Preparation method of sulfur-containing silicon polymer material and sulfur-containing silicon polymer material

Abstract

The present invention provides a method for preparing a sulfur-containing silicon polymer material and the sulfur-containing silicon polymer material, specifically relating to the technical field of polymer materials. The preparation method comprises: mixing precipitated sulfur and dimethyldivinylsilane, heating the mixture under sealed conditions to obtain a polymer product; cooling and solidifying the polymer product to obtain a solidified product; and quenching the solidified product to obtain the sulfur-containing silicon polymer material. The present application uses industrial waste precipitated sulfur and dimethyldivinylsilane as raw materials to prepare the sulfur-containing silicon polymer material, achieving resource utilization of sulfur and dimethyldivinylsilane and alleviating environmental issues caused by industrial waste.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a preparation method of a sulfur-containing silicon polymer material and the sulfur-containing silicon polymer material. Background Art

[0002] Sulfur is a common industrial waste, primarily derived from the hydrodesulfurization process of waste gases in the petroleum industry. Global sulfur production exceeds 70 million tons annually. While 90% of this is effectively utilized, the remainder remains in surface storage, occupying significant land area and potentially posing environmental risks.

[0003] Dimethyldivinylsilane (DDMS) is an unavoidable byproduct of the Wurtz process for producing silicone vinyl sealants, a key raw material for silicone rubber. Production of each ton of sealant produces 50-80 kg of DDMS. Currently, this byproduct lacks industrial applications; most is stored year-round, with only a small amount volatile, entering the atmosphere or used as fuel. This consumes significant land resources and poses environmental risks. While DDMS's structure is well-suited for the production of polymer materials, research on its applications is currently lacking.

[0004] Therefore, how to realize the resource utilization of sulfur and dimethyldivinylsilane is crucial to solving the problems of land resource occupation and environmental pollution. Summary of the Invention

[0005] In view of the above shortcomings of the prior art, the present invention provides a method for preparing a sulfur-containing silicon polymer material and a sulfur-containing silicon polymer material to improve the land resource occupation and environmental pollution problems caused by the stacking of industrial waste sulfur and dimethyldivinylsilane.

[0006] To achieve the above-mentioned and other related purposes, the present invention provides a method for preparing a sulfur-containing silicon polymer material, the preparation method comprising the following steps:

[0007] Mixing the precipitated sulfur and dimethyldivinylsilane, heating and reacting the mixture to obtain a polymer product;

[0008] Cooling and solidifying the polymerized product to obtain a solidified product;

[0009] The solidified product is quenched to obtain a sulfur-containing silicon polymer material.

[0010] In one example of the present invention, precipitated sulfur and dimethyldivinylsilane are mixed and heated to react, including: mixing the dimethyldivinylsilane and the precipitated sulfur in a reaction vessel in a mass ratio of 1:(4-19), heating the reaction vessel to 160° C. to 190° C., and reacting for 1 to 3 hours.

[0011] In one example of the present invention, the reaction container is connected to a reflux device.

[0012] In one example of the present invention, the polymer product is cured by cooling, which includes, after the heating reaction is completed, cooling the reaction container to 130° C. and continuing the reaction for 24 to 80 hours.

[0013] In one example of the present invention, quenching the solidified product comprises placing a container containing the solidified product in liquid nitrogen for 5 to 10 minutes.

[0014] In one example of the present invention, after the solidified product is quenched, it also includes a standing treatment and a purification treatment. The standing treatment includes: after the solidified product is quenched, standing at room temperature for 1 to 24 hours to obtain a crude product. After the crude product is purified, a sulfur-containing silicon polymer material is obtained.

[0015] In one example of the present invention, the purification process includes: grinding the crude product and placing it into a centrifuge tube, adding carbon disulfide and vortex mixing 3 to 5 times, then centrifuging using a centrifuge and pouring out the supernatant; repeating the above steps 3 to 5 times, and then transferring it to an oven for drying to obtain a reddish-brown film or powder sulfur-containing silicon polymer material.

