Sulfur-containing polymers, methods for their preparation, and uses thereof

Abstract

This invention provides a sulfur-containing polymer, its preparation method, and its applications. The method involves irradiating a mixture of elemental sulfur and unsaturated organic monomers at room temperature to induce a reverse sulfurization polymerization reaction. The crosslinked network structure of the sulfur-containing polymer can be adjusted by controlling light parameters such as wavelength, power density, and irradiation time. Specifically, this invention controls the power density to be 600-1300 mW / cm². 2 Irradiation time ≥2h effectively improves the photoinitiation efficiency of room temperature photoinduced reverse sulfurization polymerization, significantly shortens the reaction time, and enables efficient production of sulfur-containing polymers with adjustable crosslinking degree, gel content, swelling ratio, and glass transition temperature under mild conditions. This method overcomes the problems of low initiation efficiency and long reaction time in existing room temperature photoinduced reverse sulfurization technologies, and combines the dual advantages of low energy consumption and high preparation efficiency.

Description

Technical Field

[0001] This invention belongs to the field of photoinitiated polymerization technology, specifically relating to a sulfur-containing polymer and its preparation method. Background Technology

[0002] Elemental sulfur is a significant byproduct of petroleum refining and natural gas desulfurization, with a huge output but relatively limited utilization. Long-term stockpiling not only wastes resources but also puts pressure on the environment and storage. Reverse sulfurization polymerization provides an effective way to convert elemental sulfur into high-value products. Sulfur-containing polymers obtained through reverse sulfurization typically possess significant characteristics such as high sulfur content, dynamic sulfur-sulfur bonds, redox activity, and low solubility, thus showing broad application prospects in fields such as lithium-sulfur batteries, high-refractive-index optical materials, adsorption separation, and functional polymer materials.

[0003] Currently, the main method for reverse sulfur polymerization is still the thermally induced pathway, which typically requires high reaction temperatures. Overall, existing thermally induced methods generally suffer from technical drawbacks such as high energy consumption, long reaction cycles, and limited applicability to low-boiling-point monomers.

[0004] To overcome the limitations of high-temperature conditions, existing technologies have proposed methods for preparing sulfur-containing polymers using photo-induced reverse vulcanization at room temperature, demonstrating the feasibility of room-temperature photo-induced reverse vulcanization. However, current room-temperature photo-induced reverse vulcanization technologies generally suffer from low photoinitiation efficiency, resulting in limited polymerization rates and prolonged reaction times. Excessively low initiation efficiency not only prolongs the preparation cycle but may also affect the crosslinking integrity and performance stability of the product due to incomplete reaction. Therefore, how to effectively improve the photoinitiation efficiency and shorten the reaction time of room-temperature photo-induced reverse vulcanization polymerization remains a pressing technical problem to be solved in this field. Summary of the Invention

[0005] To address the technical problems of low photoinitiation efficiency and long reaction cycle in existing room temperature photo-induced reverse sulfurization polymerization technology, this invention provides a method for preparing sulfur-containing polymers by photoinitiated polymerization, comprising the following steps: A mixed system containing elemental sulfur and unsaturated organic monomers is exposed to light at room temperature to cause the elemental sulfur and the unsaturated organic monomers to undergo a reverse sulfurization polymerization reaction, resulting in a sulfur-containing polymer. The crosslinked network structure of the sulfur-containing polymer is adjusted by regulating the illumination parameters, wherein the illumination parameters include illumination wavelength, light power density, and irradiation time; the illumination wavelength is 350-500 nm, and the light power density is 600-1300 mW / cm². 2 The irradiation duration is ≥2h.

[0006] Furthermore, adjusting the crosslinking network structure of the sulfur-containing polymer includes adjusting at least one of the following: the degree of crosslinking, gel content, glass transition temperature, swelling ratio, and solubility of the sulfur-containing polymer.

