molecular weight of polymers, using tetrahydrofuran as the mobile phase and polystyrene as the standard to construct a standard curve. The results show that the number-average molecular weight is M... n =75kDa, Dispersion

[0113] Example 19

[0114]

[0115] A chloroform solution (229 μL) containing monomer M3 (240.4 mg) was added to a 2 mL reaction flask, resulting in a concentration of 3.0 M. A 1:1 toluene solution (10.0 μL) of BnSH / TMG initiator (0.25 M) was added at 0 °C. The reaction was stirred at 0 °C for 30 min, followed by the addition of methyl acrylate (9.0 μL) and shaking for 10 s. The resulting polymer was precipitated three times with acetone and dried in a vacuum oven (35 °C, 1 torr) to remove residual solvent, yielding the pure polymer P (M3).

[0116] The present invention performs nuclear magnetic resonance hydrogen spectrum detection on the obtained reaction solution, and the results show that the monomer conversion rate is 74%.

[0117] This invention employs gel permeation chromatography (GPC) to analyze the molecular weight of polymers, using tetrahydrofuran as the mobile phase and polystyrene as the standard to construct a standard curve. The results show that the number-average molecular weight is M... n = 40.5kDa, Dispersion

[0118] Example 20

[0119]

[0120] A chloroform solution (241 μL) containing monomer M4 (254.4 mg) was added to a 2 mL reaction flask, resulting in a concentration of 3.0 M. A 1:1 toluene solution (10.0 μL) of BnSH / TMG initiator (0.25 M) was added at 0 °C. The reaction was stirred at 0 °C for 30 min, followed by the addition of methyl acrylate (9.0 μL) and shaking for 10 s. The resulting polymer was precipitated three times with acetone and dried in a vacuum oven (35 °C, 1 torr) to remove residual solvent, yielding pure polymer P (M4).

[0121] The present invention performs nuclear magnetic resonance hydrogen spectrum detection on the obtained reaction solution, and the results show that the monomer conversion rate is 82%.

[0122] This invention employs gel permeation chromatography (GPC) to analyze the molecular weight of polymers, using tetrahydrofuran as the mobile phase and polystyrene as the standard to construct a standard curve. The results show that the number-average molecular weight is M... n =65kDa, Dispersion

[0123] Example 21

[0124]

[0125] A chloroform solution (230 μL) containing 244.6 mg of monomer M5 (3.0 M) was added to a 2 mL reaction flask. A 1:1 toluene solution (10.0 μL) of BnSH / TMG initiator (0.25 M) was added at 0 °C. The reaction was stirred at 0 °C for 30 min, followed by the addition of methyl acrylate (9.0 μL) and shaking for 10 s. The resulting polymer was precipitated three times with acetone and dried in a vacuum oven (35 °C, 1 torr) to remove residual solvent, yielding pure polymer P (M5).

[0126] The present invention performs nuclear magnetic resonance hydrogen spectrum detection on the obtained reaction solution, and the results show that the monomer conversion rate is 74%.

[0127] This invention employs gel permeation chromatography (GPC) to analyze the molecular weight of polymers, using tetrahydrofuran as the mobile phase and polystyrene as the standard to construct a standard curve. The results show that the number-average molecular weight is M... n =53kDa, Dispersion

[0128] Example 22

[0129]

[0130] A chloroform solution (268 μL) containing 282.5 mg of monomer M6 was added to a 2 mL reaction flask, resulting in a concentration of 3.0 M. A 1:1 toluene solution (10.0 μL) of BnSH / TMG initiator (0.25 M) was added at 0 °C, and the reaction was stirred at 0 °C for 30 min. Then, methyl acrylate (9.0 μL) was added and the mixture was shaken for 10 s. The resulting polymer was precipitated three times with acetone and dried in a vacuum oven (35 °C, 1 torr) to remove residual solvent, yielding pure polymer P (M6).

[0131] The present invention performs nuclear magnetic resonance hydrogen spectrum detection on the obtained reaction solution, and the results show that the monomer conversion rate is 82%.