[0016] In one example of the present invention, the purification process includes: grinding the crude product and placing it into a vacuum sublimator containing a condensing device, evacuating the gas in the vacuum sublimator to reduce the internal pressure to 20 to 50 Pa; passing condensed water into the vacuum sublimator, heating it to 150°C, and maintaining it for 6 to 24 hours; after taking out the sample, washing it with carbon disulfide 3 to 5 times, transferring it to an oven for drying, and obtaining a viscous black sulfur-containing silicon polymer material that is stable at room temperature.

[0017] The present invention also provides a sulfur-containing silicon polymer material, which is prepared by any of the above-mentioned preparation methods.

[0018] In one example of the present invention, the sulfur-containing silicon polymer material includes structural units represented by formula (1) and / or formula (2):

[0019]

[0020] Wherein, R in formula (1) and formula (2) represents a sulfur atom; Represents a sulfur chain or ring.

[0021] The present invention uses precipitated sulfur and dimethyldivinylsilane as raw materials and adopts a reverse vulcanization method to polymerize and prepare a sulfur-containing silicon polymer material. The sulfur-containing silicon polymer material obtained by reverse vulcanization polymerization can be used in multiple fields such as heavy metal adsorption, lithium-sulfur ion batteries, and electronic devices, and has good application prospects.

[0022] The preparation method of the present invention realizes the resource utilization of settled sulfur and dimethyldivinylsilane industrial waste, and can effectively improve the land occupation and environmental pollution problems caused by the storage of industrial waste. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 A flow chart of a method for preparing a sulfur-containing silicon polymer material according to an embodiment of the present invention;

[0025] Figure 2 This is the solid-state NMR carbon spectrum of the crude product of the sulfur-containing silicon polymer material in one embodiment of the present invention. DETAILED DESCRIPTION

[0026] The following describes the embodiments of the present invention through specific examples. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments. The details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the following embodiments and features in the embodiments can be combined with each other unless they conflict.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0028] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0029] As used herein, "plurality," "multiple," "multiple times," etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0030] Herein, the terms "preferred," "better," and "more preferred" are merely used to describe preferred implementations or examples and should not be construed as limiting the scope of protection of the present invention. If multiple "preferred" terms appear in a technical solution, each "preferred" term is considered independent unless otherwise specified and there are no contradictions or mutual constraints.

[0031] Herein, “further”, “further”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of the present invention.

[0032] When referring to a numerical range herein, unless otherwise specified, the distribution of the values ​​within the numerical range is considered continuous and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every value between the two numerical endpoints. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges may be combined.

[0033] Sulfur and dimethyldivinylsilane are common industrial wastes. Their surface storage not only consumes significant land resources but also poses environmental risks. In 2013, Pyun et al. discovered that sulfur can polymerize with terminal dienes at high temperatures, a process known as "reverse vulcanization." This technology provides a new path for the resourceful utilization of sulfur and dimethyldivinylsilane.

[0034] See also Figure 1 The present invention provides a method for preparing a sulfur-containing silicon polymer material, the preparation method comprising the following steps:

[0035] S1, mixing the precipitated sulfur and dimethyldivinylsilane, heating and reacting to obtain a polymer product;

[0036] S2, cooling and solidifying the reaction product to obtain a solidified product;

[0037] S3. Quenching the solidified product to obtain a sulfur-containing silicon polymer material.

[0038] The precipitated sulfur used in step S1 is a type of sulfur. The molecular formula of precipitated sulfur is S8, and it has a cyclic structure. Dimethyldivinylsilane is a byproduct produced during the production of organosilicon vinyl capping agents. The structural formula of dimethyldivinylsilane is (H2C=CH)2Si(CH3)2, which contains two vinyl groups (-CH=CH2), each of which contains a carbon-carbon double bond. Therefore, dimethyldivinylsilane is an unsaturated organosilicon compound.

[0039] When precipitated sulfur and dimethyldivinylsilane are mixed, the ring-shaped molecules of the precipitated sulfur (S8) open at high temperatures, forming active sulfur. These active sulfur molecules react with the carbon-carbon double bonds in dimethyldivinylsilane to form sulfur-carbon bonds, thus connecting the sulfur molecules and dimethyldivinylsilane molecules to form a polymer with a three-dimensional network structure. This polymer contains a high proportion of sulfur and has multiple sulfur bond dynamic crosslinking sites.