[0007] Furthermore, the illumination wavelength is 420-500nm, and the optical power density is 700-1200mW / cm². 2 The irradiation duration is ≥5.5h.

[0008] Furthermore, the illumination wavelength is 420-500nm, and the optical power density is 750-950mW / cm². 2 Or 1100-1200mW / cm 2 The irradiation duration is ≥7h.

[0009] Furthermore, the unsaturated organic monomers include organic monomers containing carbon-carbon double bonds and / or carbon-carbon triple bonds.

[0010] Furthermore, the unsaturated organic monomer includes at least one of 1,3-diisopropenylbenzene, norbornene monomers, and unsaturated vegetable oils.

[0011] Furthermore, the mass ratio of elemental sulfur to the unsaturated organic monomer is 1:0.5-2.

[0012] This invention provides a sulfur-containing polymer prepared by any of the preparation methods described above.

[0013] Furthermore, the glass transition temperature is > -10℃ and the gel content is > 40%.

[0014] This invention provides an application of the sulfur-containing polymer as described above in lithium-sulfur batteries, high-refractive-index optical materials, adsorption separation, and the preparation of functional polymer materials.

[0015] Compared with the prior art, the present invention has at least the following advantages: This invention provides a method for preparing sulfur-containing polymers by photoinitiated polymerization, wherein a mixture of elemental sulfur and unsaturated organic monomers is irradiated at room temperature, with the irradiation wavelength controlled at 350-500 nm and the light power density controlled at 600-1300 mW / cm². 2 Within this optical power density range, the illumination provides a sufficiently high photon flux, effectively increasing the concentration of active free radicals generated by ring-opening of elemental sulfur, thereby significantly improving photoinitiation efficiency and accelerating the rate of reverse sulfurization polymerization. This allows the reaction to reach sufficient crosslinking within ≥2 hours at room temperature. Compared to existing room-temperature photoinduced reverse sulfurization methods, which suffer from low initiation efficiency and long reaction times, this invention achieves efficient initiation and short-time preparation under mild conditions, combining the advantages of low energy consumption and high preparation efficiency. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0017] Figure 1 The image shows the infrared full spectrum of the room temperature light-induced reverse sulfurization polymerization products under different light wavelengths in Example 1 of this invention. Figure 2 This is a magnified infrared spectrum of the room-temperature light-induced reverse sulfurization polymerization products under different light wavelengths in Example 1 of the present invention. Figure 3 This is a graph showing the changes in gel content and solubility of the sulfur-containing polymer obtained under different light wavelengths in Example 1 of the present invention; Figure 4 The infrared full spectrum of the room temperature light-induced reverse sulfurization polymerization products under different irradiation durations in Example 2 of the present invention; Figure 5 This is a magnified infrared spectrum of the room temperature light-induced reverse sulfurization polymerization products under different irradiation durations in Example 2 of the present invention. Figure 6 This is a graph showing the glass transition temperature changes of the sulfur-containing polymers obtained under different irradiation durations in Example 2 of the present invention; Figure 7 This is a graph showing the changes in gel content and swelling ratio of the sulfur-containing polymers obtained under different light power densities in Example 3 of the present invention; Figure 8 This is a graph showing the glass transition temperature changes of the sulfur-containing polymers obtained under different light power densities in Example 3 of the present invention. Detailed Implementation The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Furthermore, the technical solutions of the various embodiments of the present invention can be combined with each other, but only if they are based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0019] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention, as well as the prior art known to those skilled in the art and the description of the invention, may be implemented using any prior art methods, devices, and materials similar to or equivalent to the methods, devices, and materials in the embodiments of the present invention.

[0020] This invention provides a method for preparing sulfur-containing polymers by photoinitiated polymerization, comprising the following steps: A mixture containing elemental sulfur and unsaturated organic monomers is exposed to light at room temperature to induce a reverse sulfurization polymerization reaction between the elemental sulfur and the unsaturated organic monomers, yielding a sulfur-containing polymer.