[0132] This invention employs gel permeation chromatography (GPC) to analyze the molecular weight of polymers, using tetrahydrofuran as the mobile phase and polystyrene as the standard to construct a standard curve. The results show that the number-average molecular weight is M... n =53kDa, Dispersion

[0133] Example 23

[0134]

[0135] A chloroform solution (268 μL) containing 280.1 mg of monomer M6C was added to a 2 mL reaction flask, resulting in a concentration of 3.0 M. A 1:1 toluene solution (10.0 μL) of BnSH / TMG initiator (0.25 M) was added at 0 °C, and the reaction was stirred at 0 °C for 30 min. Then, methyl acrylate (9.0 μL) was added and the mixture was shaken for 10 s. The resulting polymer was precipitated three times with acetone and dried in a vacuum oven (35 °C, 1 torr) to remove residual solvent, yielding pure polymer P (M6C).

[0136] The present invention performs nuclear magnetic resonance hydrogen spectrum detection on the obtained reaction solution, and the results show that the monomer conversion rate is 66%.

[0137] This invention employs gel permeation chromatography (GPC) to analyze the molecular weight of polymers, using tetrahydrofuran as the mobile phase and polystyrene as the standard to construct a standard curve. The results show that the number-average molecular weight is M... n =57kDa, Dispersion

[0138] Example 24

[0139]

[0140] A chloroform solution (243 μL) containing 254.1 mg of monomer M4T was added to a 2 mL reaction flask, resulting in a concentration of 3.0 M. A 1:1 toluene solution (10.0 μL) of BnSH / TMG initiator (0.25 M) was added at 0 °C, and the reaction was stirred at 0 °C for 30 min. Then, methyl acrylate (9.0 μL) was added and the mixture was shaken for 10 s. The resulting polymer was precipitated three times with acetone and dried in a vacuum oven (35 °C, 1 torr) to remove residual solvent, yielding pure polymer P(M4T).

[0141] The present invention performs nuclear magnetic resonance hydrogen spectrum detection on the obtained reaction solution, and the results show that the monomer conversion rate is 52%.

[0142] This invention employs gel permeation chromatography (GPC) to analyze the molecular weight of polymers, using tetrahydrofuran as the mobile phase and polystyrene as the standard to construct a standard curve. The results show that the number-average molecular weight is M... n =76kDa, Dispersion

[0143] Performance testing:

[0144] This invention employs thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) to test the thermal decomposition temperature and glass transition temperature of the polymers in Examples 17-24. Figure 5 and Figure 6 As shown, P(M6) has the highest initial decomposition temperature, T d,5％ =219℃, P(M4T) has the highest glass transition temperature, T g =40.3℃. This result indicates that the introduction of phenyl groups improves the thermal stability and glass transition temperature of the polydisulfide.

[0145] This invention uses an ellipsometer to measure the refractive index and Abbe number of the polymers in Examples 17–24. For example... Figure 7 As shown, P(M6C) has the best optical properties, with a refractive index of up to 1.64 and an Abbe number of up to 41.6.

[0146] Example 25

[0147]

[0148] Mix M1 and IsoLp2 monomers in different proportions evenly, pour the mixture into a polytetrafluoroethylene mold, and then irradiate it with 365nm light for 5 hours until it is completely cured.

[0149] Performance testing:

[0150] This invention prepares a dog bone-shaped specimen from a photocrosslinked material and performs uniaxial tensile testing. Its stress-strain curve is shown below. Figure 8As shown in (a), the crosslinked material with a ratio of 30 wt% M1-70 wt% IsoLp2 can achieve a maximum tensile strength of 40 MPa, a Young's modulus of 0.9 GPa, and an elongation at break of 9%. It is a relatively hard and brittle material, and its performance is better than other disulfide crosslinked materials reported to date, and even better than the commercial resin Prusament resin Biobased60 used for 3D printing. It is expected to be used as a recyclable photocrosslinked resin for 3D printing.

[0151] Example 26

[0152]

[0153] Add P(M1) polymer (216.7 mg, 1.02 mmol, 1.0 equiv.) to a 2 mL vial, dissolve in chloroform (1.02 mL), then add a 1:1 toluene solution of BnSH / TMG initiator (40.8 μL, 0.01 equiv.). Stir at room temperature for 1 h. Figure 9 and Figure 10 As shown, the characteristic peaks of the 1H NMR spectrum of the monomer before and after depolymerization are consistent, indicating that the monomer was recovered. Kinetic experiments also show that P(M1) has a fast degradation rate, with an 80% monomer recovery rate achieved in just 10 minutes.