[0040] The specific process of step S1 includes: mixing dimethyldivinylsilane and precipitated sulfur in a reaction container at a mass ratio of 1:(4-19), heating the reaction container to 160° C. to 190° C., and reacting for 1 to 3 hours.

[0041] The reaction vessel in this step can be a conventional glass container in the art, such as a flask, which can be either sealed or open. The reaction vessel is connected to a reflux system. During the reaction, the reflux system can reduce volatilization losses of the reactants by condensing and refluxing. It can also control the temperature of the reaction system by condensing and refluxing, preventing side reactions or decomposition caused by overheating.

[0042] Dimethyldivinylsilane and precipitated sulfur are weighed according to a set ratio and added to a reaction vessel. The set ratio can be any ratio in the range of 1: (4 to 19), such as 1:4, 1:10, 1:15 or 1:19, etc. Then, a heating device is used to heat the reaction vessel containing the reaction raw materials so that the dimethyldivinylsilane and the precipitated sulfur undergo a reverse vulcanization polymerization reaction. The heating device is, for example, an oil bath, that is, the reaction vessel is heated to 160°C to 190°C using an oil bath, and reacted at this temperature for 1 to 3 hours. Specifically, the reaction temperature can be 160°C, 170°C, 180°C or 190°C, etc.; the reaction time can be 1 hour, 2 hours or 3 hours, etc. The reaction temperature and reaction time can be selected according to actual conditions.

[0043] Step S2 is a curing treatment. After the heating reaction in step S1 is completed, the temperature of the reaction vessel is lowered to 130°C. The cooling method can be natural cooling, that is, the reaction vessel is maintained in an oil bath and naturally lowered to 130°C as the temperature of the oil bath decreases. The reaction is continued at this temperature for 24 to 80 hours. The curing treatment can convert the molten reaction product into a solid cured product, improve the thermal stability of the material, and enable it to maintain its performance even at higher temperatures. The curing treatment time can be any value within the range of 24 to 80 hours, for example, 24 hours, 40 hours, 60 hours, or 80 hours.

[0044] Step S3 is a quenching treatment, in which the solidified reaction vessel is placed in liquid nitrogen for 5 to 10 minutes, for example, 5 minutes, 8 minutes, or 10 minutes. Liquid nitrogen has a very low boiling point (-195.8°C). Using liquid nitrogen in this step can quickly cool the reaction system to an extremely low temperature, immediately stopping the reaction and avoiding excessive cross-linking or side reactions, as well as structural changes during the cooling process.

[0045] After the quenching treatment is completed, the system is stored at -20°C to obtain a reddish-brown gel-like sulfur-containing silicon polymer material.

[0046] Furthermore, after the quenching treatment is completed, it also includes a standing treatment and a purification treatment, wherein the standing treatment is to stand the solidified product after the quenching treatment at room temperature for 1 to 24 hours, for example, standing for 1 hour, 10 hours, 15 hours or 24 hours to obtain a crude product; then the crude product is crushed and ground and subjected to a purification process to obtain a sulfur-containing silicon polymer material. The crude product is usually in a block shape due to the adhesion of the polymer. If it is not refined, it is not conducive to the subsequent purification process. Therefore, after the standing treatment and before the purification treatment, the crude product is first crushed and ground to obtain a powdered crude product. There is no restriction on the particle size after crushing and grinding here. It only needs to be processed according to the conventional crushing and grinding process. It should be noted that the smaller the particles of the crude product, the more conducive it is to the purification of the product.

[0047] The purification methods in this application include but are not limited to centrifugation and sublimation. Different purification methods will result in different physical forms of the sulfur-containing silicon polymer material.

[0048] In one embodiment, purification is performed by centrifugation. The specific process is as follows: the powdered crude product is placed in a centrifuge tube, such as a 50 mL tube, and an appropriate amount of carbon disulfide is added and vortexed for 3 to 5 times, each time for 15 to 20 seconds. The product is then centrifuged in a high-speed centrifuge, for example, at 5000 x g (multiples of Earth's gravity) for 3 minutes, and the supernatant is discarded. The steps of adding carbon disulfide, vortexing, and high-speed centrifugation are repeated 3 to 5 times, and the product is then transferred to an oven for drying to obtain a reddish-brown film or powder of sulfur-containing silicon polymer material. Drying can be performed, for example, in a vacuum oven at 50°C for 12 to 24 hours.