[0021] Existing room-temperature photoinduced reverse vulcanization methods primarily focus on achieving the polymerization reaction itself under mild conditions, lacking systematic methods for controlling the effects of light wavelength, light power density, and irradiation time on the polymer crosslinking network structure and final properties. In particular, current technologies have not yet solved the problem of how to control the degree of crosslinking, gel content, glass transition temperature, swelling ratio, and solubility of the polymer through light parameters, thereby obtaining sulfur-containing polymers with controllable network structure and properties.

[0022] Therefore, in the room temperature light-induced reverse sulfurization polymerization method of the present invention, in order to achieve systematic control of the crosslinking network structure of sulfur-containing polymers, the present invention sets a series of quantifiable result indicators and establishes the structure-property relationship between the light irradiation process parameters and the result indicators.

[0023] The results indicators include: the degree of crosslinking of sulfur-containing polymers, gel content, solubility, swelling ratio, and glass transition temperature (T). g Among them, the degree of crosslinking reflects the density of crosslinking points in the polymer network structure; gel content characterizes the mass fraction of the crosslinked network portion that is insoluble in organic solvents in the total polymer; swelling ratio reflects the swelling capacity of the crosslinked network in solvents, and is negatively correlated with the crosslinking density, with higher crosslinking density resulting in a lower swelling ratio; glass transition temperature reflects the mobility of polymer chain segments and network rigidity; solubility characterizes the proportion of linear segments or oligomers in the polymer that can be dissolved in organic solvents, and is negatively correlated with the crosslinking density, with higher crosslinking density and denser network resulting in lower solubility, and the sum of solubility and gel content is 100%.

[0024] The illumination process parameters include: illumination wavelength, light power density, and irradiation time. This invention establishes a quantitative structure-property relationship between the above illumination parameters and the crosslinked network structure and material properties of sulfur-containing polymers. By precisely controlling the illumination parameters, sulfur-containing polymers with controllable crosslinking degree, gel content, glass transition temperature, and swelling ratio can be actively designed and obtained. The influence mechanism of the above parameters on the results is as follows: The wavelength of light determines the energy level of the photons and the degree of spectral matching with the elemental sulfur-monomer system. Within the preferred wavelength range of this invention, the photon energy is sufficient to efficiently initiate homolytic cleavage of sulfur-sulfur bonds, generating a high concentration of sulfur free radicals, thereby accelerating the polymerization initiation rate and affecting the final degree of crosslinking and gel content.

[0025] The optical power density determines the number of photons reaching the reaction system per unit area per unit time. Within the optical power density range defined in this invention, increasing the optical power density can increase the generation rate and steady-state concentration of active free radicals, thereby increasing the polymerization reaction rate and crosslinking density, resulting in a corresponding increase in the gel content and glass transition temperature of the obtained sulfur-containing polymer, and a corresponding decrease in the swelling ratio.

[0026] Irradiation time has a dual nature in this invention. As a result indicator, the length of irradiation time directly reflects the preparation cycle required for the polymerization reaction to reach the target degree of crosslinking, and is an important benchmark for measuring photoinitiation efficiency and reaction rate. As a process parameter, irradiation time is a key controllable variable that determines the reaction endpoint and the final state of the crosslinked network. When irradiation time is used as a parameter, its endpoint is determined according to the performance requirements of the target polymer: for example, the endpoint can be determined by the monomer conversion rate reaching a basic level and the crosslinked network basically set; at the same time, the reaction can be terminated at the irradiation time point when the corresponding parameter index is reached, based on the specific target value of the glass transition temperature of the product in the actual application, thereby obtaining a sulfur-containing polymer with a controllable network structure.

