CN1193928C - Method for preparing high quality insoluble sulphur - Google Patents
Method for preparing high quality insoluble sulphur Download PDFInfo
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- CN1193928C CN1193928C CN 02122115 CN02122115A CN1193928C CN 1193928 C CN1193928 C CN 1193928C CN 02122115 CN02122115 CN 02122115 CN 02122115 A CN02122115 A CN 02122115A CN 1193928 C CN1193928 C CN 1193928C
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- insoluble sulfur
- package stabilizer
- stabilizer
- insoluble
- sulphur
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Abstract
The present invention relates to a method for preparing high quality insoluble sulfur. More specifically, melting polymerization is carried out at the temperature of 250 to 350DEGC; quenching liquid is neutral subacidic or is a water solution containing an organic stabilizing agent; solidification is completed in 2.5 to 6.5 hours at the temperature of 55 to 75 DEG C. The obtained insoluble sulfur is stabilized by a composite stabilizer A and a composite stabilizer B and heated for 0.5 to 3.0 hours at the temperature of 50 to 80DEGC. The content of the obtained insoluble sulfur is from 97 to 98%; the obtained insoluble sulfur is high quality insoluble sulfur which has the thermal stability rate of 85 to 89% for 15 minutes at the temperature of 110 DEG C. The single-pass yield of the insoluble sulfur is from 38 to 40%.
Description
Technical field
The invention relates to a kind of preparation method of high quality insoluble sulphur, specifically, the invention relates to a kind of method of preparation high-content, high-thermostability insoluble sulfur.
Background technology
In recent years, in rubber industry, substitute common SULPHUR POWDER (being solubility sulphur) and make vulcanizer, be subjected to generally attention both domestic and external with insoluble sulfur.The variant of sulphur is a lot, and the person that generally is dissolved in dithiocarbonic anhydride is called soluble sulfur; The person is called insoluble sulfur to be insoluble to dithiocarbonic anhydride.Insoluble sulfur is the high molecular polymer of sulphur, because of it is difficult for bloom in the rubber item course of processing, so also claim " no blooming sulphur ".
The insoluble sulfur that contains 30-100% has purposes widely in rubber industry.Compare with common soluble sulfur, insoluble sulfur is used for rubber item and has the following advantages: 1. no blooming in staging life, keep the gum base ingredients homogeneous, and stable performance, and can prevent the pollution of goods to mould.2. in the sizing material of cis-butadiene cement and butyl rubber, common sulphur travelling speed is very high, and insoluble sulfur does not have transport phenomena in adjacent glue-line.3. because insoluble sulfur is a polymkeric substance, and before reaching curing temperature, it has certain chemistry and physics inertia, and after reaching curing temperature, it has one " activation stage ", i.e. chain type unzipping is accelerated vulcanization rate.So can reduce incipient scorch with depositing in the process mixing.4. shorten the vulcanization of rubber time, reduce sulfur consumption, improve the aging resistance of goods.5. help the bonding of rubber and other material.
The application of insoluble sulfur in radial not only can improve the intensity of doughnut greatly, and can increase the wear resistance and the work-ing life of tire.In developed country, the radial-ply tyre of excellent property substitutes common tire, realizes the tire meridianization, has become the tire industry development; Along with developing of automobile industry and competition, the market requirement of high-quality insoluble sulfur is with increasing.The high-performance of high quality insoluble sulphur in rubber item is used makes its price higher, is about tens of times of common sulphur; Insoluble sulfur provides an effective way for the valueization of a large amount of common sulphur of industrial by-product.Therefore, the novel preparation method of exploitation high quality insoluble sulphur has remarkable economical and social benefit.
The preparation method of insoluble sulfur has multiple, wherein comparatively commonly scorification and vapour phase processes.Compare with vapour phase processes, scorification has advantages such as polymeric reaction condition gentleness, operational safety, energy consumption are little, has avoided high-temperature evaporation method problem, the problem includes: problems such as equipment cost inflammable, explosive, perishable, that easily pollute and bring therefrom.For example: patent of invention USP4,359,452 vapour phase processes that adopted are fused sulphur to be fed in the spiral tube 500 ℃ or higher temperature vaporize.Bibliographical information is arranged, and a diameter is 200 millimeters; Height is 500 millimeters; Capacity is the vaporization still of 10 kilograms of SULPHUR POWDER, then requires it 600 ℃ of ability 15-20 kilograms per centimeter
2Pressure, and anti-sulphur corrosion.Otherwise metal-salt or metallic sulfide are sneaked in the product, can influence the stability in storage of insoluble sulfur.Scorification is general only to be needed below 400 ℃.Yet the once through yield of scorification is lower, and the product quality of insoluble sulfur is relatively poor.
Summary of the invention
The object of the invention provides a kind of method for preparing high-content, high thermal stability, high quality insoluble sulphur with scorification.
