CN115926255A - Sulfur microsphere capsule and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a sulfur microsphere capsule as well as a preparation method and application thereof, belonging to the technical field of high polymer materials. The sulfur microsphere capsule provided by the invention has a core-shell structure, wherein the shell is a POSS hybrid cross-linked polymer structure with the glass transition temperature of 132-165 ℃, and the core is sulfur; the POSS hybrid cross-linked polymer structure comprises a vinyl comonomer and cage-type polysilsesquioxane; the sulfuric acid microsphere capsule provided by the invention has the advantages of clear surface, good shape regularity and small particle size of 1.18-3.06 mu m; the glass transition temperature of the shell layer is 132-165 ℃, and the temperature range is higher than the rubber banburying temperature by 100-130 ℃, so that the sulfur microsphere capsule can be applied to the field of rubber vulcanization, and the blooming phenomenon is avoided; meanwhile, the preparation method of the sulfur microsphere capsule provided by the invention is simple, convenient to produce, low in raw material cost and suitable for actual industrial production.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a sulfur microsphere capsule and a preparation method and application thereof.
Background
Sulfur is an element widely distributed in the nature, solid powder is called sulfur, exists in various mineral structures and fossil fuels, and needs to be subjected to strict desulfurization treatment when mineral refining or fossil fuel refining processes generate a large amount of sulfur powder. Sulfur has wide application in chemical industry, and the application covers aspects of sulfuric acid manufacture, rubber vulcanization, paper making, bactericides, dyes and the like in the chemical industry. However, sulfur is easy to sublime, and sublimed sulfur and sulfur powder floating in the air are extremely easy to explode when meeting sparks in the air. In addition, sulfur is easily oxidized into sulfur dioxide in the air, the sulfur dioxide is combined with moisture in the air to form sulfurous acid, the sulfurous acid has great irritation to the lung, the sulfurous acid is also easily further oxidized to finally form sulfuric acid, and the sulfuric acid is a main component of acid rain. It is seen that safe handling, application and storage of sulfur is of great significance to the present environment and industrial fields.
Currently, one method is to gasify sulfur at high temperatures for polymerization crystallization to form insoluble crystalline sulfur polymers, which are mainly products of the foreign Flexsys company. The product is produced at home, and the performance of the product is gradually close to that of foreign products. However, the method has large energy consumption, and the crystallization polymerization sulfur has poor stability and unstable performance. Sulfur is an important vulcanizing agent in rubber products, and common sulfur is easy to generate a phenomenon of 'blooming' on the surface of the rubber products, which is a serious quality problem in the rubber industry. It is therefore essential to suppress blooming of rubber. The main reason for blooming is sulfurThe sulfur is unevenly dispersed in the rubber and is easy to agglomerate, agglomerated sulfur powder only has a vulcanization effect with sulfur in contact with the rubber in the vulcanization process, the sulfur powder inside the agglomerate cannot have a vulcanization reaction with the rubber, the sulfur powder begins to overflow to the surface of the rubber in the vulcanization process due to the low melting point of the sulfur, white frost is generated, and the uniformity of rubber vulcanization is influenced, so that the product quality is influenced. In order to solve the problem of blooming, insoluble crystal polymeric sulfur is used instead, so that the cost is high. Application No. 200910180589.7 discloses a raw material formula for producing sulfur microcapsules capable of being used as a rubber vulcanizing agent, which consists of sublimed sulfur, urea, 37% formaldehyde solution, gelatin or polyvinyl alcohol, formic acid, triethanolamine and water, a sulfur microcapsule product is prepared by an in-situ polymerization method, and a coating shell layer is melted at a certain temperature to release sulfur, so that the sulfur microcapsule product can play a role of vulcanizing rubber. Application number 200910005110.6 discloses a raw material formula for producing double-layer film sulfur microcapsules, which consists of sublimed sulfur, toluene diisocyanate, water, ethylenediamine, diethylenetriamine, urea and formaldehyde, and the double-layer film sulfur microcapsules are prepared by an interfacial polymerization method, wherein a core material of the double-layer film sulfur microcapsules is the sublimed sulfur, and a first layer of shell material is an interfacial polymerization product of the ethylenediamine, the diethylenetriamine and the toluene diisocyanate; the second shell material is urea-formaldehyde resin, and the capsule particle size is more than 100 μm. Similarly, emulsion polymerization has been reported, and sulfur is coated with polyvinyl alcohol, a copolymer of vinyl acetate and vinyltriethoxysilane, polyethylene wax, or the like, and the particle