[0027] In this invention, the gel content and swelling ratio were measured using N,N-dimethylformamide (DMF) as the test solvent, after continuous extraction using the Soxhlet extraction method for 24 hours; the glass transition temperature (T) was also measured. g The double bond conversion rate was determined using differential scanning calorimetry (DSC) in a nitrogen inert atmosphere at a heating rate of 10 °C / min, within a temperature range of -80 °C to 150 °C. The double bond conversion rate was characterized by Fourier transform infrared spectroscopy (FT-IR) at 1640 cm⁻¹. -1 Qualitative determination based on the intensity change of the characteristic absorption peak at the C=C double bond.

[0028] In some embodiments, the present invention controls the illumination wavelength to be 350-500 nm and the optical power density to be 600-1300 mW / cm². 2The irradiation duration is ≥2 hours. The basic controllable construction of a photo-induced reverse vulcanization polymer crosslinking network is achieved at room temperature. Room temperature reverse vulcanization polymerization is stably initiated, and an effective crosslinking network can be formed across the entire range. Compared to the problems of fewer side reactions in short wavelength (<300nm) and low initiation efficiency in long wavelength (>500nm), the polymerization conversion rate is stable in this range, meeting the molding requirements of basic sulfur-containing polymers. The glass transition temperature is greater than -10℃, compared to the unpolymerized mixed system (without a fixed T). g or T g (Extremely low), has formed a polymer chain segment structure with a certain rigidity, realizing the transformation from liquid / low melting point mixture to solid polymer; the gel content has reached the basic level (>40%), and a continuous three-dimensional cross-linked network has been formed, which solves the technical defect of the traditional room temperature reverse sulfur polymerization reaction cycle of 24-72h, shortens the reaction start-up completion time to the lower limit of 2h, provides a basic process window for the structural control of sulfur-containing polymers, and greatly improves the preparation efficiency and reduces energy consumption.

[0029] In some more specific embodiments, the present invention controls the illumination wavelength to be 420-500 nm (more specifically, the illumination wavelength can also be 420-480 nm or 420-500 nm), and the optical power density to be 700-1200 mW / cm². 2 The irradiation duration is ≥5.5h. This achieves precise densification control of the cross-linked network, improves the efficiency of the sulfurization polymerization reaction, significantly enhances the double bond conversion rate, and results in a more complete polymerization reaction (1640 cm⁻¹). -1 (The absorption peak of the C=C double bond is significantly weakened); the gel content is >80%, that is, the density of the cross-linked network is significantly optimized, the structural stability of the product is improved; the glass transition temperature is greater than 45℃.

[0030] In some more specific embodiments, the present invention controls the illumination wavelength to be 420-500 nm (more specifically, the illumination wavelength can also be 420-480 nm or 420-500 nm), and the optical power density to be 750-950 mW / cm². 2 Or 1100-1200mW / cm 2 The irradiation time is ≥7h. The efficiency of the sulfurization polymerization reaction is improved, the double bond conversion rate is significantly increased, and the polymerization reaction is more complete; the gel content is >90%, meaning the cross-linking network density is significantly optimized, and the product structural stability is improved; the glass transition temperature is greater than 50℃.

[0031] In some more specific embodiments, the present invention controls the illumination wavelength to be 420-500 nm (more specifically, the illumination wavelength can also be 420-480 nm or 420-500 nm), and the optical power density to be 750-950 mW / cm². 2The irradiation time is ≥7h. The efficiency of the sulfurization polymerization reaction is improved, the double bond conversion rate is significantly increased, and the polymerization reaction is more complete; the gel content is >90%, that is, the density of the cross-linked network is significantly optimized, and the structural stability of the product is improved; the glass transition temperature is greater than 70℃, and the swelling ratio is less than 20%.

[0032] For example, the illumination wavelength can be 350nm, 380nm, 400nm, 420nm, 435nm, 450nm, 480nm, 500nm, and any value between 350nm and 500nm, or a range of any two values; the optical power density can be 600mW / cm². 2 700mW / cm 2 750mW / cm 2 800mW / cm 2 900mW / cm 2 950mW / cm 2 1000mW / cm 2 1200mW / cm 2 1300mW / cm 2 and 600mW / cm 2 With 1300mW / cm 2 The irradiation duration can be any value between 2h, 4h, 5h, 5.5h, 6h, 7h, 8h, and any value not less than 2h, or any range of two values.