[0154] Example 27

[0155]

[0156] Add P(M2) polymer (226.4 mg, 1.0 mmol, 1.0 equiv.) to a 2 mL vial, dissolve it in tetrahydrofuran (1.0 mL), and then add a 1:1 toluene solution of BnSH / TMG initiator (40.8 μL, 0.01 equiv.). Stir at room temperature for 20 min to achieve a monomer recovery rate of 74.6%.

[0157] Example 28

[0158]

[0159] Add P(M3) polymer (240.4 mg, 1.0 mmol, 1.0 equiv.) to a 2 mL vial, dissolve it in tetrahydrofuran (1.0 mL), and then add a 1:1 toluene solution of BnSH / TMG initiator (40.8 μL, 0.01 equiv.). Stir at room temperature for 20 min to achieve a monomer recovery rate of 87.9%.

[0160] Example 29

[0161]

[0162] Add P(M4) polymer (254.4 mg, 1.0 mmol, 1.0 equiv.) to a 2 mL vial, dissolve it in tetrahydrofuran (1.0 mL), and then add a 1:1 toluene solution of BnSH / TMG initiator (40.8 μL, 0.01 equiv.). Stir at room temperature for 20 min to achieve a monomer recovery rate of 76.0%.

[0163] Example 30

[0164]

[0165] Add P(M5) polymer (268.4 mg, 1.0 mmol, 1.0 equiv.) to a 2 mL vial, dissolve it in tetrahydrofuran (1.0 mL), and then add a 1:1 toluene solution of BnSH / TMG initiator (40.8 μL, 0.01 equiv.). Stir at room temperature for 20 min to achieve a monomer recovery rate of 78.7%.

[0166] Example 31

[0167]

[0168] Add P(M6) polymer (282.5 mg, 1.0 mmol, 1.0 equiv.) to a 2 mL vial, dissolve it in tetrahydrofuran (1.0 mL), and then add a 1:1 toluene solution of BnSH / TMG initiator (40.8 μL, 0.01 equiv.). Stir at room temperature for 20 min to achieve a monomer recovery rate of 66.6%.

[0169] Example 32

[0170]

[0171] Add P(M6C) polymer (280.4 mg, 1.0 mmol, 1.0 equiv.) to a 2 mL vial, dissolve it in tetrahydrofuran (1.0 mL), and then add a 1:1 toluene solution of BnSH / TMG initiator (40.8 μL, 0.01 equiv.). Stir at room temperature for 20 min to achieve a monomer recovery rate of 73.8%.

[0172] Example 33

[0173]

[0174] Add P(M4T) polymer (254.4 mg, 1.0 mmol, 1.0 equiv.) to a 2 mL vial, dissolve it in tetrahydrofuran (1.0 mL), and then add a 1:1 toluene solution of BnSH / TMG initiator (40.8 μL, 0.01 equiv.). Stir at room temperature for 20 min to achieve a monomer recovery rate of 58.1%.

[0175] The above description is only a partial embodiment of the present invention and is not intended to limit the present invention. Any modifications or substitutions made within the spirit and principles of the present invention are included within the scope of protection of the present invention.

Claims

1. A 4-aryl-1,2-dithiocyclopentane monomer, the general structural formula of which is shown in formula (I): in, R represents one or more substituents on the benzene ring, selected from hydrogen, alkyl, aryl, alkoxy, aryloxy, benzyloxy, siloxy, and halogen.

2. The 4-aryl-1,2-dithiocyclopentane monomer as described in claim 1, characterized in that, The alkyl group is a C1-C12 alkyl group, the aryl group is a C6-C12 aryl group or a substituted aryl group, the alkoxy group is a C1-C12 alkoxy group, the aryloxy group is a C6-C12 aryloxy group or a substituted aryloxy group, the siloxy group is a trialkylsiloxy group, and the halogen is selected from fluorine, chlorine, bromine, and iodine.