[0049] In another embodiment, purification is performed by sublimation. Specifically, the powdered crude product is placed in a vacuum sublimator connected to a condenser, and the gas within the vacuum sublimator is evacuated to maintain an internal pressure of 20 to 50 Pa. Condensed water is introduced into the vacuum sublimator, heated to 150°C, and maintained at this temperature for 6 to 24 hours. The sample is then removed and washed three to five times with carbon disulfide. The sample is then transferred to an oven for drying to obtain a viscous black sulfur-containing silicon polymer material that is stable at room temperature. For example, this drying method involves drying in a vacuum oven at 50°C for 12 to 24 hours.

[0050] In other embodiments, purification can also be achieved by calcination. For example, calcination can be performed in a tube furnace at 240°C for 6 hours under nitrogen. The sample is then removed and washed three times with carbon disulfide. The sample is then dried in an oven to obtain a viscous black sulfur-containing silicon polymer material that is stable at room temperature.

[0051] The present invention also provides a sulfur-containing silicon polymer material, which is prepared by a reverse vulcanization polymerization reaction using precipitated sulfur and dimethyldivinylsilane as raw materials. The preparation process of the sulfur-containing silicon polymer material can be referred to the preparation method of the present invention described above and will not be described in detail here.

[0052] The sulfur-containing silicon polymer material of the present invention includes structural units represented by formula (1) and / or formula (2):

[0053]

[0054] Wherein, R in formula (1) and formula (2) represents a sulfur atom, "" represents a sulfur chain or ring of indeterminate length. The length of the sulfur chain or ring can be determined through testing and analysis. The structural formula of the sulfur-containing silicon polymer material can be tested and analyzed using solid-state nuclear magnetic resonance, elemental analysis, and ICP-OES (inductively coupled plasma optical emission spectrometry). The sulfur-rich silicon polymer obtained by desulfurization exhibits outstanding advantages, including excellent mercury and heavy metal adsorption, stable lithium-sulfur battery material properties, excellent thermal insulation, optical properties with a high reflectivity factor, excellent antibacterial properties, and self-healing or recyclability.

[0055] The technical solutions of the present invention are described in detail below through several specific examples and comparative examples. Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available or can be prepared by conventional methods in the art, and the instruments used in the examples are all commercially available.

[0056] Example 1

[0057] 4.5020 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, and then 0.5016 g of dimethyldivinylsilane was added and mixed. The reaction system was heated to 185°C using a heating device, and stirred at this temperature for 1 hour; then the temperature was lowered to 130°C (the temperature of the heating device was adjusted to 130°C, and the reaction system was naturally cooled to 130°C), and solidified at this temperature for 24 hours; then the reaction vessel was taken out and quenched under liquid nitrogen for 5 minutes, and then the reaction vessel was stored at -20°C to obtain a reddish-brown gel sulfur-containing silicon polymer material.

[0058] Example 2

[0059] 4.5007g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, followed by the addition of 0.5006g of dimethyldivinylsilane. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour. The temperature was then lowered to 130°C (by adjusting the temperature of the heating device to 130°C and allowing the reaction system to naturally cool to 130°C) and cured at this temperature for 24 hours. The reaction vessel was then removed and quenched in liquid nitrogen for 8 minutes. The reaction vessel was then stored at -20°C to produce a reddish-brown gel containing sulfur and silicon.

[0060] Example 3

[0061] 4.0142 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, and then 1.0105 g of dimethyldivinylsilane was added and mixed. The reaction system was heated to 185°C using a heating device and stirred for 1.5 hours; then the temperature was lowered to 130°C (the temperature of the heating device was adjusted to 130°C, and the reaction system was naturally cooled to 130°C), and solidified at this temperature for 45 hours; then the reaction vessel was taken out and placed in liquid nitrogen for quenching for 5 minutes, and then the reaction vessel was stored at -20°C to obtain a reddish-brown gel containing sulfur and silicon polymer material.

