CN114348969A - Preparation method of insoluble sulfur - Google Patents
Preparation method of insoluble sulfur Download PDFInfo
- Publication number
- CN114348969A CN114348969A CN202210029501.7A CN202210029501A CN114348969A CN 114348969 A CN114348969 A CN 114348969A CN 202210029501 A CN202210029501 A CN 202210029501A CN 114348969 A CN114348969 A CN 114348969A
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- CN
- China
- Prior art keywords
- insoluble sulfur
- stabilizer
- temperature
- finished product
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 715
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 714
- 239000011593 sulfur Substances 0.000 title claims abstract description 705
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000003381 stabilizer Substances 0.000 claims abstract description 231
- 239000000047 product Substances 0.000 claims abstract description 199
- 238000010791 quenching Methods 0.000 claims abstract description 77
- 230000000171 quenching effect Effects 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 74
- 239000011265 semifinished product Substances 0.000 claims abstract description 74
- 239000007788 liquid Substances 0.000 claims abstract description 60
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000007873 sieving Methods 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000011049 filling Methods 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- 238000000605 extraction Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 103
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 65
- 238000006116 polymerization reaction Methods 0.000 claims description 65
- 238000010438 heat treatment Methods 0.000 claims description 51
- 239000003921 oil Substances 0.000 claims description 51
- 235000019198 oils Nutrition 0.000 claims description 51
- 229920000642 polymer Polymers 0.000 claims description 38
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 19
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical group C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 16
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- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- KKOXKGNSUHTUBV-LSDHHAIUSA-N zingiberene Chemical compound CC(C)=CCC[C@H](C)[C@H]1CC=C(C)C=C1 KKOXKGNSUHTUBV-LSDHHAIUSA-N 0.000 description 1
- 229930001895 zingiberene Natural products 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Abstract
The invention provides a preparation method of insoluble sulfur, which comprises the steps of sequentially carrying out extraction, drying, sieving and oil charge treatment on an insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product; the drying treatment refers to uniformly mixing the product obtained by extraction with a stabilizer and then carrying out vacuum drying; the stabilizer is stabilizer A or stabilizer B or a mixture of stabilizer A and stabilizer C or a mixture of stabilizer B and stabilizer C or a mixture of stabilizer A, stabilizer B and stabilizer C; wherein, the invention adopts low-temperature melting method when preparing the insoluble sulfur semi-finished product, and adjusts the technological parameters of the reaction and the type of the quenching liquid; the invention adds dispersant 1 during oil-filling treatment. The method is simple, solves the problem that the content of the insoluble sulfur prepared by a low-temperature melting method in the prior art is low, and also solves the problem that the thermal stability and the storage stability of the insoluble sulfur prepared by the prior art are to be further improved.
Description
Technical Field
The invention belongs to the technical field of sulfur production, and particularly relates to a preparation method of insoluble sulfur.
Background
Insoluble sulfur (IS for short) IS a thermoplastic linear high-molecular homopolymer, and has the characteristics of no toxicity, combustibility and insolubility in carbon disulfide. The insoluble sulfur has physical and chemical inertness, and can be used for vulcanizing rubber to prevent the rubber from frosting and scorching, so the insoluble sulfur is often used as a vulcanizing agent of a radial tire to improve the wear resistance and prolong the service life of the radial tire. However, insoluble sulfur is a metastable substance and factors such as high temperature, induction of alkaline substances, or long term storage may cause depolymerization of insoluble sulfur into ordinary sulfur. While ordinary sulfur itself has S8Cyclic structure, S8The ring structure is heated to open a ring to form a chain-shaped free radical monomer with unsaturated sulfur atoms at two ends, the free radical monomer carries out reversible polymerization reaction to grow insoluble sulfur linear polymers with different lengths, the chains with different lengths collide with each other to prolong the length of the polymerization chain, so that adjacent S atoms share 2 electrons to form an 8-electron stable structure, and the two ends of the polymer are still unstable (S)8)nThe unstable structure is rapidly depolymerized from both ends of the chain and finally converted into ordinary sulfur, if it is affected by high temperature, alkaline substance induction, or the like. In the prior art, a stabilizer IS usually added in the processes of IS polymerization, quenching, extraction, oil filling and the like, and the stabilizer can block the end group sulfur atom of IS and delay the conversion from insoluble sulfur to soluble sulfur.
As a first choice rubber vulcanizing agent of the radial tire, high-quality insoluble sulfur IS still in short supply, and the market has higher demand for high-stability IS. However, the insoluble sulfur finished product with good quality still depends on foreign import, and the high-quality insoluble sulfur finished product in China is in need of further improvement.
It is well known that the stabilizers commonly used in the art of insoluble sulfur technology are mainly halogen donors, olefins and redox species, but the stabilizing effect still needs to be improved. A plurality of methods are used for improving the stability of insoluble sulfur, for example, patent CN200810141306.3 discloses that common sulfur is used as a raw material, the raw material is melted at 250-350 ℃, gasified at high temperature, quenched and hung into tablets, dried, crushed, extracted, and then added with a stabilizer consisting of an antioxidant, isobutyl xanthate and styrene, wherein the mass ratio of the antioxidant to the isobutyl xanthate to the styrene is 1-2: 1-3: 0.5-2. Patent CN201810276046.4 reports that an IS60 insoluble sulfur semi-finished product IS obtained by using liquid sulfur as a raw material and sequentially carrying out gasification, quenching, tabletting, curing, crushing and sieving treatment, the semi-finished product IS extracted, the extracted product IS mixed with a stabilizer consisting of ammonium persulfate and ethylsodium xanthate according to the mass ratio of 3: 4-5, and then the mixture IS dried, sieved and oil-filled to obtain an IS90 insoluble sulfur finished product.
The xanthate chemicals can invade into human body through epidermis and mucous membrane to cause damage to organs such as nervous system and liver, and sodium alkylxanthate reagents such as isobutyl xanthate and ethyl sodium xanthate which are related in the patents are all xanthate chemicals, so that the health of workers is damaged in the production process, and potential safety hazard exists. Although the stabilizers reported in the prior art can improve the stability of insoluble sulfur to a certain extent, the market demand for high-quality insoluble sulfur prompts people to continuously develop new stabilizers and stabilizing processes, breaks through the potential hazards and technical limitations in the prior art, and obtains insoluble sulfur products with high thermal stability and long-term storage stability.
In the prior art, a low-temperature melting method (200-440 ℃) is commonly adopted in the technical field of insoluble sulfur, and has the advantages of low polymerization reaction temperature, safe equipment normal-pressure operation, no generation of three wastes, low equipment investment and the like, however, the content of the prepared insoluble sulfur is low (30% -60%), and the insoluble sulfur is reported to be prepared by a low-temperature melting method (the preparation technology of the insoluble sulfur, the chemical development, 2015, 34 (5): 1389 + 1394.) and the like, the polymerization temperature is 260 ℃, the polymerization reaction is 1h, room-temperature deionized water is adopted as quenching liquid, the curing temperature of a product is60 ℃, the curing time is 4h, and the content of the obtained insoluble sulfur is about 35%; research on the synthesis method and production process of Asahi (2009, 7 (36): 97-100.) reports that a plastic mixture of IS and soluble sulfur with a content of about 30% IS obtained by heating liquid sulfur to 200-446.4 ℃ and spraying the liquid sulfur into an aqueous quenching medium; the low-temperature melting method is adopted to quench the quenching liquid at the conditions of the polymerization temperature of 260 ℃, the heating rate of 2 ℃/min, the polymerization reaction time of 1h and the room temperature, and the content of the prepared insoluble sulfur is 36-38 percent.
Therefore, there is a need in the market to develop a method for preparing insoluble sulfur that can solve the above problems.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of insoluble sulfur.
The invention aims to provide a preparation method of insoluble sulfur aiming at the defects of relatively poor thermal stability and storage stability of the insoluble sulfur prepared in the prior art, and the invention aims to solve the problems by adding a specific kind of stabilizer in the production process of the insoluble sulfur.
The invention aims to solve the problem of low content of insoluble sulfur prepared by a low-temperature melting method in the prior art by optimizing and designing a preparation process of the insoluble sulfur, adding a specific kind of stabilizer, a specific kind of dispersant and the like.
In order to achieve the purpose, the invention adopts the following scheme:
a method for preparing insoluble sulfur comprises sequentially extracting semi-finished product of insoluble sulfur, drying, sieving, and filling oil to obtain finished product of insoluble sulfur;
the drying treatment refers to uniformly mixing the product obtained by extraction with a stabilizer and then carrying out vacuum drying; the sieving treatment refers to sieving with a 100-mesh sieve;
the stabilizer is a stabilizer A or a stabilizer B, and the addition amount of the stabilizer is 0.5-1.0% of the quality of the product obtained by extraction; within the range, the problems that the addition amount of the stabilizer is too large, the stability of insoluble sulfur is enhanced but the enhancement is not obvious and the cost is increased can be solved, and the problems that the stabilization effect is weakened and the long-term storage stability cannot be effectively ensured due to the fact that the addition amount of the stabilizer is too small can be solved;
or the stabilizer is a mixture of a stabilizer A and a stabilizer B in a mass ratio of 1-5: 5-1, a mixture of a stabilizer A and a stabilizer C in a mass ratio of 1-5: 1-2, a mixture of a stabilizer B and a stabilizer C in a mass ratio of 1-5: 1-3, a mixture of a stabilizer A and a stabilizer B and a stabilizer C in a mass ratio of 1-5: 1-3: 1, and the adding amount of the stabilizer is 0.5-0.8% of the mass of the product obtained by extraction; the stabilizer A, the stabilizer B and the stabilizer C are added simultaneously to achieve a synergistic stabilizing effect on the IS, and the IS IS better stabilized under the same adding amount; the addition amount IS reduced while the IS stability IS ensured, the value of the addition amount of the stabilizer IS 0.5-0.8% of the quality of the product obtained by extraction, and the production cost can be reduced; within the range, the problems that the addition amount of the stabilizer is too large, the stability of insoluble sulfur is enhanced but the enhancement is not obvious and the cost is increased can be solved, and the problems that the stabilization effect is weakened and the long-term storage stability cannot be effectively ensured due to the fact that the addition amount of the stabilizer is too small can be solved;
stabilizer a is [ [2- (benzylthio) ethyl ] thio ] benzene; the stabilizer B is DOPO; the stabilizer C is alpha-methyl styrene, p-methyl styrene, isopropenyl benzene, turpentine, lemon oil, terpene, dibenzothiazyl disulfide or dimercaptobenzothiazole.