[0033] In some embodiments, the unsaturated organic monomer includes organic monomers containing carbon-carbon double bonds and / or carbon-carbon triple bonds.

[0034] In some embodiments, the unsaturated organic monomer includes at least one of 1,3-diisopropenylbenzene, norbornene monomers, and unsaturated vegetable oils.

[0035] In some embodiments, the mass ratio of elemental sulfur to the unsaturated organic monomer is 1:0.5-2.

[0036] In some embodiments, the method for preparing sulfur-containing polymers by photoinitiated polymerization according to the present invention is carried out entirely at room temperature under inert gas protection, without heating or the addition of catalysts or solvents. The specific operation steps and key control details are as follows: S1. Raw material weighing and mixing: Weigh elemental sulfur and organic monomers containing unsaturated bonds according to a preset mass ratio. The elemental sulfur can be industrial-grade sublimed sulfur, and the unsaturated organic monomers can be monomers containing carbon-carbon double / triple bonds (including but not limited to 1,3-diisopropenylbenzene, norbornene monomers, and unsaturated vegetable oils). Add both directly to a quartz photoreaction tube and gently shake or stir at room temperature until they are evenly mixed. No grinding or pre-dissolving heating is required to avoid monomer volatilization or side reactions caused by high temperature.

[0037] S2. Reaction Atmosphere Protection: Seal the photoreaction tube containing the mixed system, evacuate it, and then introduce an inert gas (nitrogen / argon). Repeat this process three times to completely remove air and oxygen from the system, preventing the oxidation of sulfur and degradation of the polymer during the light exposure. Maintain positive pressure protection with inert gas throughout the process to ensure that the reaction proceeds stably in an oxygen-free environment.

[0038] S3. Photoreaction and Precise Parameter Control: Fix the sealed photoreaction tube in the photochemical reactor, turn on the light source, and adjust the light conditions according to the preset parameters: Illumination wavelength: Precisely controlled at 350-500nm using a narrowband filter / tunable wavelength LED light source to avoid side reactions caused by stray light; Optical power density: calibrated in real time using an optical power meter and controlled to be 600-1300 mW / cm². 2 To ensure a stable input of light energy; Irradiation duration: Timing begins from the moment the light source is turned on, and the irradiation duration is strictly controlled to be ≥2 hours. The reaction time is precisely adjusted according to the requirements of different implementation examples. The entire reaction is maintained at room temperature (20-30℃), requiring no external cooling or heating. The system exhibits no significant temperature rise, making it mild and safe.

[0039] S4. Reaction Termination and Product Collection: After the preset irradiation time is reached, immediately turn off the light source to terminate the reaction; after the reaction system cools naturally to room temperature, open the photoreaction tube and use a scraper to directly remove the solid sulfur-containing polymer. The target product can be obtained without complex post-processing steps such as extraction, precipitation, and washing.

[0040] This invention provides a sulfur-containing polymer prepared by the preparation method described above.

[0041] To facilitate a further understanding of the present invention by those skilled in the art, the following examples are provided: Example 1 Weigh 50.0 mg of elemental sulfur and 50.0 mg of 1,3-diisopropenylbenzene, add them to a 20 ml photoreaction tube and mix thoroughly. Under inert gas protection, conduct reverse sulfurization polymerization reactions at room temperature using light sources with wavelengths of 380 nm, 400 nm, 435 nm, and 450 nm, respectively, for 6 hours, with a light power density of 1200 mW / cm². 2After the reaction was complete, the sulfur-containing polymer was removed using a scraper. The resulting sample was characterized by infrared spectroscopy and gel content testing; the results are shown below. Figure 1 , Figure 2 and Figure 3 .