[0062] Example 4

[0063] 4.2548 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, and then 0.7502 g of dimethyldivinylsilane was added and mixed. The reaction system was heated to 190°C using a heating device and stirred at this temperature for 2 hours; then the temperature was lowered to 130°C (the temperature of the heating device was adjusted to 130°C, and the reaction system was allowed to cool naturally to 130°C), and solidified at this temperature for 45 hours; then the reaction vessel was taken out and quenched under liquid nitrogen for 10 minutes, and then the reaction vessel was stored at -20°C to obtain a reddish-brown gel-containing sulfur and silicon polymer material.

[0064] Example 5

[0065] 4.4963 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, and then 0.4986 g of dimethyldivinylsilane was added and mixed. The reaction system was heated to 160°C using a heating device and stirred at this temperature for 3 hours; then the temperature was lowered to 130°C (the temperature of the heating device was adjusted to 130°C, and the reaction system was naturally cooled to 130°C), and solidified at this temperature for 45 hours; then the reaction vessel was taken out and quenched under liquid nitrogen for 5 minutes, and then the reaction vessel was stored at -20°C to obtain a reddish-brown gel containing sulfur and silicon polymer material.

[0066] Example 6

[0067] 4.4979 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, and then 0.5101 g of dimethyldivinylsilane was added and mixed. The reaction system was heated to 175°C using a heating device and stirred at this temperature for 1 hour; then the temperature was lowered to 130°C (the temperature of the heating device was adjusted to 130°C, and the reaction system was naturally cooled to 130°C), and solidified at this temperature for 45 hours. Then, the reaction vessel was taken out and quenched under liquid nitrogen for 5 minutes. Then, the reaction vessel was stored at -20°C to obtain a reddish-brown gel containing sulfur and silicon polymer material.

[0068] Example 7

[0069] 4.5088 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, and then 0.5097 g of dimethyldivinylsilane was added and mixed. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour; then the temperature was lowered to 130°C (the temperature of the heating device was adjusted to 130°C, and the reaction system was naturally cooled to 130°C), and solidified at this temperature for 45 hours. Then, the reaction vessel was taken out and quenched under liquid nitrogen for 5 minutes. Then, the system was stored at -20°C to obtain a reddish-brown gel containing sulfur and silicon polymer material.

[0070] Example 8

[0071] 4.7531 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, followed by the addition of 0.2519 g of dimethyldivinylsilane. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour. The temperature was then lowered to 130°C (the heating device was adjusted to 130°C and the reaction system was allowed to cool naturally to 130°C) and cured at this temperature for 45 hours. The reaction vessel was then removed and quenched in liquid nitrogen for 5 minutes, and then allowed to stand at room temperature for 24 hours to produce a crude product. The crude product was crushed and ground into a powder. The powdered crude product was grouped into 50 mL centrifuge tubes, 1 g each. 35 mL of carbon disulfide was added and vortexed three times for 20 seconds each. The mixture was then centrifuged at 5000 x g for 3 minutes using a high-speed centrifuge, and the supernatant was discarded. The steps of adding carbon disulfide to the centrifuge tube, vortex mixing, and centrifugation were repeated three times, and then the tube was transferred to a vacuum oven at 50° C. and dried for 24 hours to obtain a dark reddish-brown thin film polymer material.

[0072] Example 9

[0073] 4.5039 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, followed by the addition of 0.5068 g of dimethyldivinylsilane. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour. The temperature was then lowered to 130°C (the heating device temperature was adjusted to 130°C, and the reaction system was allowed to cool naturally to 130°C) and solidified at this temperature for 45 hours. The reaction vessel was then removed and quenched in liquid nitrogen for 5 minutes, and then the reaction vessel was left at room temperature for 24 hours to obtain a crude product. The crude product was crushed and ground into a powder, and the powder was grouped into 50 mL centrifuge tubes, 1 g per group. 35 mL of carbon disulfide was added and vortexed three times for 20 seconds each time. The mixture was then centrifuged at 5000 x g for 3 minutes using a high-speed centrifuge, and the supernatant was discarded. The steps of adding carbon disulfide to the centrifuge tube, vortex mixing, and centrifugation were repeated three times, and then the tube was transferred to a vacuum oven at 50° C. and dried for 24 hours to obtain a dark reddish-brown thin film polymer material.