As a preferred technical scheme:
in the above method for preparing insoluble sulfur, the terpene is monoterpene, sesquiterpene, diterpene, triterpene or tetraterpene, preferably limonene, pinene, camphene, zingiberene, caryophyllene, camphene or squalene.
According to the preparation method of the insoluble sulfur, the temperature of vacuum drying is 55-60 ℃, the time is 1-5 hours, and the pressure is60 kPa; the drying temperature is in the range, so that the problem that the insoluble sulfur is degraded due to overhigh temperature to reduce the content of the insoluble sulfur in the final product can be avoided, and the problem that the drying efficiency is reduced due to overlow temperature can be avoided.
According to the preparation method of the insoluble sulfur, the oil filling treatment IS to stir and mix the insoluble sulfur semi-finished product and filling oil uniformly, and a certain amount of the dispersing agent 1 IS added, wherein the addition amount of the dispersing agent 1 IS 0.3-0.6% of the mass of the insoluble sulfur semi-finished product, in this range, the problems that the addition amount IS too small and the dispersing effect on the IS IS not obvious can be avoided, and the problems that the addition amount IS too large, the gain effect IS not obvious and the application of the IS product in rubber IS influenced can be avoided, and the dispersing agent 1 IS fatty acid amide polyoxyethylene ether, isooctanol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, fatty acid diethanolamide, fatty alcohol polyoxyethylene ester, methoxypolyethylene glycol or allyl alcohol polyoxyalkyl ether.
Filling oil IS commonly used as a dispersant in the prior art, naphthenic oil and aromatic oil in the filling oil generally have a dispersing effect on IS oil and can also be called as a dispersant, other dispersants are used while the filling oil IS used, and the filling oil IS named as a dispersant 1 for distinguishing the filling oil from the other dispersants;
in the invention, a certain amount of dispersant 1 is added in the oil-filling treatment step to achieve the dispersion effect; the default oil-filled treatment step of the industry is that insoluble sulfur is firstly crushed and poured into a reaction kettle which has an oily extractant and can be stirred for extraction, and then the oily extractant dissolved with soluble sulfur is filtered by a filter pressing method to obtain oil-filled insoluble sulfur; if the dispersant 1 IS added in the oil-filling process, the dispersant 1 can play a role in isolating insoluble sulfur particles, reducing the surface energy of insoluble sulfur and preventing IS from aggregating due to surface static electricity, so that the purpose of dispersion IS achieved; an excessive amount of the dispersant 1 causes a waste of the reagent, and an insufficient amount of the dispersant 1 causes insufficient dispersion, so that the amount of the dispersant 1 added is closely related to the dispersing effect of the dispersant 1.
According to the preparation method of the insoluble sulfur, the filling oil is naphthenic oil, aromatic oil or white oil, and the mass of the filling oil accounts for 15-35% of that of the insoluble sulfur semi-finished product; the cost of the filling oil and the stability and the service performance of the obtained IS product are comprehensively considered, and the adding amount of the filling oil IS in the range; in the range, the problem that the use performance of the IS product cannot meet the actual requirement due to excessive addition of the filling oil IS avoided, for example, the mechanical property of an application material IS reduced, the filling oil plays a stabilizing role in the IS, and the stability of the IS product IS reduced due to too little filling oil.
The preparation method of the insoluble sulfur comprises the following steps:
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 230-270 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 0.75-2.5 h to obtain a polymer;
the sulfur polymerization reaction belongs to a reversible exothermic reaction, and when the polymerization temperature is lower, the reaction rate is slow, the conversion rate is high, and the average molecular weight is large; when the polymerization temperature is high, the reaction rate is high, the long-chain polymerized sulfur is broken into short-chain polymers or depolymerized into monomers, the conversion rate of insoluble sulfur is reduced, the average molecular weight is small, the polymerization rate is gradually reduced along with the rise of the temperature, the depolymerization rate is gradually increased, and the yield of the obtained insoluble sulfur is reduced;
the reaction rate is accelerated due to too high temperature rise rate, but the number of monomers for chain growth is small, so that the growth of a polymerized sulfur long chain is restricted, a polymer with high molecular weight cannot be formed, and the yield of the obtained insoluble sulfur is reduced; meanwhile, the high temperature increases the collision chance of the monomer and the free radical, so that the molecular weight distribution of the insoluble sulfur is widened, and the purity is reduced; on the contrary, the temperature rise rate is too low, the induction period of the polymerization reaction is prolonged, and the production efficiency of insoluble sulfur is greatly reduced;
the polymerization time is too short, the polymerization chain length of sulfur cannot be effectively prolonged, and the yield of insoluble sulfur is reduced; if the polymerization time is too long, the long-chain insoluble sulfur will be broken into short-chain polymers or depolymerized into monomers, and the yield of the insoluble sulfur is also reduced;
the invention adopts a low-temperature melting method, and the normal sulfur IS converted into high-molecular polymeric sulfur (namely insoluble sulfur IS) to the maximum extent by optimizing and regulating the heating rate, the polymerization temperature and the polymerization time of the sulfur polymerization reaction, thereby being beneficial to improving the conversion rate of the semi-finished product of the insoluble sulfur;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is a weakly acidic aqueous solution with the pH value of 5-6 adjusted by nitric acid, or an aqueous solution containing ethylene glycol, wherein the ethylene glycol accounts for 15-35% of the weight of water; the temperature of the quenching liquid is-4 to-16 ℃; the quenching liquid is refrigerated by adopting a machine refrigeration mode, preferably, a glycol refrigerator or a low-temperature constant-temperature tank is used for refrigerating (no matter the glycol refrigerator or the low-temperature constant-temperature tank is applicable to a weak acid aqueous solution or an ethylene glycol aqueous solution), and the temperature of the quenching liquid is up to the temperature of the quenching liquid; the ethylene glycol refrigerator is preferably purchased from Wuxi Guanya constant temperature refrigeration technology ltd with the model of LC (-25-5 ℃), and the low temperature constant temperature tank is preferably purchased from Nanken Jingfan electronic technology ltd with the model of KDC-0520 (-120-100 ℃);
in the process of preparing the insoluble sulfur semi-finished product, the temperature of a quenching liquid is adopted to carry out low-temperature quenching at the temperature of-4 to-16 ℃, the insoluble sulfur molecular chain is frozen, and glycol in the quenching liquid can be used as a stabilizing agent of the insoluble sulfur semi-finished product to carry out end capping on the insoluble sulfur semi-finished product, so that the conversion of the insoluble sulfur to soluble orthorhombic crystal sulfur is reduced under the freezing action and the end capping action of the glycol, the conversion rate of the insoluble sulfur semi-finished product is improved, and the insoluble sulfur semi-finished product is obtained;
in the prior art, carbon disulfide is commonly used as a quenching liquid in the technical field of insoluble sulfur, the quenching temperature is 50-60 ℃, the carbon disulfide is toxic as the quenching liquid, and the quenching temperature is 50-60 ℃, so that molecular chains of the insoluble sulfur cannot be rapidly frozen, reaction balance for generating the insoluble sulfur is reversely moved, and the yield of the insoluble sulfur is reduced;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving treatment.
According to the preparation method of the insoluble sulfur, the curing treatment temperature is 45-60 ℃, and the time is 4-6 hours.
According to the preparation method of the insoluble sulfur, the crushing treatment is to crush the insoluble sulfur to 80-150 meshes, the crushing treatment cannot ensure that the particle size is uniform, and the obtained 80-150 meshes are only in an average range of one size.
In the method for preparing insoluble sulfur, the sieving treatment refers to sieving through a 100-mesh sieve.
According to the preparation method of insoluble sulfur, the content of the insoluble sulfur in the finished product of the insoluble sulfur is 93-98.5%, and the prejudice in the field is overcome (namely the content of the insoluble sulfur prepared by a low-temperature melting method is only 30-60%); the stability of the insoluble sulfur finished product is 80-85% after being heated for 15min at the temperature of 105 ℃, 62-70% after being kept at the constant temperature of 120 ℃ for 15min, 75-80% after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, and 58-65% after being heated for 15min at the temperature of 120 ℃; the mass of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 93-98% of the total mass of insoluble sulfur.
The principle of the invention is as follows:
one of the technical problems to be solved by the invention is to further improve the stability of insoluble sulfur, and the invention is realized by selecting a specific stabilizer which is one, two or three of a stabilizer A, a stabilizer B and a stabilizer C, and the specific mechanism is as follows:
[2- (benzylthio) ethyl group in stabilizer A]Sulfur based radicals]The benzene has a stable flexible methylene bond in the molecular structure and is connected with a sulfur atom, the two ends of the structure have high-temperature stable benzene ring structures, and the insoluble sulfur which is not subjected to stabilization treatment is broken from the two ends to generate (S)8)nThe unstable structure (n is a positive integer greater than or equal to 2) can be combined with a methylene bond, phenyl or benzyl in the stabilizer A, so that sulfur atoms at two ends of the unstable structure reach an 8-electron stable structure, the breaking speed of a polymeric sulfur atom chain is inhibited, the recombined new structure can provide high-temperature stability of insoluble sulfur, and p electrons on the sulfur atoms at two ends of the stable insoluble sulfur structure can form a p-pi conjugated stable structure with a large pi bond of a benzene ring, so that the thermal stability of an insoluble sulfur finished product can be improved, the storage time can be prolonged, and the stable structure has good storage stability; and the electron cloud on the benzene ring in the stabilizer A can also generate coupling effect (mutual stabilization effect between the electron cloud and the electrons) with the sulfur free radical which is not blocked, thereby achieving the purpose ofFor the purpose of stabilizing the sulfur radicals; in addition, the structure of the stabilizer A also has a flexible aliphatic hydrocarbon chain with a certain chain length and containing sulfur atoms, and the flexible aliphatic hydrocarbon chain can be embedded into an S-S bond of insoluble sulfur to form a cross-linking bond, so that the stability of the insoluble sulfur is further improved;
the active P-H of DOPO in the stabilizer B is connected with a strong electron-withdrawing group, and can form active H atoms under the action of sulfur free radicals, and the active H atoms can seal the end of the sulfur free radicals, so that the sulfur atoms form an 8-electron stable structure, and the stability of insoluble sulfur is effectively improved; the DOPO can stabilize insoluble sulfur, and the DOPO can be used as an excellent flame retardant and can play a flame retardant role, so that the use safety of an insoluble sulfur finished product is effectively improved;
the compound containing unsaturated double bonds or benzene rings in the stabilizer C can enhance the coupling effect of electron cloud and sulfur free radicals, can form bonds with the sulfur free radicals at the same time, plays a role in sealing the sulfur free radicals, and further plays a role in synergistically stabilizing insoluble sulfur with [ [2- (benzylthio) ethyl ] thio ] benzene and DOPO.