size is generally 100 μm or more. The second type is a physical coating method of polymer, which is to coat the polymer with sulfur by adding emulsifier into the existing water-soluble polymer, and the coated polymer has large particles, is difficult to coat tightly, and has a low melting point of the shell, for example, patent application No. 201110203772.1 coats polymer substances such as stearic acid, polyethylene resin, natural rubber and the like. In the patent application No. 201210224588.X, water-soluble polymers such as gelatin and cyclodextrin and natural polymers such as arabic gum and xanthan gum are coated with sulfur. The third kind is the physical coating technology of inorganic particles, which is to add emulsifier to the inorganic particles, then mix them with sulfur to coat them, then dry them, the drying temperature of the inorganic matter is high, the inorganic matter is agglomerated after drying, it needs to be driedPulverizing, sieving, and breaking coating; thus, it is difficult to achieve uniform and effective coating. Patent application No. 201510306288.X, using SiO 2 The film and the polymer film are coated, and the particle size of the product is 6.3-15 mu m. In the patent with application number 201510289745.9, inorganic silicon dioxide is used as a shell layer to carry out sulfur coating, the particle size of the prepared particles is 0.8-5 mu m, and in the preparation process of the inorganic material coating, the particles are agglomerated again in the drying process, powder needs to be ground, crushed and sieved again, and the coated capsules are damaged and have irregular appearance; for example, in the application No. 201610410842.3, inorganic powder is mixed with water, modifier is added to form coating emulsion, and then the coating emulsion is added into inorganic powder suspension, and sulfur is added after uniform stirring to prepare modified sulfur; such can also make the topography irregular.
Disclosure of Invention
Based on the situation, the invention aims to overcome the defects of the prior art and provide the sulfur microsphere capsule with small particle size, high shell glass transition temperature, clear surface and regular appearance, and the preparation method and the application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a sulfur microsphere capsule, the sulfur microsphere capsule has a core-shell structure, the shell is a POSS hybrid cross-linked polymer structure with a glass transition temperature of 132-165 ℃, and the core is sulfur; the POSS hybrid cross-linked polymer structure comprises the following components: vinyl comonomers and cage polysilsesquioxane.
According to the sulfur microsphere capsule provided by the invention, a hybridization crosslinking mode is adopted, and the synergistic effect of hydrogen bond action and cage type polysilsesquioxane hybridization crosslinking copolymerization is utilized, so that the glass transition temperature of a shell layer can be effectively improved, the glass transition temperature of an obtained product is 132-165 ℃, and the amphiphilic performance of the sulfur microsphere capsule can be realized through vinyl comonomer selection; meanwhile, the sulfuric acid microsphere capsule with the core-shell structure provided by the technical scheme of the invention has the advantages of small particle size of 1.18-3.06 mu m, clear surface and good shape regularity.
As a preferred embodiment of the sulfur microsphere capsule of the present invention, in the core-shell structure, the mass ratio of the core to the shell is: shell = (80-90): (10-20); exemplarily, in the present invention, the mass ratio of core and shell can be.
The inventor researches and discovers that the mass ratio of the core to the shell in the sulfur microsphere capsule can influence the particle size and the stability, if the mass of the core is too much and the shell layer is thinner, the core is easy to damage in the application process by extrusion, and if the mass of the core is too little, the subsequent use effect is reduced; and because the nucleus is cheap sulfur, the mass of the nucleus layer is relatively high as much as possible to achieve corresponding economic effect, namely, excellent uniformity and regularity can be obtained under the condition of high mass of the nucleus layer.
As a preferred embodiment of the sulfur microsphere capsule of the present invention, the mass ratio of the vinyl comonomer to the cage-type polysilsesquioxane is that the vinyl comonomer: cage polysilsesquioxane =100: (1-10).
Preferably, the mass ratio of the vinyl comonomer to the cage-type polysilsesquioxane is the mass ratio of the vinyl comonomer: cage polysilsesquioxane =100: (2.5-8).
The inventor researches and discovers that the mass ratio of the vinyl comonomer to the cage-type polysilsesquioxane influences the appearance and the structure of a product, if the mass of the vinyl comonomer is too large, the crosslinking density of the microspheres is insufficient, the microspheres are not favorable for tight coating, if the mass of the vinyl comonomer is too small, the flexibility of the microspheres is influenced, and the cost is increased, and when the mass ratio of the vinyl comonomer to the cage-type polysilsesquioxane is 100 (1-10), particularly 100: (2.5-8), the obtained sulfur microsphere capsule has optimal comprehensive performance.