[0074] Example 10

[0075] 4.5022 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, followed by the addition of 0.5030 g of dimethyldivinylsilane. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour. The temperature was then lowered to 130°C (the heating device temperature was adjusted to 130°C, and the reaction system was allowed to cool naturally to 130°C) and cured at this temperature for 65 hours. The reaction vessel was then removed and quenched in liquid nitrogen for 5 minutes, and then allowed to stand at room temperature for 24 hours to obtain a crude product. The crude product was crushed and ground into a powder. The powder was then grouped into 50 mL centrifuge tubes, 1 g each. 35 mL of carbon disulfide was added and vortexed three times for 20 seconds each. The mixture was then centrifuged at 5000 x g for 3 minutes using a high-speed centrifuge, and the supernatant was discarded. The steps of adding carbon disulfide to the centrifuge tube, vortex mixing, and centrifugation were repeated three times, and then the tube was transferred to a vacuum oven at 50° C. and dried for 24 hours to obtain a dark reddish-brown thin film polymer material.

[0076] Example 11

[0077] 4.5036 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, followed by the addition of 0.5048 g of dimethyldivinylsilane. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour. The temperature was then lowered to 130°C (the temperature of the heating device was adjusted to 130°C, and the reaction system was allowed to cool naturally to 130°C). The mixture was cured at this temperature for 65 hours. The reaction vessel was then removed and quenched in liquid nitrogen for 5 minutes. The reaction vessel was then left at room temperature for 24 hours to produce a crude product. The crude product was crushed and ground into a powder. The powder was then grouped into 50 mL centrifuge tubes, 1 g per group. 35 mL of carbon disulfide was added and vortexed three times for 20 seconds each. The mixture was then centrifuged at 5000 x g for 3 minutes using a high-speed centrifuge, and the supernatant was discarded. The steps of adding carbon disulfide to the centrifuge tube, vortex mixing, and centrifugation were repeated three times, and then the tube was transferred to a vacuum oven at 50° C. and dried for 24 hours to obtain a dark reddish-brown solid polymer material.

[0078] Example 12

[0079] 4.4976 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux system, followed by the addition of 0.5022 g of dimethyldivinylsilane. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour. The temperature was then lowered to 130°C (the heating device was adjusted to 130°C and the reaction system was allowed to cool naturally to 130°C) and cured at this temperature for 65 hours. The reaction vessel was then removed and allowed to stand at room temperature for 48 hours to produce a crude product. The crude product was crushed to a powder and grouped into 50 mL centrifuge tubes. 35 mL of carbon disulfide was added and vortexed three times for 20 seconds each. The mixture was then centrifuged at 5000 x g for 3 minutes, and the supernatant was discarded. The addition of carbon disulfide, vortexing, and centrifugation were repeated three times. The mixture was then transferred to a vacuum oven at 50°C and dried for 24 hours to produce a dark reddish-brown solid polymer material.

[0080] Example 13

[0081] 4.4976 g of precipitated sulfur was added to a closed reaction vessel connected to a reflux device, and then 0.5041 g of dimethyldivinylsilane was added and mixed. The reaction system was heated to 185° C. using a heating device, and stirred at this temperature for 1 hour; then the temperature was lowered to 130° C. (the temperature of the heating device was adjusted to 130° C., and the reaction system was naturally cooled to 130° C.), and solidified at this temperature for 80 hours; then the reaction container was taken out, placed under liquid nitrogen for quenching for 5 minutes, and then the reaction container was placed at room temperature for 24 hours to obtain a crude product. The crude product was crushed and ground into powder, and the powdered crude product was grouped and loaded into a 60 mL flat-bottom sublimator, 1 g per group. The interior of the sublimator was evacuated to reduce the air pressure to about 30 Pa, and then condensed water was introduced into the sublimator and heated to 150°C, maintained at this temperature for 6 hours. The black viscous substance at the bottom of the sublimator was taken out, washed with carbon disulfide 3 times, and then transferred to a vacuum oven at 50°C and continued to dry for 24 hours to obtain a black viscous sulfur- and silicon-containing polymer material.