The second technical problem to be solved by the invention is that the insoluble sulfur prepared by the low-temperature melting method in the prior art has low content (30-60%), so the invention can prepare the insoluble sulfur with the content of 93-98.5% by the low-temperature melting method, which depends on the four aspects: the polymerization reaction temperature and time of the sulfur are different from those of the prior art, the heating rate is limited, and the soluble sulfur is converted to the insoluble sulfur to the maximum extent on the basis of ensuring the stability of the obtained insoluble sulfur; the quenching liquid is different from the prior art, and the quenching liquid containing glycol is adopted, and the quenching temperature is-4 to-16 ℃ for low-temperature quenching; the stabilizer is different from the prior art; the dispersant 1 is different from the prior art;
the specific explanation about the mutual matching of the four aspects can realize the preparation of the insoluble sulfur with the content of 93-98.5% by adopting a low-temperature melting method is as follows:
firstly, optimizing the heating rate, polymerization temperature and polymerization time of sulfur polymerization reaction
Firstly, the temperature rise rate affects the conversion rate of insoluble sulfur, the IS conversion rate IS the largest when the temperature rise rate IS 5 ℃/min, and the IS conversion rate IS reduced when the temperature rise rate IS too high or too low, namely: the reaction rate is accelerated due to too high temperature rise rate, but the number of monomers for chain growth is small, so that the growth of a polymerized sulfur long chain is restricted, a polymer with high molecular weight cannot be formed, and the yield of the obtained insoluble sulfur is reduced; on the contrary, if the temperature rise rate is too low, the induction period of the polymerization reaction is prolonged, and the production efficiency of insoluble sulfur is greatly reduced; therefore, the proper temperature rise rate IS adjusted to ensure the high-efficiency conversion of common sulfur to IS;
the polymerization temperature affects the polymerization reaction rate, the reaction equilibrium shift and the length of the reaction chain, ultimately affecting the yield of IS, i.e.: the sulfur polymerization reaction belongs to a reversible exothermic reaction, and when the polymerization temperature is lower, the reaction rate is slow, the conversion rate is high, and the average molecular weight is large; when the polymerization temperature is high, the reaction rate is high, the long-chain polymerized sulfur is broken into short-chain polymers or depolymerized into monomers, the conversion rate of insoluble sulfur is reduced, the average molecular weight is small, the polymerization rate is gradually reduced along with the rise of the temperature, the depolymerization rate is gradually increased, and the yield of the obtained insoluble sulfur is reduced; meanwhile, the high temperature increases the collision chance of the monomer and the free radical, so that the molecular weight distribution of the insoluble sulfur is widened, and the purity is reduced; the common sulfur is S8The ring structure is thermally activated to open S at a temperature higher than 159 DEG C8A ring, which forms a chain-shaped free radical monomer with unsaturated sulfur atoms at two ends, and the polymer monomer IS subjected to reversible free radical polymerization reaction to generate long-chain polymers (namely the main body of the IS) with different lengths; the temperature range of the common melting method for preparing the insoluble sulfur is approximately between 200 and 440 ℃, however, in the prior art, the yield of the insoluble sulfur obtained by overhigh or overlow temperature is usually about 30 percent, and the requirement of practical application cannot be met;
the polymerization time also influences the chain length of sulfur polymerization, the polymerization time is too short, the polymer chains cannot collide with each other in time, the polymer chains cannot be effectively prolonged, and the yield of insoluble sulfur is reduced; the polymerization time is too long, the long-chain insoluble sulfur can be broken into short-chain polymers or depolymerized into monomers at high temperature, and the yield of the insoluble sulfur is also reduced; thus, too long and too short polymerization times ultimately reduce IS yield;
in the above, the temperature rise rate, the polymerization temperature and the polymerization time of the sulfur polymerization reaction finally influence the yield of the IS, so that the invention discovers that the IS product with higher yield and better stability can be obtained within the temperature range of 230-270 ℃ and the polymerization time of 0.75-2.5 h by optimizing the temperature rise rate, the polymerization temperature and the polymerization time;
secondly, the type and quenching conditions of the quenching liquid can also influence the yield of the IS, the quenching liquid IS a weakly acidic aqueous solution with the pH value of 5-6 or an aqueous solution containing glycol, the temperature of the quenching liquid IS selected from-4 to-16 ℃, and the aqueous solution IS safe and environment-friendly and has the advantages of safety, no toxicity, greenness and environmental protection compared with the commonly used carbon disulfide quenching liquid in the prior art; the stability of IS IS reduced under an alkaline condition, the stability of IS in the environment can be effectively ensured by adopting a weak acid environment, and active H atoms in ethylene glycol can end the end group free radicals of IS to play a role in stabilizing insoluble sulfur; more importantly, compared with the quenching temperature of 50-60 ℃ adopted in the prior art, the quenching temperature of minus C (-4-minus 16 ℃) which IS easy to realize IS adopted, so that the 'freezing' of the polymerization reaction balance can be effectively finished in a short time, the polymerization reaction IS terminated, and the influence of factors such as balance movement or high temperature on the IS yield IS prevented;
thirdly, as described in the above mechanism, the structural characteristics of the stabilizer A and the stabilizer B per se and the end capping or coupling effect on the insoluble sulfur increase the stability of the insoluble sulfur, and the stabilizer IS mixed in the drying process, so that the thermal stability of the insoluble sulfur can be improved by the mixed stabilizer, and the degradation of the IS caused by the drying temperature can be effectively avoided;
adding the dispersant 1 and filling oil simultaneously in oil filling treatment, wherein the dispersant 1 can fully permeate to the surface layer of the IS particles to play a lubricating role, and the surface of the IS particles adsorbs the dispersant to play roles in isolating aggregation effect caused by interaction among insoluble sulfur particles, reducing the surface energy of insoluble sulfur and preventing the IS from aggregating due to surface static electricity, thereby achieving effective dispersion of the IS and having better dispersion effect on the IS compared with the filling oil which plays a role in dispersion and stabilization and IS commonly used in the prior art;
in the above way, under the action of various stabilizing measures such as optimization operation and the like in the steps of polymerization reaction, quenching treatment, drying treatment and oil-filling treatment for preparing insoluble sulfur, the IS product with high stability and good dispersibility can be obtained.
Advantageous effects
(1) According to the preparation method of insoluble sulfur, the stabilizer is added when the semi-finished product of the insoluble sulfur is dried, the formula of the stabilizer is optimized, the stabilizer has a heat-resistant structure, the sensitivity of the insoluble sulfur to temperature can be reduced, and the thermal stability of the obtained insoluble sulfur finished product is effectively ensured;
(2) according to the preparation method of insoluble sulfur, the dispersing agent is added during oil filling treatment, so that the obtained insoluble sulfur finished product is fully dispersed, the mass of insoluble sulfur particles with the particle size of less than 100 micrometers accounts for 93-98% of the total mass of insoluble sulfur, and the particle size of the insoluble sulfur does not exceed 150 micrometers;
(3) according to the preparation method of insoluble sulfur, a low-temperature melting method is adopted, and the insoluble sulfur with the content of 93-98.5% is prepared by optimizing process conditions, compared with the insoluble sulfur prepared by the same low-temperature melting method in the prior art, the content of the insoluble sulfur (30-60%) is high, meanwhile, the stability of the obtained insoluble sulfur finished product can reach 85% at a constant temperature of 105 ℃ for 15min, and 70% at a constant temperature of 120 ℃ for 15 min; the prepared insoluble sulfur has the advantages of thermal stability, storage stability and dispersibility, and is beneficial to ensuring the application effect of the insoluble sulfur in the tire industry.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The test methods referred to in the examples are as follows:
the insoluble sulfur content test method is carried out according to the method described in the China rubber industry Association autonomous Standard XXZB/ZJ 1201-2013 high thermal stability insoluble sulfur 4.4; wherein, the insoluble sulfur content calculation formula is as follows: the insoluble sulfur content is the mass of insoluble sulfur/total amount of sulfur element × 100%.
The thermal stability of the insoluble sulphur was determined by heating the sample at 105 ℃ and 120 ℃ for 15min, respectively, and then rapidly cooling the sample to determine the mass fraction of insoluble sulphur in the elemental sulphur of the sample, as described in XXZB/ZJ 1201-2013 "high thermal stability insoluble sulphur" 4.8.
After the insoluble sulfur is stored for 9 months at normal temperature (the insoluble sulfur should be prevented from being directly irradiated by sunlight during the storage process, the ventilation and the drying are kept, the pressure agglomeration is prevented, the mixture with alkaline substances, halogen, phosphorus, metal powder, charcoal, black ash or other oxidants is avoided, the storage temperature is 25 ℃, and the relative humidity during the storage process does not exceed 40 percent), the stability is still carried out according to the method described in XXZB/ZJ 1201-2013 high-heat-stability insoluble sulfur 4.8.4.1 and 4.8.4.2, the sample is respectively heated for 15min at 105 ℃ and 120 ℃, the sample is rapidly cooled by an ice water bath, and then the mass of the insoluble sulfur accounts for the mass fraction of the elemental sulfur of the sample. And taking the arithmetic mean value of the results of the two parallel tests as a determination result, wherein the absolute difference value of the results of the two parallel tests is not more than 0.50%.