As a preferred embodiment of the sulfur microsphere capsule of the present invention, the cage-type polysilsesquioxane is an ethylene-terminal cage-type polysilsesquioxane or a cage-type polysilsesquioxane containing a reactive functional terminal group, and specifically, the cage-type polysilsesquioxane is at least one of octaaminopropyl cage-type polysilsesquioxane and a derivative thereof, octaglycidyl cage-type polysilsesquioxane and a derivative thereof, octacarboxyethylene cage-type polysilsesquioxane and a derivative thereof, and octamethacryloxypropyl cage-type polysilsesquioxane and a derivative thereof.
Preferably, the cage polysilsesquioxane is octamethacryloxypropyl cage polysilsesquioxane (MMA-POSS).
As a preferred embodiment of the sulfur microsphere capsule according to the present invention, the vinyl comonomer is at least one of styrene and its derivatives, methyl methacrylate and its derivatives, hydroxyethyl methyl acrylate and its derivatives, vinyl acrylate and its derivatives, methacrylamide and its derivatives, glycidyl methacrylate and its derivatives, methacrylic acid and its derivatives, octyl methacrylate and its derivatives, butyl methacrylate and its derivatives.
Preferably, the vinyl comonomer is a compound of styrene and hydroxyethyl methacrylate, wherein the mass ratio of styrene to hydroxyethyl methacrylate is (1-3) to (1-3).
As a preferable embodiment of the sulfur microsphere capsule, the particle size of the sulfur microsphere capsule is 1.1-3.1 μm; in the present invention, the particle size of the sulfur microsphere capsule may be 1.1. Mu.m, 1.2. Mu.m, 1.3. Mu.m, 1.4. Mu.m, 1.5. Mu.m, 1.6. Mu.m, 1.7. Mu.m, 1.8. Mu.m, 1.9. Mu.m, 2.0. Mu.m, 2.1. Mu.m, 2.2. Mu.m, 2.3. Mu.m, 2.4. Mu.m, 2.5. Mu.m, 2.6. Mu.m, 2.7. Mu.m, 2.8. Mu.m, 2.9. Mu.m, 3.0. Mu.m, 3.1. Mu.m, etc.
In addition, the invention also provides a preparation method of the sulfur microsphere capsule, which comprises the following steps: sequentially adding sulfur, a dispersing agent and a vinyl comonomer into a first organic solvent for uniform dispersion, then adding a free radical initiator and an acetone solution of cage type polysilsesquioxane to obtain a reaction system, reacting the reaction system at the temperature of 50-90 ℃ for 6-24h in a protective gas environment, filtering, washing and drying after the reaction is finished, thus obtaining the sulfur microsphere capsule.
As a preferred embodiment of the preparation method of the present invention, the first organic solvent is at least one of toluene, THF, DMF, acetone, 1, 4-dioxane; the dispersing agent is a mixture of a second organic solvent and a stabilizing agent, the stabilizing agent is at least one of sodium octadecyl carboxylate, polyallyl alcohol (PVA), polymethylbenzene amide, carboxymethyl cellulose, gelatin, sodium alginate and silicon dioxide suspension, and the second organic solvent is at least one of DMF, carbon disulfide, THF and toluene; the free radical initiator is azo initiator and/or organic peroxide initiator.
Preferably, the azo initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the organic peroxide initiator is at least one of cumene hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide tert-butyl peroxide and diisopropyl peroxydicarbonate.
As a preferable embodiment of the preparation method of the invention, in the reaction system, the ratio of the total mass of the first organic solvent, the second organic solvent and the acetone to the total mass of the sulfur, the stabilizer, the vinyl comonomer, the free radical initiator and the cage type polysilsesquioxane is (4-10): 1; the mass of the stabilizer accounts for 0.01-0.5% of the total mass of the reaction system.
Under the reaction conditions provided by the invention, the reaction yield can be ensured.
As a preferred embodiment of the preparation method of the present invention, the washing is performed by using carbon disulfide, and the carbon disulfide can clean and remove sulfur adsorbed on the surface.
As a preferable embodiment of the preparation method of the invention, the drying temperature is 20-80 ℃, and the drying time is 1-10h.
As a preferred embodiment of the preparation method of the present invention, the protective gas is an inert gas or nitrogen.
In addition, the invention also provides application of the sulfur microsphere capsule in the fields of rubber safety vulcanizing agents, rubber materials, energy toughening materials, pesticides, fine chemical engineering, insect killing, antibiosis or functional materials.