[0082] Example 14

[0083] 4.4982 g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux device, followed by the addition of 0.5011 g of dimethyldivinylsilane. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour. The temperature was then lowered to 130°C (the heating device temperature was adjusted to 130°C, and the reaction system was allowed to cool naturally to 130°C) and solidified at this temperature for 65 hours. The reaction vessel was then removed and quenched in liquid nitrogen for 5 minutes, and then the reaction vessel was left at room temperature for 24 hours to obtain a crude product. The crude product was crushed into a powder and placed in a glass boat, which was then loaded into the glass tube of a tube furnace. Nitrogen was introduced into the tube furnace and heated to 240°C for 6 hours. The black viscous substance at the bottom of the glass boat was removed, washed three times with carbon disulfide, and then transferred to a vacuum oven at 50°C and dried for 24 hours to obtain a black viscous sulfur- and silicon-containing polymer material.

[0084] Example 15

[0085] 4.4976 g of precipitated sulfur was added to a closed reaction vessel connected to a reflux device, and then 0.5041 g of dimethyldivinylsilane was added and mixed. The reaction system was heated to 185° C. using a heating device, and stirred at this temperature for 1 hour; then the temperature was lowered to 130° C. (the temperature of the heating device was adjusted to 130° C., and the reaction system was naturally cooled to 130° C.), and solidified at this temperature for 65 hours; then the reaction container was taken out, placed under liquid nitrogen for quenching for 5 minutes, and then the reaction container was placed at room temperature for 24 hours to obtain a crude product. The crude product was crushed and ground into powder, and the powdered crude product was grouped into a 60 mL flat-bottom sublimator, 1 g per group. The interior of the sublimator was evacuated to reduce the air pressure to about 30 Pa, and then condensed water was introduced into the sublimator and heated to 150°C, maintained at this temperature for 24 hours. The black viscous substance at the bottom of the sublimator was taken out, washed with carbon disulfide three times, and then transferred to a vacuum oven at 50°C and continued to dry for 24 hours to obtain a black viscous sulfur- and silicon-containing polymer material.

[0086] Example 16

[0087] 4.4969g of precipitated sulfur was added to a sealed reaction vessel connected to a reflux system, followed by the addition of 0.5083g of dimethyldivinylsilane. The reaction system was heated to 185°C using a heating device and stirred at this temperature for 1 hour. The temperature was then lowered to 130°C (the heating device temperature was adjusted to 130°C, and the reaction system was allowed to cool naturally to 130°C) and cured at this temperature for 45 hours. The reactor was then removed and quenched, and the system was allowed to stand at room temperature for 24 hours to produce a crude product. The crude product was crushed and ground into a powder, and the powdered crude product was grouped into 1g groups in a 60mL flat-bottom sublimator. The sublimator was evacuated to reduce the pressure to approximately 30 Pa. The reaction vessel was then removed and quenched under liquid nitrogen for 5 minutes. The reaction vessel was then allowed to stand at room temperature for 24 hours to produce the crude product. The crude product was crushed and ground into powder, and the powdered crude product was grouped and loaded into a 60 mL flat-bottom sublimator, 1 g per group. The interior of the sublimator was evacuated to reduce the air pressure to about 30 Pa, and then condensed water was introduced into the sublimator and heated to 150°C, maintained at this temperature for 24 hours. The black viscous substance at the bottom of the sublimator was taken out, washed with carbon disulfide three times, and then transferred to a vacuum oven at 50°C and continued to dry for 24 hours to obtain a black viscous sulfur- and silicon-containing polymer material.

[0088] After quenching, Examples 1 to 7 were not purified to obtain gel-like sulfur- and silicon-containing polymer materials. After quenching, Examples 8 to 12 used a purification method of centrifugal washing to separate impurities from the products, to obtain dark reddish-brown film-like or solid polymer materials. After quenching, Examples 13, 15, and 16 used a purification method of sublimation washing, and Example 14 used a purification method of tubular furnace calcination. In all cases, the products were heated, and heating may cause decomposition of certain heat-sensitive components or changes in the degree of polymerization, thereby obtaining black, viscous sulfur- and silicon-containing polymer materials.