Insoluble sulfur particle size distribution test: the particle size distribution of the insoluble sulfur is subjected to particle size analysis test on a sample by adopting an LS 13320 laser particle size analyzer, specifically, absolute ethyl alcohol is used as a dispersing agent, an insoluble sulfur sample is added, ultrasonic stirring is carried out for 15min, insoluble sulfur dispersion liquid is prepared, and then the particle size analysis test is carried out on the insoluble sulfur dispersion liquid, wherein the mass concentration of the insoluble sulfur in the insoluble sulfur dispersion liquid is 0.01%, and the mass concentration of the insoluble sulfur is the mass percentage of the insoluble sulfur in the insoluble sulfur dispersion liquid. The test thus gives the proportion of the mass of insoluble sulphur particles with a particle size of <100 μm to the total mass of insoluble sulphur.
Method for calculating yield of stabilizer a: the mass of the actually obtained stabilizer a accounts for the mass of the theoretically obtained stabilizer a.
Lithium thiomethyl is manufactured by The homemade process according to The references "e.j. corey and d.seebach, phenylthiomethylthiomethylthiomethylphium and Bis (phenylthio) methythium, The Journal of Organic Chemistry,1966,4098". The method specifically comprises the following steps: dissolving a certain amount of thioanisole in 45mL of dry tetrahydrofuran to obtain a thioanisole solution; dissolving a certain amount of n-butyllithium in n-hexane according to the volume ratio of 1:5 to prepare a n-butyllithium solution; then taking a certain amount of 1, 4-diazabicyclo [2.2.2]Adding octane into the flask, adding the solution of thioanisole, and heating at 0 deg.C under N2Stirring uniformly under protection, dropwise adding n-butyllithium solution while stirring, and immediately generating complex precipitate; taking out the precipitate, and quickly filtering for later use; wherein the molar volume ratio of the thioanisole to the tetrahydrofuran is 0.03 mol: 45 mL; 1, 4-diazabicyclo [2.2.2]The molar ratio of octane, thioanisole and n-butyllithium is 3:3: 3.2.
Chloromethyl phenylsulfide was purchased from merck Sigma-Aldrich; tetrahydrofuran and toluene were both purchased from alatin; the palladium catalyst was purchased from Merck Sigma-Aldrich and had a purity of 98%.
The industrial sulfur is purchased from Jinyuangteng commercial Co., Ltd, Beijing, the purity of the sulfur is more than or equal to 99.5%, and the sulfur is in powder form, and the average grain diameter is 0.05-0.2 mm.
Example 1
A preparation method of a stabilizer for preparing insoluble sulfur comprises the following specific steps:
(1) preparation of raw materials:
phenylthiomethyl lithium solution: adding lithium thiomethyl into tetrahydrofuran according to the mass-to-volume ratio of 1g:10mL to prepare a lithium thiomethyl solution;
chloromethyl phenylsulfide solution: adding chloromethyl phenylsulfide into toluene according to the mass-volume ratio of 1g to 10mL to prepare chloromethyl phenylsulfide solution;
palladium catalyst: bis (tri-tert-butylphosphino) palladium;
(2) dropwise adding the phenylthiomethyl lithium solution into the chloromethyl phenylsulfide solution, dropwise adding within 10min, adding a palladium catalyst, uniformly stirring, and reacting at the temperature of 25 ℃ for 3h to obtain a stabilizer A; wherein the molar ratio of the phenylthiomethyl lithium to the chloromethyl phenylsulfide is 0.9: 1; the addition amount of the palladium catalyst accounts for 1.5 percent of the amount of the chloromethyl phenylsulfide substance;
the stabilizer A obtained was [ [2- (benzylthio) ethyl ] thio ] benzene, the yield was 76%.
Example 2
A preparation method of a stabilizer for preparing insoluble sulfur comprises the following specific steps:
(1) preparation of raw materials:
phenylthiomethyl lithium solution: adding lithium thiomethyl into tetrahydrofuran according to the mass-to-volume ratio of 1g:11mL to prepare a lithium thiomethyl solution;
chloromethyl phenylsulfide solution: adding chloromethyl phenylsulfide into toluene according to the mass-volume ratio of 1g:11mL to prepare chloromethyl phenylsulfide solution;
palladium catalyst: bis (tri-tert-butylphosphino) palladium;
(2) dropwise adding the phenylthiomethyl lithium solution into the chloromethyl phenylsulfide solution, dropwise adding the solution within 10min, adding a palladium catalyst, uniformly stirring, and reacting at the temperature of 25 ℃ for 4h to obtain a stabilizer A; wherein the molar ratio of the phenylthiomethyl lithium to the chloromethyl phenylsulfide is 0.9: 1; the addition amount of the palladium catalyst accounts for 2 percent of the amount of the chloromethyl phenylsulfide substance;
the stabilizer A obtained was [ [2- (benzylthio) ethyl ] thio ] benzene, the yield was 82%.
Example 3
A preparation method of a stabilizer for preparing insoluble sulfur comprises the following specific steps:
(1) preparation of raw materials:
phenylthiomethyl lithium solution: adding lithium thiomethyl into tetrahydrofuran according to the mass-to-volume ratio of 1g:12mL to prepare a lithium thiomethyl solution;
chloromethyl phenylsulfide solution: adding chloromethyl phenylsulfide into toluene according to the mass-volume ratio of 1g:13mL to prepare chloromethyl phenylsulfide solution;
palladium catalyst: bis (tri-tert-butylphosphino) palladium;
(2) dropwise adding the phenylthiomethyl lithium solution into the chloromethyl phenylsulfide solution, dropwise adding within 10min, adding a palladium catalyst, uniformly stirring, and reacting at the temperature of 25 ℃ for 5h to obtain a stabilizer A; wherein the molar ratio of the phenylthiomethyl lithium to the chloromethyl phenylsulfide is 1: 1; the addition amount of the palladium catalyst accounts for 3.5 percent of the amount of the chloromethyl phenylsulfide substance;
the stabilizer A obtained was [ [2- (benzylthio) ethyl ] thio ] benzene, the yield was 90%.
Example 4
A preparation method of a stabilizer for preparing insoluble sulfur comprises the following specific steps:
(1) preparation of raw materials:
phenylthiomethyl lithium solution: adding lithium thiomethyl into tetrahydrofuran according to the mass-to-volume ratio of 1g:12mL to prepare a lithium thiomethyl solution;
chloromethyl phenylsulfide solution: adding chloromethyl phenylsulfide into toluene according to the mass-volume ratio of 1g:15mL to prepare chloromethyl phenylsulfide solution;
palladium catalyst: bis (tri-tert-butylphosphino) palladium;
(2) dropwise adding the phenylthiomethyl lithium solution into the chloromethyl phenylsulfide solution, dropwise adding within 10min, adding a palladium catalyst, uniformly stirring, and reacting at the temperature of 25 ℃ for 5h to obtain a stabilizer A; wherein the molar ratio of the phenylthiomethyl lithium to the chloromethyl phenylsulfide is 1: 1; the addition amount of the palladium catalyst accounts for 5 percent of the amount of the chloromethyl phenylsulfide substance;
the stabilizer A obtained was [ [2- (benzylthio) ethyl ] thio ] benzene, the yield was 88%.
Example 5
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C and a stabilizer A prepared in example 1; the stabilizer C is alpha-methyl styrene; the mass ratio of the stabilizer A to the stabilizer C is 1: 1.
Example 6
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C and a stabilizer A prepared in example 2; the stabilizer C is p-methylstyrene; the mass ratio of the stabilizer A to the stabilizer C is 1: 2.
Example 7
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C and a stabilizer A prepared in example 3; the stabilizer C is isopropenylbenzene; the mass ratio of the stabilizer A to the stabilizer C is 2: 1.
Example 8
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C and a stabilizer A prepared in example 4; the stabilizer C is turpentine; the mass ratio of the stabilizer A to the stabilizer C is 3: 1.
Example 9
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C and a stabilizer A prepared in example 1; the stabilizing agent C is lemon oil; the mass ratio of the stabilizer A to the stabilizer C is 4: 1.
Example 10
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C and a stabilizer A prepared in example 1; the stabilizing agent C is limonene; the mass ratio of the stabilizer A to the stabilizer C is 5: 1.
Example 11
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C and a stabilizer A prepared in example 1; the stabilizer C is dibenzothiazyl disulfide; the mass ratio of the stabilizer A to the stabilizer C is 5: 2.
Example 12
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C and a stabilizer A prepared in example 1; the stabilizer C is dimercapto benzothiazole; the mass ratio of the stabilizer A to the stabilizer C is 4: 2.
Example 13
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer B and a stabilizer A prepared in example 1; the stabilizer B is DOPO; the mass ratio of the stabilizer A to the stabilizer B is 1: 1.
Example 14
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer B and a stabilizer A prepared in example 2; the stabilizer B is DOPO; the mass ratio of the stabilizer A to the stabilizer B is 5: 3.
Example 15
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer B and a stabilizer A prepared in example 3; the stabilizer B is DOPO; the mass ratio of the stabilizer A to the stabilizer B is 1: 3.
Example 16
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C, a stabilizer B and a stabilizer A prepared in example 1; the stabilizer C is alpha-methyl styrene; the stabilizer B is DOPO; the mass ratio of the stabilizer A to the stabilizer B to the stabilizer C is 1:1: 1.
Example 17
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C, a stabilizer B and a stabilizer A prepared in example 2; the stabilizer C is turpentine; the stabilizer B is DOPO; the mass ratio of the stabilizer A to the stabilizer B to the stabilizer C is 4:1: 1.
Example 18
An insoluble stabilizer for preparing sulfur is a mixture of a stabilizer C, a stabilizer B and a stabilizer A prepared in example 3; the stabilizing agent C is limonene; the stabilizer B is DOPO; the mass ratio of the stabilizer A to the stabilizer B to the stabilizer C is 5:3: 1.
Example 19
A stabilizer for preparing insoluble sulfur is stabilizer B, and stabilizer B is DOPO.
Example 20
A stabilizer for preparing insoluble sulfur is a mixture of stabilizer C and stabilizer B; the stabilizer C is alpha-methyl styrene; the stabilizer B is DOPO; the mass ratio of the stabilizer B to the stabilizer C is 1: 1.