[0042] in, Figure 1 The infrared full spectrum of the products under different light wavelengths proves that room temperature reverse sulfurization polymerization was successfully initiated at all wavelengths from 380 to 450 nm. Figure 2 These are magnified infrared spectra of the products under different illumination wavelengths, 1640 cm⁻¹. -1 The absorption peak of the C=C double bond gradually weakens with increasing wavelength, and the double bond conversion rate is highest at wavelengths of 435 nm and 450 nm. Figure 3 The graph shows the changes in gel content and solubility of the product under different light wavelengths. The test results of the three solvents, THF, DCM, and DMF, show the same trend. Specifically, when the solvent is DMF, the gel content is 92% at a wavelength of 435nm and 83% at a wavelength of 450nm.

[0043] Example 2 Weigh 50.0 mg of elemental sulfur and 50.0 mg of 1,3-diisopropenylbenzene, add them to a 20 ml photoreaction tube and mix thoroughly. Under inert gas protection and at room temperature, use a wavelength of 435 nm and a power density of 800 mW / cm². 2 Sulfur-containing polymer samples were irradiated with a light source for 2 h, 4 h, 5 h, 6 h, and 7 h, respectively, to obtain samples under different irradiation times. The samples were characterized by infrared spectroscopy, and their glass transition temperatures were measured. The results are shown in the figures below. Figure 4 , Figure 5 and Figure 6 .

[0044] Figure 4 The infrared full spectrum of the products under different irradiation times proves that room temperature reverse sulfurization polymerization was successfully initiated under different irradiation times. Figure 5 The infrared magnified spectra of the products under different irradiation times show that when the irradiation time is >5h, the absorption peak of the C=C double bond basically disappears, and the reaction reaches equilibrium. Figure 6 The graph shows the glass transition temperature variation of the product under different irradiation durations, T g T gradually increases over time, reaching its peak at 6 hours. g It reached a peak temperature of 52.25℃.

[0045] Example 3 Weigh 50.0 mg of elemental sulfur and 50.0 mg of 1,3-diisopropenylbenzene, add them to a 20 ml photoreaction tube and mix thoroughly. Under inert gas protection and at room temperature, use a light source with a wavelength of 435 nm and a wavelength of 800 mW / cm². 2 900mW / cm 2 1000mW / cm 2 and 1200mW / cm 2 Sulfur-containing polymer samples were obtained under different light power densities after irradiation for 8 hours. The gel content, swelling ratio, and glass transition temperature of the obtained samples were tested, and the results are shown in the table below. Figure 7 and Figure 8 .

[0046] Figure 7 The graph shows the changes in gel content and swelling ratio of the product under different light power densities (800-900 mW / cm²). 2 The highest gel content and lowest swelling ratio were observed, with a power ≥1000mW / cm². 2 The network structure subsequently exhibits defects. Specifically, at an optical power density of 800 mW / cm², [the defects occur]. 2 900mW / cm 2 1000mW / cm 2 1200mW / cm 2 When the solvent is DMF, the gel contents are 94.6%, 95%, 82%, and 93%, respectively, and the swelling ratios are 15.5%, 16.7%, 25.4%, and 28.5%, respectively.

[0047] Figure 8 The graph shows the glass transition temperature of the product under different light power densities, 800-900 mW / cm². 2 Time T g Maintaining the temperature above 76℃, excessive power will cause T g Significant decrease.

[0048] Comparative Example 1 Weigh 50.0 mg of elemental sulfur and 50.0 mg of 1,3-diisopropenylbenzene, add them to a 20 ml photoreaction tube and mix thoroughly. Under inert gas protection and at room temperature, use a 300 nm light source at 800 mW / cm². 2 Sulfur-containing polymer samples were obtained by irradiation under certain conditions for 8 hours. The gel content, swelling ratio, and glass transition temperature of the obtained samples were tested.