3. The 4-aryl-1,2-dithiocyclopentane monomer as described in claim 2, characterized in that, R is selected from groups with the following structures:

4. A method for preparing the 4-aryl-1,2-dithiocyclopentane monomer according to any one of claims 1 to 3, comprising the following steps: Step a: Dissolve the allylbenzene derivative in an organic solvent, and add Br at room temperature. + reagents, Br – The reagents and additives were stirred for a period of time, and the insoluble matter was removed by filtration. The solvent was then evaporated to dryness to obtain a mixture of intermediates 1,3-dibromide and 1,2-dibromide. Step b: The mixture of 1,3-dibromide and 1,2-dibromide was dissolved in dimethyl sulfoxide, potassium thioacetate was added and stirred at room temperature for a period of time, and then alkali and alcohol were added and refluxed and stirred for a period of time. After the reaction, the mixture was cooled to room temperature and purified to obtain 4-aryl-substituted 1,2-dithiocyclopentane monomer.

5. The preparation method according to claim 4, characterized in that, The organic solvent mentioned in step a is selected from one or more of 1,2-dichloroethane, dichloromethane, tetrahydrofuran, toluene, and acetone; the Br + The reagent is selected from one or more of N-bromosuccinimide, N-bromophthalimide, and dibromohydantoin; the Br – The reagent is selected from one or more of zinc bromide, lithium bromide, potassium bromide, sodium bromide, magnesium bromide, copper bromide, iron bromide, and tetrabutylammonium bromide; the additive is selected from one or more of trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, 1,3-diphenylurea, 1,3-diphenylthiourea, and 1,3-(3',5'-bistrifluoromethyl)phenylthiourea.

6. A polydisulfide having the general structural formula shown in formula (II): in, n represents the degree of polymerization; R represents one or more substituents on the benzene ring, selected from hydrogen, alkyl, aryl, alkoxy, aryloxy, benzyloxy, siloxy, and halogen.

7. The polydisulfide as described in claim 6, characterized in that, The alkyl group is a C1-C12 alkyl group, the aryl group is a C6-C12 aryl group or a substituted aryl group, the alkoxy group is a C1-C12 alkoxy group, the aryloxy group is a C6-C12 aryloxy group or a substituted aryloxy group, the siloxy group is a trialkylsiloxy group, and the halogen is selected from fluorine, chlorine, bromine, and iodine.

8. The polydisulfide as described in claim 6, characterized in that, R is selected from groups with the following structures:

9. The polydisulfide as described in claim 6, characterized in that, The number-average molecular weight of the polydisulfide is greater than or equal to 3 kDa, and the molecular weight distribution is 1.0 to 2.

0.

10. A method for preparing the polydisulfide according to any one of claims 6 to 9, comprising: The 4-aryl-1,2-dithiocyclopentane monomer shown in formula (I) was dissolved in an organic solvent, and an initiator and a base were added to carry out a ring-opening polymerization reaction. Finally, a quencher was added to obtain the polydisulfide shown in formula (II).

11. The preparation method according to claim 10, characterized in that, The organic solvent is selected from one or more of chloroform, dichloromethane, tetrahydrofuran, and toluene; the initiator is selected from one or more of benzyl mercaptan, dodecyl mercaptan, and p-methoxythiophenol; the base is selected from one or more of tetramethylguanidine, tert-butylimino-tris(dimethylamino)phosphine, and tetrahydropyrrole; and the quencher is selected from one or more of methyl acrylate, m-chlorophenyl isocyanate, and trifluoroacetic acid.

12. A method for preparing a photocurable resin, comprising using the 4-aryl-1,2-dithiocyclopentane monomer according to any one of claims 1 to 3 and a crosslinking agent to prepare the photocurable resin, comprising: After mixing the 4-aryl-1,2-dithiocyclopentane monomer with the crosslinking monomer, stir until completely mixed, pour into a mold, evacuate, and irradiate with 365nm light until completely cured.

13. The method as described in claim 12, characterized in that, The crosslinking monomer is selected from one or more of PEG4Lp2, IsoLp2 and GlyLp3:

14. The crosslinked resin obtained by the method for preparing photocurable resin according to claim 12 or 13.

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