Example 21
A stabilizer for preparing insoluble sulfur is a mixture of stabilizer C and stabilizer B; the stabilizer C is isopropenylbenzene; the stabilizer B is DOPO; the mass ratio of the stabilizer B to the stabilizer C is 3: 1.
Example 22
A stabilizer for preparing insoluble sulfur is a mixture of stabilizer C and stabilizer B; the stabilizer C is dibenzothiazyl disulfide; the stabilizer B is DOPO; the mass ratio of the stabilizer B to the stabilizer C is 5: 3.
Example 23
An insoluble sulfur preparation stabilizer substantially as in example 10 except that the stabilizer C is pinene.
Example 24
An insoluble sulfur production stabilizer, substantially as in example 10, except that stabilizer C is camphene.
Example 25
An insoluble sulphur preparation stabiliser substantially as described in example 10, except that stabiliser C is shogaol.
Example 26
An insoluble sulfur production stabilizer substantially as in example 10, except that the stabilizer C is caryophyllene.
Example 27
An insoluble sulfur production stabilizer substantially as in example 10 except that stabilizer C is camphene.
Example 28
An insoluble sulphur stabiliser as hereinbefore described with reference to example 10, except that stabiliser C is squalene.
Example 29
A preparation method of insoluble sulfur comprises the following specific steps:
(1) preparing an insoluble sulfur semi-finished product;
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 230 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 0.75h to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is a weak acidic aqueous solution with the pH value of 5 regulated by nitric acid, and the temperature of the quenching liquid is-4 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving; the temperature of the curing treatment is 45 ℃ and the time is6 h; the sieving treatment refers to sieving with a 100-mesh sieve;
(2) sequentially extracting, drying, sieving and oil-charging the insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product;
wherein, the drying treatment refers to that the product obtained by extraction and the stabilizer prepared in the embodiment 1 are evenly mixed and then dried for 5 hours in vacuum under the conditions that the temperature is 55 ℃ and the pressure is60 kPa; the addition of the stabilizer is 0.5 percent of the quality of the product obtained by extraction; the sieving treatment refers to sieving with a 100-mesh sieve;
the oil filling treatment is that the screened insoluble sulfur semi-finished product and naphthenic oil are stirred and mixed evenly, and a certain amount of fatty acid amide polyoxyethylene ether is added, wherein the addition amount of the fatty acid amide polyoxyethylene ether is 0.3 percent of the mass of the screened insoluble sulfur semi-finished product; the quality of the naphthenic oil accounts for 15% of the quality of the sieved insoluble sulfur semi-finished product.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.5 percent; the stability of the insoluble sulfur finished product is 81.4% after being heated for 15min at the temperature of 105 ℃, 63.2% after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 75.8% after being heated at the temperature of 105 ℃ for 9 months after being stored at normal temperature, the stability of the insoluble sulfur finished product is 59.7% after being heated at the temperature of 120 ℃ for 15min, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 93.6% of the total insoluble sulfur.
Comparative example 1
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that the temperature increase rate in step S1 is 10 ℃/min.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 87%; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 77%, the stability after being heated for 15min at the constant temperature of 120 ℃ is 57%, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 72%, the stability after being heated for 15min at the temperature of 120 ℃ is 56.7%, and the content of insoluble sulfur particles with the particle size of less than 100 mu m of the insoluble sulfur finished product accounts for 91.5% of the total insoluble sulfur.
Compared to example 29, the insoluble sulfur content of comparative example 1 was reduced, the thermal stability of the insoluble sulfur at 105 ℃ or 120 ℃ was reduced, and the storage stability was correspondingly reduced, because the rapid temperature rise increased the chance of collision of the monomer with the radical for a short time, so that the molecular weight distribution of the insoluble sulfur was broadened, the purity was reduced, and the content of the insoluble sulfur was reduced. The heating rate is too high, the reaction rate is accelerated, but the quantity of monomers for increasing the insoluble sulfur chain is small, the increase of the polymerized sulfur chain is restricted, a polymer with high molecular weight cannot be formed, the yield of the obtained insoluble sulfur is reduced, the polymerized sulfur cannot reach a certain polymerization degree, the polymerized sulfur is more easily degraded by the influence of factors such as environmental temperature, the thermal stability of the obtained insoluble sulfur is greatly reduced, and the storage stability is reduced.
Comparative example 2
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that the temperature increase rate in step S1 is 1 ℃/min.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 88 percent; the stability of the insoluble sulfur finished product is 78.2% after being heated for 15min at the temperature of 105 ℃, 57.4% after being kept at the constant temperature of 120 ℃ for 15min, 71.5% after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, 56.2% after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 92.6% of the total insoluble sulfur.
The insoluble sulfur content, thermal stability and storage stability of comparative example 2 are much less than example 29 compared to example 29, because the induction period of the polymerization increases at lower temperature rise rate,. S8The concentration of chain-like double-end radicals of the structure gradually increases along with the reaction, the viscosity of a polymerization reaction system also continuously increases, the rearrangement among polymer chains is hindered, and the polymerization system contains more (S)8)nChain-like double-ended radicals of unstable structure, stabilizing the insoluble sulfur obtainedThe sexual performance is reduced. And as the sulfur polymerization reaction belongs to a reversible exothermic reaction, along with the slow rise of the reaction temperature, the depolymerization rate of insoluble sulfur is increased, and long-chain polymers are degraded to generate short chains or monomers, so that the conversion rate of the insoluble sulfur is reduced, and the content of the insoluble sulfur in products generated by the polymerization reaction is reduced.
Comparative example 3
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that the heating temperature in step S1 is 200 ℃.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 86.8 percent; the stability of the insoluble sulfur finished product after being heated for 15min at 105 ℃ is 79.5%, the stability after being heated for 15min at 120 ℃ is 59.7%, the stability after being heated for 15min at 105 ℃ after being stored for 9 months at normal temperature is 73.9%, the stability after being heated for 15min at 120 ℃ is 57.4%, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 92.4% of the total insoluble sulfur.
The content of insoluble sulfur of comparative example 3 IS much less than that of example 29, compared to example 29, because the conversion of IS not as high at a temperature of 200 c as at a temperature of 230 c, and thus the yield of insoluble sulfur in comparative example 3 IS lower, resulting in a decrease in the content of insoluble sulfur.
Comparative example 4
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that the heating temperature in step S1 is 440 ℃.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 72.7 percent; the stability of the insoluble sulfur finished product is 77.8 percent after being heated for 15min at the temperature of 105 ℃, 57.9 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 71.3 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, the stability of the insoluble sulfur finished product is 56 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 92.2 percent of the total insoluble sulfur.
Compared with example 29, the content of insoluble sulfur in comparative example 4 is much less than that in example 29, because the polymerization rate becomes gradually smaller and the depolymerization rate becomes gradually larger as the temperature increases, and a large amount of long chains of the polymerized sulfur at high temperature are decomposed into short chains of small molecules, so that the reaction proceeds toward the depolymerization direction, which results in a great decrease in product purity and a decrease in yield of the obtained insoluble sulfur.
Comparative example 5
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that the polymerization reaction time in step S1 was 0.5 hours.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 81 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 79.3 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 59.6 percent, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 74 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 57.5 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 92.1 percent of the total insoluble sulfur mass.
The content of insoluble sulfur of comparative example 5 is much less than that of example 29, compared to example 29, because the polymerization time is too short, the polymer chains have no time to collide with each other, the polymer chains cannot be effectively extended, which will decrease the yield of insoluble sulfur, and the content of insoluble sulfur finally obtained decreases.
Comparative example 6
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that the polymerization reaction time in step S1 is 3 hours.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 88.7 percent; the stability of the insoluble sulfur finished product is 79.6 percent after being heated for 15min at the temperature of 105 ℃, 58.8 percent after being kept at the constant temperature of 120 ℃ for 15min, 73.7 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, 57.2 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m of the insoluble sulfur finished product accounts for 91.8 percent of the total insoluble sulfur mass.
The insoluble sulfur content of comparative example 6 is lower than that of example 29, compared to example 29, because the polymerization time is too long, the long-chain insoluble sulfur will be broken into short-chain polymers or depolymerized into monomers at high temperature, and the yield of insoluble sulfur will be reduced.
Comparative example 7
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that the quenching liquid in step S2 is carbon disulfide.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 92.8 percent; the stability of the insoluble sulfur finished product is 76.3 percent after being heated for 15min at the temperature of 105 ℃, 56.3 percent after being kept at the constant temperature of 120 ℃ for 15min, 69.8 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, 55.1 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m of the insoluble sulfur finished product accounts for 91.7 percent of the total mass of the insoluble sulfur.
Compared with example 29, the heat stability and long-term storage stability of the insoluble sulfur in comparative example 7 are much lower than those of example 29, because the quenching liquid in example 29 IS a weakly acidic aqueous solution with the pH adjusted to 5 by nitric acid, the stability of IS in a weak acid environment can be effectively ensured, the damage to the stability of the insoluble sulfur by alkaline substances in the production process IS avoided, and hydrogen ions in an acid environment can also stabilize the terminal free radicals of the insoluble sulfur and block the free radicals at the chain ends, so that the heat stability and long-term storage stability of the insoluble sulfur are improved, while the quenching liquid in comparative example 7 adopts chemically inert carbon disulfide as the quenching liquid and does not have the effect.
Comparative example 8
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer to be dried in the step (2) is α -methylstyrene.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 92.2 percent; the stability of the insoluble sulfur finished product is 75.4% after being heated for 15min at the temperature of 105 ℃, 52.8% after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 66.7% after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, the stability of the insoluble sulfur finished product is 50.3% after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 91.3% of the total insoluble sulfur.