The sulfur microsphere capsule provided by the invention has good coating effect and tight coating, and the glass transition temperature of the shell layer is higher and is between 132 and 165 ℃.
Compared with the prior art, the invention has the beneficial effects that:
on the first hand, the sulfur microsphere capsule provided by the invention adopts a hybrid crosslinking mode, and utilizes a hydrogen bond or cage type polysilsesquioxane chemical hybrid crosslinking copolymerization synergistic effect, so that the glass transition temperature of a shell layer can be effectively improved, the glass transition temperature is increased, specifically, the glass transition temperature is 132-165 ℃, and the amphiphilic property of the sulfur microsphere capsule can be realized through vinyl comonomer selection;
in the second aspect, the sulfuric acid microsphere capsule with the core-shell structure provided by the technical scheme of the invention has the advantages of clear surface, good shape regularity and small particle size of 1.1-3.1 mu m, so that tight coating can be ensured;
in a third aspect, the shell glass transition temperature of the sulfur microsphere capsule provided by the invention is 132-165 ℃, and the temperature range is higher than the rubber banburying temperature by 100-130 ℃, so that the sulfur microsphere capsule provided by the invention can be applied to the field of rubber vulcanization, and the blooming phenomenon is avoided;
in a fourth aspect, the preparation method of the sulfur microsphere capsule provided by the invention is simple, convenient to produce, low in raw material cost and suitable for actual industrial production.
Drawings
FIG. 1 is a fluorescence microscope photograph of the sulfur microsphere capsule prepared in example 1;
FIG. 2 is a DSC result chart of the sulfur microsphere capsule prepared in example 1, wherein A is a full temperature chart, and B is a partial enlarged view of the vicinity of 160 ℃ in the A chart.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
The raw materials used in the examples and comparative examples of the present application are specifically as follows:
octamethacryloxypropyl cage polysilsesquioxane (MMA-POSS): purchased from Hybrid Plastics, usa, MA0702;
octaaminopropyl cage polysilsesquioxane: purchased from Hybrid Plastics, usa, AM0270;
styrene: 100-42-5 of Jinxin chemical Co., ltd;
hydroxyethyl methacrylate: shanghai chemical agents, inc., 868-77-9;
propenyl polyether: PA923622, kuntongjiang chemical agents ltd;
in the examples and comparative examples, the experimental methods used were conventional unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified, and in parallel experiments, the materials used were identical unless otherwise specified.
Example 1
The embodiment of the invention provides a sulfur microsphere capsule, and the preparation method of the sulfur microsphere capsule comprises the following steps:
adding 100 parts of industrial sulfur into 200 parts of a first organic solvent (160 parts of toluene and 40 parts of DMF), uniformly stirring and dispersing, then adding 20 parts of a dispersing agent (the dispersing agent is a PVA solution with the concentration of 2 percent, namely the mass of a stabilizer PVA accounts for 0.066 percent of the total mass of the reaction system, the second organic solvent is a mixture of toluene and DMF, the mass ratio of toluene to DMF is 8.
Example 2
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that the vinyl comonomer is changed into 5 parts of styrene and 15 parts of hydroxyethyl methacrylate.
Example 3
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that 15 parts of styrene and 5 parts of hydroxyethyl methacrylate are used as the vinyl comonomer.
Example 4
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that the total mass parts of the added vinyl comonomer and the cage-type polysilsesquioxane are consistent with the embodiment 1, but the vinyl comonomer: cage polysilsesquioxane = 100.
Example 5
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that the total mass parts of the added vinyl comonomer and the cage-type polysilsesquioxane are consistent with the embodiment 1, but the vinyl comonomer: cage polysilsesquioxane = 100.
Example 6
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that the total mass parts of the added vinyl comonomer and the cage-type polysilsesquioxane are consistent with the embodiment 1, but the vinyl comonomer: cage polysilsesquioxane = 100.
Example 7
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that the reaction system is reacted for 6 hours at the temperature of 90 ℃ in a protective gas environment.
Example 8
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that octa-methacryloxypropyl cage-type polysilsesquioxane is replaced by octa-aminopropyl cage-type polysilsesquioxane.
Example 9
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that 20 parts of styrene is used for replacing the vinyl comonomer.
Example 10
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that PVA is replaced by a silicon dioxide suspension.
Example 11
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that 160 parts of toluene and 40 parts of 1, 4-dioxane are adopted as a first organic solvent.