[0049] Results: Under 300 nm illumination, the reaction system did not form a separable solid crosslinked sulfur-containing polymer, and the characteristic absorption peak of the C=C double bond in the infrared spectrum did not decrease significantly, indicating that elemental sulfur and 1,3-diisopropenylbenzene did not undergo sufficient reverse sulfurization polymerization.

[0050] Comparative Example 2 Weigh 50.0 mg of elemental sulfur and 50.0 mg of 1,3-diisopropenylbenzene, add them to a 20 ml photoreaction tube and mix thoroughly. Under inert gas protection and at room temperature, use a light source with a wavelength of 520 nm and an intensity of 800 mW / cm². 2 Sulfur-containing polymer samples were obtained by irradiation under certain conditions for 8 hours. The gel content, swelling ratio, and glass transition temperature of the obtained samples were tested.

[0051] Results: Under 520 nm illumination, the reaction system did not undergo significant solidification and no separable solid crosslinked sulfur-containing polymer was formed. The characteristic absorption peak of the C=C double bond in the infrared spectrum remained basically intact, indicating that the photon energy at this wavelength was insufficient to effectively induce ring-opening of elemental sulfur and initiate the reverse sulfurization polymerization reaction.

[0052] The above technical solutions of the present invention are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made under the technical concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included in the patent protection scope of the present invention.

Claims

1. A method for preparing sulfur-containing polymers by photoinitiated polymerization, characterized in that, Including the following steps: A mixed system containing elemental sulfur and unsaturated organic monomers is exposed to light at room temperature to cause the elemental sulfur and the unsaturated organic monomers to undergo a reverse sulfurization polymerization reaction, resulting in a sulfur-containing polymer. The crosslinked network structure of the sulfur-containing polymer is adjusted by regulating the illumination parameters, wherein the illumination parameters include illumination wavelength, light power density, and irradiation time; the illumination wavelength is 350-500 nm, and the light power density is 600-1300 mW / cm². 2 The irradiation duration is ≥2h.

2. The method for preparing sulfur-containing polymers by photoinitiated polymerization according to claim 1, characterized in that, The adjustment of the crosslinking network structure of the sulfur-containing polymer includes adjusting at least one of the following: the degree of crosslinking, gel content, glass transition temperature, swelling ratio, and solubility of the sulfur-containing polymer.

3. The method for preparing sulfur-containing polymers by photoinitiated polymerization according to claim 1, characterized in that, The illumination wavelength is 420-500 nm, and the optical power density is 700-1200 mW / cm². 2 The irradiation duration is ≥5.5h.

4. The method for preparing sulfur-containing polymers by photoinitiated polymerization according to claim 1, characterized in that, The illumination wavelength is 420-500 nm, and the optical power density is 750-950 mW / cm². 2 Or 1100-1200mW / cm 2 The irradiation duration is ≥7h.

5. The method for preparing sulfur-containing polymers by photoinitiated polymerization according to claim 1, characterized in that, The unsaturated organic monomers include organic monomers containing carbon-carbon double bonds and / or carbon-carbon triple bonds.

6. The method for preparing sulfur-containing polymers by photoinitiated polymerization according to claim 1, characterized in that, The unsaturated organic monomers include at least one of 1,3-diisopropenylbenzene, norbornene monomers, and unsaturated vegetable oils.

7. The method for preparing sulfur-containing polymers by photoinitiated polymerization according to claim 1, characterized in that, The mass ratio of elemental sulfur to the unsaturated organic monomer is 1:0.5-2.

8. A sulfur-containing polymer, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.

9. The sulfur-containing polymer according to claim 8, characterized in that, Glass transition temperature > -10℃, gel content > 40%.

10. The application of the sulfur-containing polymer of claim 8 or 9 in lithium-sulfur batteries, high-refractive-index optical materials, adsorption separation and preparation of functional polymer materials.

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