Compared with example 29, the thermal stability and long-term storage stability of the insoluble sulfur in the comparative example 8 are much lower than those of example 29, because the stabilizer a prepared in example 1 is introduced into example 29, the stabilizer has a stable flexible methylene bond in the molecular structure to connect with the sulfur atom, and the two ends of the structure have high-temperature stable benzene ring structures, and can stabilize the terminal radical of the insoluble sulfur through electron cloud coupling and end capping, and the stabilizer can be recombined with the insoluble sulfur to form a new structure, and the p electrons on the sulfur atom at the two ends of the new structure can form a p-pi conjugated stable structure with the large pi bond of the benzene ring, so that the breaking speed of the polymerized sulfur atom chain is inhibited, the thermal stability of the sulfur insoluble product can be effectively improved, the storage time can be prolonged, and the storage stability of the insoluble sulfur can be improved. In addition, the structure of the stabilizer A also has a flexible aliphatic hydrocarbon chain with a certain chain length and containing sulfur atoms, and the flexible aliphatic hydrocarbon chain can be embedded into an S-S bond of insoluble sulfur to form a cross-linking bond, so that the stability of the insoluble sulfur is further improved. In comparative example 8, the stabilizer may generate new free radicals while the end groups of the insoluble sulfur are capped, thereby inducing depolymerization of the insoluble sulfur and reducing the stability of the insoluble sulfur.
Comparative example 9
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that no fatty acid amide polyoxyethylene ether is added in the oil-extended treatment in the step (2).
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 92.7 percent; the stability of the insoluble sulfur finished product is 79.7 percent after being heated for 15min at the temperature of 105 ℃, 61.2 percent after being kept at the constant temperature of 120 ℃ for 15min, 74.2 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, 57.7 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 85.5 percent of the total insoluble sulfur.
Compared with example 29, the insoluble sulfur in comparative example 9 has much lower dispersibility than that of example 29, because the fatty acid amide polyoxyethylene ether IS added in example 29, the fatty acid amide polyoxyethylene ether can effectively improve the dispersibility of the insoluble sulfur, the insoluble sulfur can be dispersed by exerting the functions of isolating insoluble sulfur particles, reducing the surface energy of the insoluble sulfur and preventing IS particles from aggregating due to surface static electricity, and the larger the content of the insoluble sulfur particles with the particle size of less than 100 μm in the total insoluble sulfur mass fraction IS, the better the dispersibility of the insoluble sulfur IS.
Comparative example 10
A process for producing insoluble sulfur, which is substantially the same as in example 29, except that the temperature of the quenching liquid in step S2 is 50 ℃.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 86.9 percent; the stability of the insoluble sulfur finished product is 79.5 percent after being heated for 15min at the temperature of 105 ℃, 61.5 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 74.3 percent, the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 120 ℃ is 57.5 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 92.4 percent of the total insoluble sulfur.
Compared with the example 29, the content of the insoluble sulfur in the comparative example 10 is much lower than that in the example 29, because the quenching liquid with the temperature of-4 ℃ is adopted to carry out low-temperature quenching in the process of preparing the insoluble sulfur semi-finished product in the example 29, the insoluble sulfur molecular chain is frozen, and the glycol in the quenching liquid can be used as a stabilizing agent of the insoluble sulfur semi-finished product to block the insoluble sulfur semi-finished product, so that the conversion from the insoluble sulfur to the soluble orthorhombic crystal sulfur is reduced under the freezing action of reaction balance and the blocking action of the glycol on the insoluble sulfur, the conversion rate of the insoluble sulfur semi-finished product is improved, and the content of the insoluble sulfur is higher. In comparative example 10, the quenching effect using the temperature condition of 50 ℃ was not as good as that in example 29 of the present invention, the reaction could not be rapidly frozen in equilibrium, and the insoluble sulfur content was relatively slightly low.
Comparative example 11
A process for preparing insoluble sulfur, which is substantially the same as in example 29, except that the stabilizer for the drying treatment is a mixture of an antioxidant 1010, isobutylxanthate and styrene in a mass ratio of 1:2: 1.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 92%; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 76%, the stability after being heated for 15min at the temperature of 120 ℃ is 53%, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 64.5%, the stability after being heated for 15min at the temperature of 105 ℃ is 48.6%, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 90% of the total insoluble sulfur.
Compared with example 29, the thermal stability and long-term storage stability of the insoluble sulfur in comparative example 11 are much less than those of example 29, because the stabilizer a prepared in example 1 is introduced into example 29, the stabilizer has a stable flexible methylene bond in the molecular structure to connect with the sulfur atom and has a high-temperature stable benzene ring structure at two ends of the structure, the terminal radical of the insoluble sulfur can be stabilized by electron cloud coupling and end capping, and the stabilizer can be recombined with the insoluble sulfur to form a new structure, the p electrons on the sulfur atom at two ends of the new structure can form a p-pi conjugated stable structure with a large pi bond of the benzene ring, thereby inhibiting the breaking speed of the polymerized sulfur atom chain, effectively improving the thermal stability of the sulfur insoluble product, prolonging the storage time and improving the storage stability of the insoluble sulfur. In addition, the structure of the stabilizer A also has a flexible aliphatic hydrocarbon chain with a certain chain length and containing sulfur atoms, and the flexible aliphatic hydrocarbon chain can be embedded into an S-S bond of insoluble sulfur to form a cross-linking bond, so that the stability of the insoluble sulfur is further improved. The end-capped structure of the insoluble sulfur capped by the stabilizer in the comparative example 11 is not as stable as the structure in the example 29, because the insoluble sulfur is capped by the isobutyl xanthate and the styrene, and a conjugated stable structure cannot be formed between the sulfur atom and the stabilizer after the end capping, so that the prepared insoluble sulfur product is easy to degrade in the high-temperature or long-term storage process, while the isobutyl xanthate is poor in chemical stability and easy to decompose in an acidic medium, and the stability of the insoluble sulfur is reduced due to the comprehensive factors.
Comparative example 12
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer for the drying treatment is a mixture of ammonium persulfate and sodium ethylxanthate in a mass ratio of 3: 5.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 91 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 73 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 50 percent, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 62.7 percent, the stability after being heated for 15min at the temperature of 105 ℃ is 43.8 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m of the insoluble sulfur finished product accounts for 91.8 percent of the total insoluble sulfur mass.
Compared with example 29, the thermal stability and long-term storage stability of the insoluble sulfur in the comparative example 12 are much lower than those of example 29, because the stabilizer a prepared in example 1 is introduced into example 29, the stabilizer has a stable flexible methylene bond in the molecular structure to connect with the sulfur atom, and the two ends of the structure have high-temperature stable benzene ring structures, and can stabilize the terminal radical of the insoluble sulfur through electron cloud coupling and end capping, and the stabilizer can be recombined with the insoluble sulfur to form a new structure, and the p electrons on the sulfur atom at the two ends of the new structure can form a p-pi conjugated stable structure with the large pi bond of the benzene ring, thereby inhibiting the breaking speed of the polymerized sulfur atom chain, effectively improving the thermal stability of the sulfur insoluble product, prolonging the storage time and improving the storage stability of the insoluble sulfur. In addition, the structure of the stabilizer A also has a flexible aliphatic hydrocarbon chain with a certain chain length and containing sulfur atoms, and the flexible aliphatic hydrocarbon chain can be embedded into an S-S bond of insoluble sulfur to form a cross-linking bond, so that the stability of the insoluble sulfur is further improved. The stabilizer ammonium persulfate in the comparative example 12 has deliquescence and is acidic when meeting water, can be gradually decomposed when placed at normal temperature, can be decomposed to release oxygen at higher temperature, and the ethyl sodium xanthate has poor chemical stability, and is easily decomposed by the ammonium persulfate which is weakly acidic after meeting the deliquescence, so that the instability of the stabilizer ammonium persulfate and the ethyl sodium xanthate can cause the reduction of the stabilization effect of the stabilizer ammonium persulfate and the ethyl sodium xanthate on insoluble sulfur in the high-temperature or long-term storage process, and finally the reduction of the stability of the insoluble sulfur is caused.
Example 30
A preparation method of insoluble sulfur comprises the following specific steps:
(1) preparing an insoluble sulfur semi-finished product;
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 235 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 1h to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is a weak acidic aqueous solution with pH value of 5 adjusted by nitric acid; the temperature of the quenching liquid is-8 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving; the temperature of the curing treatment is 50 ℃, and the time is6 h; the sieving treatment refers to sieving with a 100-mesh sieve;
(2) sequentially extracting, drying, sieving and oil-charging the insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product;
wherein, the drying treatment refers to uniformly mixing the extracted product with the stabilizer prepared in the embodiment 2, and then drying the mixture in vacuum for 4 hours at the temperature of 56 ℃ and the pressure of 60 kPa; the adding amount of the stabilizer is 1 percent of the quality of the product obtained by extraction; the sieving treatment refers to sieving with a 100-mesh sieve;
the oil filling treatment is that the screened insoluble sulfur semi-finished product and naphthenic oil are stirred and mixed evenly, and a certain amount of isooctanol polyoxyethylene ether phosphate is added, wherein the addition amount of the isooctanol polyoxyethylene ether phosphate is 0.5 percent of the mass of the screened insoluble sulfur semi-finished product; the quality of the naphthenic oil accounts for 20 percent of the quality of the screened insoluble sulfur semi-finished product.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 95.5 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 82%, the stability after being heated for 15min at the temperature of 120 ℃ is 65.6%, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 76.1%, the stability after being heated for 15min at the temperature of 120 ℃ is 62.5%, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 95% of the total insoluble sulfur.
Example 31
A preparation method of insoluble sulfur comprises the following specific steps:
(1) preparing an insoluble sulfur semi-finished product;
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 240 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 1.2h to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is a weak acidic aqueous solution with pH value of 5 adjusted by nitric acid; the temperature of the quenching liquid is-16 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving; the temperature of the curing treatment is 55 ℃, and the time is 5 h; the sieving treatment refers to sieving with a 100-mesh sieve;
(2) sequentially extracting, drying, sieving and oil-charging the insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product; the sieving treatment refers to sieving with a 100-mesh sieve;
wherein, the drying treatment refers to that the product obtained by extraction and the stabilizer prepared in the embodiment 3 are evenly mixed and then dried for 3 hours in vacuum under the conditions that the temperature is 57 ℃ and the pressure is60 kPa; the addition of the stabilizer is 0.8 percent of the quality of the product obtained by extraction;
the oil filling treatment is that the screened insoluble sulfur semi-finished product and aromatic oil are stirred and mixed evenly, and a certain amount of alkylphenol polyoxyethylene ether phosphate is added, wherein the addition amount of the alkylphenol polyoxyethylene ether phosphate is 0.6 percent of the mass of the screened insoluble sulfur semi-finished product; the mass of the aromatic oil accounts for 25% of the mass of the sieved insoluble sulfur semi-finished product.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 98.5 percent; the stability of the insoluble sulfur finished product is 85% after heating for 15min at the temperature of 105 ℃, 70% after keeping the temperature for 15min at the temperature of 120 ℃, 80% after storing for 9 months at normal temperature and heating for 15min at the temperature of 105 ℃, 65% after heating for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 98% of the total insoluble sulfur mass.