Example 12
This example provides a sulphur microsphere capsule, the only difference between the process for the preparation of sulphur microsphere capsules and example 1 is that the reaction system is reacted at a temperature of 120 ℃ for 6h in a protective gas environment.
Example 13
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that a PVA solution with the concentration of 20% is added (namely the mass of a stabilizer PVA accounts for 0.66% of the total mass of a reaction system).
Comparative example 1
The embodiment of the invention provides a sulfur microsphere capsule, and the only difference between the preparation method of the sulfur microsphere capsule and the embodiment 1 is that no POSS crosslinking agent is added.
Comparative example 2
This comparative example provides a sulfur microsphere capsule prepared by a process that differs from example 1 only in that the total parts by mass of the added vinyl comonomer and cage polysilsesquioxane remains the same as in example 1, but the vinyl comonomer: cage polysilsesquioxane = 100.
Comparative example 3
The comparative example of the present invention provides a sulfur microsphere capsule, which was prepared by a method different from that of example 1 only in that the vinyl comonomer was replaced with 10 parts of styrene and 10 parts of a propylene-terminated polyether.
Examples of effects
The results of the tests of the present invention the sulfur microsphere capsules prepared in examples 1 to 13 and comparative examples 1 to 3 were subjected to morphology test, particle size measurement, core-shell quality test, shell glass transition temperature test, and dispersion property test in the rubber vulcanization process,
the specific test method is as follows:
(1) The method for testing the sulfur content comprises the following steps: placing the coated sulfur into CS 2 By soaking in the solvent of (2) for 4h, filtering, and evaporating the filtrate to remove CS 2 Weighing to obtain the weight of sulfur in the coating, and dividing the weight of the sulfur by the weight of the coated microspheres to obtain the ratio of the sulfur content to the core-shell weight.
(2) And (3) testing the appearance and the sulfur coating property of the coated sulfur:
because the sulfur has the fluorescence property, the core part of the coated particle has the fluorescence property, so the morphology of the particle can be observed by using a fluorescence polarization microscope, and the uniformity of sulfur coating in the particle or whether the particle is coated with the sulfur can be observed by using the fluorescence property of the particle.
(3) Particle size testing: the particle size can be measured using a fluorescence polarization microscope and magnification, and the statistical average of the microsphere diameter is calculated by statistical analysis software.
(4) Glass transition temperature (T) of shell g ): GB/T19466.2-2004, using TA differential scanning calorimetry, N 2 The flow rate is 40mL/min, and the heating speed is 10 ℃/min;
the results obtained from the tests are shown in table 1;
TABLE 1
As can be seen from Table 1, the particle size, the core-shell mass ratio and the morphology of the sulfur microsphere capsules obtained by different preparation methods are different, when the technical scheme of the invention is adopted, the yield of the obtained sulfur microsphere capsules is more than 82%, the sulfur content is more than 80%, the particle size of the obtained sulfur microsphere capsules is between 1.18 and 3.06 μm, and the core-shell mass ratio is (80-90): (10-20), the glass transition temperature of the shell layer is 132-165 ℃; wherein, the polarized fluorescence microscope photo of the sulfur microsphere capsule prepared in example 1 is shown in fig. 1, and as can be seen from fig. 1, the obtained sulfur microsphere capsule has uniform particle size and good regularity, and the DSC test result is shown in fig. 2.
As can be seen from examples 1-3, when the types of the vinyl comonomers are consistent, the change of the addition amount thereof can affect the core-shell mass ratio and the yield of the finally formed sulfur microsphere capsule, and also can affect the particle size and the glass transition temperature of the product, and when the mass ratio of styrene to hydroxyethyl methacrylate in the used vinyl comonomers is 1; it can be seen from example 1, example 9 and comparative example 3 that when different vinyl comonomers are used, in particular outside the ranges given in the present invention, the morphology of the resulting product is irregular and the particle size increases significantly.
As can be seen from examples 1,4 to 6 and comparative example 2, when the total parts by mass of the vinyl comonomer and the cage-type polysilsesquioxane added were kept the same, but the mass ratio of the two was different, the particle regularity became smaller as the POSS content increased, the POSS content was further increased, the yield was decreased, and the thermal properties were also decreased, and the mixing with the rubber was not uniform, when the mass ratio of the vinyl comonomer and the cage-type polysilsesquioxane was 100: (1-10), the yield obtained is 88% or more, the particle diameter is between 1.25 and 2.10 μm, the glass transition temperature is between 140 and 165 ℃, and when it is further preferable that the mass ratio of the vinyl comonomer to the cage-type polysilsesquioxane is 100: (2.5-8), the obtained yield is more than 92%, the grain diameter is 1.4-1.52 μm, the glass transition temperature is more than 160 ℃, and the comprehensive performance is better.