[0089] The polymer materials of Examples 1 to 16 are all prepared by using precipitated sulfur and dimethyldivinylsilane as raw materials and polymerization reaction using the reverse vulcanization technology. The reason why they show different physical states of color is because purification can remove excess sulfur in the reactants, and physical purification and chemical purification affect their molecular states. The polymer materials prepared in Examples 1 to 16 contain structural units represented by formula (1) and / or formula (2), which can be tested and analyzed by solid nuclear magnetic resonance, elemental analysis, ICP-OES (inductively coupled plasma emission spectrometer), etc. The crushed crude product prepared according to the conditions in Example 9 was characterized by its solid nuclear magnetic carbon spectrum, and the data are as follows: Figure 2As shown, the carbon atom signals in different structures of the polymer material are numbered in the figure. This data proves that the polymer material includes the structural units represented by formula (1) and / or formula (2). This polymer material can be used in various fields such as lithium-sulfur batteries, molybdenum sulfide two-dimensional electronic devices, and replacing conventional asphalt, and has good application prospects.

[0090] The present invention uses sedimented sulfur and dimethyldivinylsilane as raw materials and adopts a reverse vulcanization polymerization method to produce a sulfur-containing silicon polymer material. This sulfur-containing silicon polymer material obtained by reverse vulcanization polymerization can be used in a variety of fields such as heavy metal adsorption, lithium-sulfur ion batteries, and electronic devices, and has excellent application prospects. The present invention realizes the resource utilization of sedimented sulfur and dimethyldivinylsilane industrial waste, which can effectively alleviate the land occupation and environmental pollution problems caused by industrial waste storage. Therefore, the present invention effectively overcomes some practical problems in the prior art and has high utilization value and application significance.

[0091] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A method for preparing a sulfur-containing silicon polymer material, characterized in that: The following steps are involved: Mixing the precipitated sulfur and dimethyldivinylsilane, heating and reacting the mixture to obtain a polymer product; Cooling and solidifying the polymerized product to obtain a solidified product; The solidified product is quenched to obtain a sulfur-containing silicon polymer material.

2. The preparation method according to claim 1, characterized in that The method comprises mixing the precipitated sulfur and dimethyldivinylsilane and heating them for reaction, comprising: mixing the dimethyldivinylsilane and the precipitated sulfur in a reaction container at a mass ratio of 1:(4-19), heating the reaction container to 160° C. to 190° C., and reacting for 1 to 3 hours.

3. The preparation method according to claim 2, characterized in that The reaction container is connected with a reflux device.

4. The preparation method according to claim 1, characterized in that The polymer product is cooled and solidified, comprising: after the heating reaction is completed, the reaction container is cooled to 130° C., and the reaction is continued for 24 to 80 hours.

5. The preparation method according to claim 1, characterized in that The solidified product is quenched, comprising: placing a reaction container containing the solidified product in liquid nitrogen for 5 to 10 minutes.

6. The preparation method according to claim 1, characterized in that After the solidified product is quenched, the method further includes a standing treatment and a purification treatment. The standing treatment includes: after the solidified product is quenched, standing at room temperature for 1 to 24 hours to obtain a crude product. After the crude product is purified, a sulfur-containing silicon polymer material is obtained.

7. The preparation method according to claim 6, characterized in that The purification process includes: grinding the crude product and placing it into a centrifuge tube, adding carbon disulfide and vortex mixing 3 to 5 times, then centrifuging it using a centrifuge and discarding the supernatant; repeating the above steps 3 to 5 times, and then transferring it to an oven for drying to obtain a reddish-brown film or powder sulfur-containing silicon polymer material.

8. The preparation method according to claim 6, characterized in that The purification process includes: grinding the crude product and then placing it into a vacuum sublimator containing a condensing device, evacuating the gas in the vacuum sublimator to reduce the internal pressure to 20 to 50 Pa; introducing condensed water into the vacuum sublimator, heating it to 150° C., and maintaining it for 6 to 24 hours; taking out the sample, washing it with carbon disulfide 3 to 5 times, and transferring it to an oven for drying to obtain a viscous black sulfur-containing silicon polymer material that is stable at room temperature.

9. A sulfur-containing silicon polymer material, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 8.

10. The sulfur-containing silicon polymer material according to claim 9, characterized in that: The sulfur-containing silicon polymer material includes structural units represented by formula (1) and / or formula (2): Wherein, R in formula (1) and formula (2) represents a sulfur atom; Represents a sulfur chain or ring.

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