Example 32
A preparation method of insoluble sulfur comprises the following specific steps:
(1) preparing an insoluble sulfur semi-finished product;
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 245 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 1.4h to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is a weak acidic aqueous solution with pH value of 5 adjusted by nitric acid; the temperature of the quenching liquid is-14 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving; the temperature of the curing treatment is 50 ℃, and the time is 5 h; the sieving treatment refers to sieving with a 100-mesh sieve;
(2) sequentially extracting, drying, sieving and oil-charging the insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product;
wherein, the drying treatment refers to that the product obtained by extraction and the stabilizer prepared in the embodiment 4 are evenly mixed and then dried for 2 hours in vacuum under the conditions that the temperature is 58 ℃ and the pressure is60 kPa; the addition of the stabilizer is 0.6 percent of the quality of the product obtained by extraction; the sieving treatment refers to sieving with a 100-mesh sieve;
the oil filling treatment is that the screened insoluble sulfur semi-finished product is evenly mixed with aromatic oil by stirring, and a certain amount of fatty alcohol polyoxyethylene ether phosphate is added, wherein the addition amount of the fatty alcohol polyoxyethylene ether phosphate is 0.5 percent of the mass of the screened insoluble sulfur semi-finished product; the mass of the aromatic oil accounts for 27 percent of the mass of the sieved insoluble sulfur semi-finished product.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 98 percent; the stability of the insoluble sulfur finished product is 84.3 percent after being heated for 15min at the temperature of 105 ℃, 67.9 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 78.4 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, the stability of the insoluble sulfur finished product is 64.1 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 97.7 percent of the total mass of the insoluble sulfur.
Example 33
A preparation method of insoluble sulfur comprises the following specific steps:
(1) preparing an insoluble sulfur semi-finished product;
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 250 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 1.5h to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is an aqueous solution containing ethylene glycol, and the ethylene glycol accounts for 15% of the weight of the water; the temperature of the quenching liquid is-12 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving; the temperature of the curing treatment is60 ℃, and the time is 4 hours; the sieving treatment refers to sieving with a 100-mesh sieve;
(2) sequentially extracting, drying, sieving and oil-charging the insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product;
wherein, the drying treatment refers to that the product obtained by extraction and the stabilizer prepared in the embodiment 5 are evenly mixed and then dried for 1 hour in vacuum under the conditions that the temperature is 59 ℃ and the pressure is60 kPa; the addition of the stabilizer is 0.5 percent of the quality of the product obtained by extraction; the sieving treatment refers to sieving with a 100-mesh sieve;
oil filling treatment, namely uniformly stirring and mixing the screened insoluble sulfur semi-finished product and aromatic oil, and adding a certain amount of fatty acid diethanolamide, wherein the addition amount of the fatty acid diethanolamide is 0.4% of the mass of the screened insoluble sulfur semi-finished product; the mass of the aromatic oil accounts for 30% of the mass of the sieved insoluble sulfur semi-finished product.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 97.3 percent; the stability of the insoluble sulfur finished product is 84.6 percent after being heated for 15min at the temperature of 105 ℃, 68 percent after being heated for 15min at the temperature of 120 ℃, 77.6 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, 64.6 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 96.5 percent of the total insoluble sulfur.
Example 34
A preparation method of insoluble sulfur comprises the following specific steps:
(1) preparing an insoluble sulfur semi-finished product;
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 260 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 1.8h to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is an aqueous solution containing ethylene glycol, and the ethylene glycol accounts for 20% of the weight of the water; the temperature of the quenching liquid is-10 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving; the temperature of the curing treatment is 53 ℃, and the time is 4 hours; the sieving treatment refers to sieving with a 100-mesh sieve;
(2) sequentially extracting, drying, sieving and oil-charging the insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product;
wherein, the drying treatment refers to that the product obtained by extraction and the stabilizer prepared in the embodiment 6 are evenly mixed and then dried for 2 hours in vacuum under the conditions that the temperature is60 ℃ and the pressure is60 kPa; the addition of the stabilizer is 0.6 percent of the quality of the product obtained by extraction; the sieving treatment refers to sieving with a 100-mesh sieve;
the oil filling treatment is that the screened insoluble sulfur semi-finished product and white oil are stirred and mixed evenly, and a certain amount of fatty alcohol polyoxyethylene ester is added, wherein the addition amount of the fatty alcohol polyoxyethylene ester is 0.3 percent of the mass of the screened insoluble sulfur semi-finished product; the mass of the white oil accounts for 32% of the mass of the sieved insoluble sulfur semi-finished product.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 96.8 percent; the stability of the insoluble sulfur finished product is 83.7 percent after being heated for 15min at the temperature of 105 ℃, 66.7 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 77.2 percent, the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 120 ℃ is 63.5 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 95.2 percent of the total mass of the insoluble sulfur.
Example 35
A preparation method of insoluble sulfur comprises the following specific steps:
(1) preparing an insoluble sulfur semi-finished product;
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 265 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 2h to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is an aqueous solution containing ethylene glycol, and the ethylene glycol accounts for 25% of the weight of the water; the temperature of the quenching liquid is-12 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving; the temperature of the curing treatment is 58 ℃ and the time is 4 hours; the sieving treatment refers to sieving with a 100-mesh sieve;
(2) sequentially extracting, drying, sieving and oil-charging the insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product;
wherein, the drying treatment refers to that the product obtained by extraction and the stabilizer prepared in the embodiment 7 are evenly mixed and then dried for 3 hours in vacuum under the conditions that the temperature is 58 ℃ and the pressure is60 kPa; the addition of the stabilizer is 0.7 percent of the quality of the product obtained by extraction; the sieving treatment refers to sieving with a 100-mesh sieve;
the oil filling treatment is that the screened insoluble sulfur semi-finished product and white oil are stirred and mixed evenly, and a certain amount of methoxy polyethylene glycol is added, wherein the addition amount of the methoxy polyethylene glycol is 0.5 percent of the mass of the screened insoluble sulfur semi-finished product; the white oil accounts for 34% of the mass of the sieved insoluble sulfur semi-finished product.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 96.1 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 82%, the stability after being heated for 15min at the temperature of 120 ℃ is 64.5%, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 76.8%, the stability after being heated for 15min at the temperature of 120 ℃ is 62.3%, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 95.8% of the total insoluble sulfur.
Example 36
A preparation method of insoluble sulfur comprises the following specific steps:
(1) preparing an insoluble sulfur semi-finished product;
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 270 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 2.5 hours to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is an aqueous solution containing ethylene glycol, and the ethylene glycol accounts for 35% of the weight of the water; the temperature of the quenching liquid is-8 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving; the temperature of the curing treatment is60 ℃, and the time is 4 hours; the sieving treatment refers to sieving with a 100-mesh sieve;
(2) sequentially extracting, drying, sieving and oil-charging the insoluble sulfur semi-finished product to obtain an insoluble sulfur finished product;
wherein, the drying treatment refers to that the product obtained by extraction and the stabilizer prepared in the embodiment 8 are evenly mixed and then dried for 4 hours in vacuum under the conditions that the temperature is 55 ℃ and the pressure is60 kPa; the addition of the stabilizer is 0.8 percent of the quality of the product obtained by extraction; the sieving treatment refers to sieving with a 100-mesh sieve;
the oil filling treatment is that the screened insoluble sulfur semi-finished product and white oil are stirred and mixed evenly, and a certain amount of allyl alcohol polyoxyalkyl ether is added, wherein the addition amount of the allyl alcohol polyoxyalkyl ether is 0.6 percent of the mass of the screened insoluble sulfur semi-finished product; the mass of the white oil accounts for 35% of the mass of the sieved insoluble sulfur semi-finished product.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 95.2 percent; the stability of the insoluble sulfur finished product is 81.5 percent after being heated for 15min at the temperature of 105 ℃, 63.6 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 75.7 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, the stability of the insoluble sulfur finished product is 60.4 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 94.6 percent of the total insoluble sulfur mass.
Example 37
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in step (2) is the one produced in example 9.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 95 percent; the stability of the insoluble sulfur finished product is 81.5 percent after being heated for 15min at the temperature of 105 ℃, 63.9 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 75.6 percent, the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 120 ℃ is 61.2 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 94.2 percent of the total insoluble sulfur mass.
Example 38
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 10.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.6 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 81 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 63.4 percent, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 75.1 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 60.8 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.6 percent of the total insoluble sulfur mass.
Example 39
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 11.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.7 percent; the stability of the insoluble sulfur finished product is 81.3 percent after being heated for 15min at the temperature of 105 ℃, 63.6 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 75.3 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, the stability of the insoluble sulfur finished product is 61.0 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 93.8 percent of the total mass of the insoluble sulfur.
Example 40
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 12.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.5 percent; the stability of the insoluble sulfur finished product is 81.2% after heating for 15min at the temperature of 105 ℃, 63.5% after keeping the temperature for 15min at the temperature of 120 ℃, 75.2% after storing for 9 months at normal temperature and heating for 15min at the temperature of 105 ℃, 60.9% after heating for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.5% of the total insoluble sulfur mass.
EXAMPLE 41
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 13.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 95.4 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 82%, the stability after being heated for 15min at the temperature of 120 ℃ is 64.5%, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 76%, the stability after being heated for 15min at the temperature of 120 ℃ is 62.2%, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.3% of the total insoluble sulfur.