As can be seen from example 1, example 7 and example 12, the temperature and time of the reaction during the preparation process also have an influence on the properties of the product, and when the temperature of the reaction is too high, the regularity of the obtained product shows a certain deterioration trend compared with that of example 1, but is better than that of the product in comparative example 1 as a whole.
As can be seen from examples 1 and 13, the amount of the dispersant also affects the regularity of the product, and it is more preferable that the regularity of the obtained particles is excellent when the mass of the stabilizer in the dispersant is 0.01 to 0.5% of the total mass of the reaction system; when the mass percentage of the stabilizer in example 13 is outside the preferred range of the present invention, the regularity of the obtained product has a tendency to decrease compared with example 1, but is superior to the regularity of the product in comparative example 1 as a whole.
As can be seen from example 1 and comparative example 1, when no POSS crosslinker was added, the morphology of the resulting product was irregular, and the yield decreased, the particle size of the product increased, and the glass transition temperature decreased.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or similar material design ideas can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The sulfur microsphere capsule is characterized by having a core-shell structure, wherein the shell is a POSS hybrid cross-linked polymer structure with a glass transition temperature of 132-165 ℃, and the core is sulfur; the POSS hybrid cross-linked polymer structure comprises the following components: vinyl comonomers and cage polysilsesquioxane.
2. The sulfur microsphere capsule according to claim 1, wherein in the core-shell structure, the mass ratio of the core to the shell is core: shell = (80-90): (10-20).
3. The sulfur microsphere capsule of claim 1, wherein the mass ratio of the vinyl comonomer to the cage polysilsesquioxane is the weight ratio of the vinyl comonomer: cage polysilsesquioxane =100: (1-10).
4. The sulfur microsphere capsule of claim 1, wherein the cage polysilsesquioxane is at least one of octaaminopropyl cage polysilsesquioxane and its derivatives, octaglycidylpropyl cage polysilsesquioxane and its derivatives, octacarboxypropylene cage polysilsesquioxane and its derivatives, and octamethacryloxypropyl cage polysilsesquioxane and its derivatives.
5. The sulfur microsphere capsule of claim 1, wherein the vinyl comonomer is at least one of styrene and its derivatives, methyl methacrylate and its derivatives, hydroxyethyl methyl acrylate and its derivatives, vinyl acrylate and its derivatives, methacrylamide and its derivatives, glycidyl methacrylate and its derivatives, methacrylic acid and its derivatives, octyl methacrylate and its derivatives, butyl methacrylate and its derivatives.
6. The sulfur microsphere capsule of claim 1, wherein the particle size of the sulfur microsphere capsule is from 1.1 to 3.1 μm.
7. The process for the preparation of sulphur microsphere capsules according to any of claims 1 to 6, comprising the steps of: sequentially adding sulfur, a dispersing agent and a vinyl comonomer into a first organic solvent for uniform dispersion, then adding a free radical initiator and an acetone solution of cage-type polysilsesquioxane to obtain a reaction system, reacting the reaction system at 50-90 ℃ for 6-24 hours in a protective gas environment, filtering, washing and drying after the reaction is finished, and obtaining the sulfur microsphere capsule.
8. The method according to claim 7, wherein the first organic solvent is at least one of toluene, THF, DMF, acetone, 1, 4-dioxane; the dispersing agent is a mixture of a second organic solvent and a stabilizing agent, the stabilizing agent is at least one of sodium octadecyl carboxylate, polyallyl alcohol, polymethylbenzene amide, carboxymethyl cellulose, gelatin, sodium alginate and silicon dioxide suspension, and the second organic solvent is at least one of DMF, carbon disulfide, THF and toluene; the free radical initiator is azo initiator and/or organic peroxide initiator.
9. The preparation method according to claim 8, wherein the ratio of the total mass of the first organic solvent, the second organic solvent and acetone to the total mass of the sulfur, the stabilizer, the vinyl comonomer, the radical initiator and the cage-type polysilsesquioxane in the reaction system is (4-10): 1; the mass of the stabilizer accounts for 0.01-0.5% of the total mass of the reaction system.
10. The use of the sulfur microsphere capsule according to any one of claims 1 to 6 in the fields of rubber safety vulcanizing agents, rubber materials, energy toughening materials, pesticides, fine chemicals, pesticides and antibacterial or functional materials.
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