Example 42
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in step (2) is the one produced in example 14.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 95.7 percent; the stability of the insoluble sulfur finished product is 82.2% after heating for 15min at the temperature of 105 ℃, 64.9% after keeping the temperature for 15min at the temperature of 120 ℃, 76.2% after heating for 15min at the temperature of 105 ℃ after storing for 9 months at normal temperature, 62.4% after heating for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.6% of the total insoluble sulfur mass.
Example 43
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in step (2) is the one produced in example 15.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 95.1 percent; the stability of the insoluble sulfur finished product is 81.6 percent after being heated for 15min at the temperature of 105 ℃, the stability is 64.1 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 75.8 percent after being stored for 9 months at normal temperature and being heated for 15min at the temperature of 105 ℃, the stability of the insoluble sulfur finished product is 61.5 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 93.1 percent of the total mass of the insoluble sulfur.
Example 44
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 16.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 96.2 percent; the stability of the insoluble sulfur finished product is 82.8 percent after being heated for 15min at the temperature of 105 ℃, 65.1 percent after being kept at the constant temperature of 120 ℃ for 15min, 76.5 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, 62.6 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m of the insoluble sulfur finished product accounts for 93.7 percent of the total mass of the insoluble sulfur.
Example 45
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 17.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 96.3 percent; the stability of the insoluble sulfur finished product after being heated for 15min at 105 ℃ is 83.2%, the stability after being kept at the constant temperature of 120 ℃ for 15min is 65.4%, the stability after being heated for 15min at 105 ℃ after being stored for 9 months at normal temperature is 77%, the stability after being heated for 15min at 120 ℃ is 63.2%, and the content of insoluble sulfur particles with the particle size of less than 100 mu m of the insoluble sulfur finished product accounts for 93.5% of the total insoluble sulfur.
Example 46
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 18.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 96.5 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 83.5 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 66.3 percent, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 77.4 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 63.7 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m of the insoluble sulfur finished product accounts for 94.2 percent of the total insoluble sulfur mass.
Example 47
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 19.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 93 percent; the stability of the insoluble sulfur finished product is 80% after being heated for 15min at the temperature of 105 ℃, 62% after being heated for 15min at the temperature of 120 ℃, 75% after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, 58% after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93% of the total insoluble sulfur.
Example 48
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 20.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94%; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 81 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 62.3 percent, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 75.1 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 58.8 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.2 percent of the total insoluble sulfur mass.
Example 49
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 21.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.1 percent; the stability of the insoluble sulfur finished product is 81.2% after heating for 15min at the temperature of 105 ℃, 62.8% after keeping the temperature for 15min at the temperature of 120 ℃, 75.3% after storing for 9 months at normal temperature and heating for 15min at the temperature of 105 ℃, 59% after heating for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.1% of the total insoluble sulfur mass.
Example 50
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 22.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.2 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 81.3 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 63 percent, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 75.4 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 59.2 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.3 percent of the total insoluble sulfur.
Example 51
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 23.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.8 percent; the stability of the insoluble sulfur finished product is 81.2% after heating for 15min at the temperature of 105 ℃, 63.3% after keeping the temperature for 15min at the temperature of 120 ℃, 75.1% after storing for 9 months at normal temperature and heating for 15min at the temperature of 105 ℃, 61.2% after heating for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.4% of the total insoluble sulfur mass.
Example 52
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 24.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.5 percent; the stability of the insoluble sulfur finished product after being heated for 15min at the temperature of 105 ℃ is 81 percent, the stability after being heated for 15min at the constant temperature of 120 ℃ is 63.1 percent, the stability after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature is 75.3 percent, the stability after being heated for 15min at the temperature of 120 ℃ is 61.1 percent, and the content of insoluble sulfur particles with the particle size of less than 100 mu m of the insoluble sulfur finished product accounts for 93.2 percent of the total insoluble sulfur mass.
Example 53
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 25.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.8 percent; the stability of the insoluble sulfur finished product is 81.5 percent after being heated for 15min at the temperature of 105 ℃, 63.4 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 75.4 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, the stability of the insoluble sulfur finished product is 61.3 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 93.5 percent of the total mass of the insoluble sulfur.
Example 54
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 26.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.6 percent; the stability of the insoluble sulfur finished product is 81.4% after heating for 15min at the temperature of 105 ℃, 63.2% after keeping the temperature for 15min at the temperature of 120 ℃, 75.2% after storing for 9 months at normal temperature and heating for 15min at the temperature of 105 ℃, 61.4% after heating for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.4% of the total insoluble sulfur mass.
Example 55
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 27.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.8 percent; the stability of the insoluble sulfur finished product is 81.3 percent after being heated for 15min at the temperature of 105 ℃, 63.5 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 75.6 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, the stability of the insoluble sulfur finished product is 62 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 93.5 percent of the total insoluble sulfur mass.
Example 56
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 28.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 95 percent; the stability of the insoluble sulfur finished product is 81.5 percent after being heated for 15min at the temperature of 105 ℃, 63.7 percent after being kept at the constant temperature of 120 ℃ for 15min, the stability of the insoluble sulfur finished product is 75.8 percent after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, the stability of the insoluble sulfur finished product is 61.8 percent after being heated for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 93.2 percent of the total mass of the insoluble sulfur.
Example 57
An insoluble sulfur production stabilizer, substantially as in example 10, except that the stabilizer C is β -carotene.
Example 58
A process for producing insoluble sulfur which is substantially the same as in example 29 except that the stabilizer in the step (2) is the one produced in example 57.
The content of insoluble sulfur in the prepared insoluble sulfur finished product is 94.7 percent; the stability of the insoluble sulfur finished product is 81.2% after heating for 15min at the temperature of 105 ℃, 63.2% after keeping the temperature for 15min at the temperature of 120 ℃, 75% after storing for 9 months at normal temperature and heating for 15min at the temperature of 105 ℃, 61% after heating for 15min at the temperature of 120 ℃, and the content of insoluble sulfur particles with the particle size of less than 100 mu m in the insoluble sulfur finished product accounts for 93.3% of the total insoluble sulfur.
Claims (10)
1. A preparation method of insoluble sulfur is characterized in that a semi-finished product of the insoluble sulfur is sequentially extracted, dried, sieved and oil-filled to obtain a finished product of the insoluble sulfur;
the drying treatment refers to uniformly mixing the product obtained by extraction with a stabilizer and then carrying out vacuum drying;
the stabilizer is a stabilizer A or a stabilizer B, and the addition amount of the stabilizer is 0.5-1.0% of the quality of the product obtained by extraction;
or the stabilizer is a mixture of a stabilizer A and a stabilizer B in a mass ratio of 1-5: 5-1, a mixture of a stabilizer A and a stabilizer C in a mass ratio of 1-5: 1-2, a mixture of a stabilizer B and a stabilizer C in a mass ratio of 1-5: 1-3, a mixture of a stabilizer A and a stabilizer B and a stabilizer C in a mass ratio of 1-5: 1-3: 1, and the adding amount of the stabilizer is 0.5-0.8% of the mass of the product obtained by extraction;
stabilizer a is [ [2- (benzylthio) ethyl ] thio ] benzene; the stabilizer B is DOPO; the stabilizer C is alpha-methyl styrene, p-methyl styrene, isopropenyl benzene, turpentine, lemon oil, terpene, dibenzothiazyl disulfide or dimercaptobenzothiazole.
2. The method for preparing insoluble sulfur according to claim 1, wherein the terpene is a monoterpene, a sesquiterpene, a diterpene, a triterpene or a tetraterpene.
3. The method for preparing insoluble sulfur according to claim 1, wherein the temperature of vacuum drying is 55-60 ℃, the time is 1-5 h, and the pressure is60 kPa.
4. The preparation method of insoluble sulfur according to any one of claims 1 to 3, wherein the oil-filling treatment is to uniformly mix the screened insoluble sulfur semi-finished product and filling oil, and a certain amount of dispersant 1 is added, the addition amount of the dispersant 1 is 0.3 to 0.6 percent of the mass of the screened insoluble sulfur semi-finished product, and the dispersant 1 is fatty acid amide polyoxyethylene ether, isooctanol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, fatty acid diethanolamide, fatty alcohol polyoxyethylene ester, methoxypolyethylene glycol or allyl alcohol polyoxyalkyl ether.
5. The method for preparing insoluble sulfur according to claim 4, wherein the filling oil is naphthenic oil, aromatic oil or white oil, and the filling oil accounts for 15-35% of the mass of the sieved insoluble sulfur semi-finished product.
6. The method for preparing insoluble sulfur according to claim 4, wherein the preparation of the semi-finished product of insoluble sulfur comprises the following steps:
s1, taking industrial sulfur as a raw material, heating the industrial sulfur to 230-270 ℃ at a heating rate of 5 ℃/min, and carrying out polymerization reaction for 0.75-2.5 h to obtain a polymer;
s2, placing the polymer obtained in the step S1 in a quenching liquid for quenching treatment; the quenching liquid is a weakly acidic aqueous solution with the pH value of 5-6 adjusted by nitric acid, or an aqueous solution containing ethylene glycol, wherein the ethylene glycol accounts for 15-35% of the weight of water; the temperature of the quenching liquid is-4 to-16 ℃;
s3, obtaining an insoluble sulfur semi-finished product through curing, crushing and sieving treatment.
7. The method for preparing insoluble sulfur according to claim 6, wherein the temperature of the curing treatment in step S3 is 45-60 ℃ for 4-6 hours.
8. The method for preparing insoluble sulfur according to claim 6, wherein the pulverization in step S3 is to pulverize insoluble sulfur to 80-150 mesh.
9. The method according to claim 6, wherein the sieving treatment in step S3 is a 100 mesh sieve.
10. The method for preparing insoluble sulfur according to claim 6, wherein the content of insoluble sulfur in the finished product of insoluble sulfur is 93-98.5%; the stability of the insoluble sulfur finished product is 80-85% after being heated for 15min at the temperature of 105 ℃, 62-70% after being kept at the constant temperature of 120 ℃ for 15min, 75-80% after being heated for 15min at the temperature of 105 ℃ after being stored for 9 months at normal temperature, and 58-65% after being heated for 15min at the temperature of 120 ℃; the mass of insoluble sulfur particles with the particle size of less than 100 mu m accounts for 93-98% of the total mass of insoluble sulfur.
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