For achieving the above object, technical scheme of the present invention is: disclose a kind of preparation method of high quality insoluble sulphur, melt polymerization carries out under lower temperature, and the melt polymerization temperature is at 250-350 ℃; Quenching liquid is neutrality, slightly acidic or the aqueous solution that contains organic stablizer; Be solidificated in 55-75 ℃, finish in 2.5-6.5 hour; Resulting insoluble sulfur adopts one package stabilizer A and one package stabilizer B, and stablizes in 0.5-3.0 hour 50-80 ℃ of heating; One package stabilizer A is an organic metal salt; One package stabilizer B is an alkenes compounds.
Quenching liquid is neutral, slightly acidic (HNO
3Regulate pH 4.5-6) or contain the aqueous solution of organic stabilizers such as Virahol, tetramethylolmethane, sorbyl alcohol.
One package stabilizer A is for containing organic salts such as metal ion Pb; One package stabilizer B is for containing alkenes compounds such as dodecylene-1 grade.
One package stabilizer A contains in the organic salt of metal ion Pb, Ba, Mg, Li, Zn, Al, Sn one or more; One package stabilizer B be dodecylene-1 arranged, contain vaccenic acid-1, in the benzo cyclopropylene, propenylbenzene, a-vinyl toluene, p-methylstyrene, turps, terpenes one or more.
The add-on of one package stabilizer A is 0.01-0.05% (to an insoluble sulfur), and the add-on of one package stabilizer B is 0.5-1.8% (to an insoluble sulfur).
One package stabilizer A and one package stabilizer B amount ratio are 1: 20-180 (weight).
The preparation method of a kind of high quality insoluble sulphur of the present invention carries out according to the following steps: according to the selected sulphur raw material of the present invention is industrial top grade sulphur.Before the raw materials melt polymerization, use N
2Displacement 10-20min.When reaching the fusing point of common sulphur, at first become low viscosity liquid sulphur S
λ(noncrystal) continues to be heated to 159 ℃, and the viscosity of Molten sulphur can increase suddenly, can increase 100 times.Under this temperature, ring-type sulphur is subjected to thermal excitation, and ring is opened, and becomes the both-end free radical.Along with the rising of temperature, this both-end free radical generates long-chain both-end free radical through chain polymerization.When temperature reaches 250-350 ℃, polymkeric substance from reactor bottom blowing, is entered suddenly in the quenching aqueous solution, the polymerization equilibrium under the high temperature " is freezed ", polyreaction promptly can stop.Obtain a kind of sulphur polymer elastomer this moment, it is insoluble and mixture soluble sulfur.
Quenching liquid of the present invention is neutrality, slightly acidic or the aqueous solution that contains organic stablizer.Quenching liquid can add nitric acid and regulate pH4.5-6.Stablizer can be selected for use: Virahol, tetramethylolmethane, sorbyl alcohol etc.According to the present invention, contain the elastic material of solubility and insoluble sulfur, through 55-75 ℃, heat and be cured in 2.5-6.5 hour, promptly obtain the crumbly mass that is easy to pulverize.Through pulverizing, the 100-200 order that sieves extracts crumbly mass with dithiocarbonic anhydride, obtains insoluble sulfur after the extraction, and its content is at 98.5-99%.The insoluble sulfur that obtain this moment is a kind of metastable state material, and the trend of returning low molecule sulphur is still arranged.For the polymer molecule that makes insoluble sulfur is difficult for degraded, need to add stablizer.
The present invention selects two class one package stabilizers for use: one package stabilizer A and one package stabilizer B.One package stabilizer A, as: the organic salt that contains Pb, Ba, Mg, Li, Zn, Al, Sn; And one package stabilizer B, as: dodecylene-1, octadecylene-1, benzo cyclopropylene, alpha-methyl styrene, propenylbenzene, turps, Vinylstyrene, p-methylstyrene, terpenes etc.The add-on of one package stabilizer A is 0.01-0.05% (to an insoluble sulfur), and the add-on of one package stabilizer B is 0.5-1.8% (to an insoluble sulfur).The insoluble sulfur that adds stablizer through 50-80 ℃ of heating 0.5-3.0 hour, promptly obtains insoluble sulfur content at 97-98%; 110 ℃, 15 minutes thermal stability rates are the 85-89% high quality insoluble sulphur.The insoluble sulfur once through yield is 38-40%.Can carry out oil-filled as required.
The thermal stability rate calculation formula:
Ts: thermal stability rate
W
1: the insoluble sulfur example weight that experiment takes by weighing
W
2: the example weight of residual insoluble sulfur is according to method provided by the invention after heat is surely tested, and common sulphur promptly obtains the insoluble sulfur of high-content, high thermal stability rate through polymerization, quenching, curing, pulverizing, extraction, stable, dry.
Below by embodiment in detail the present invention is described in detail:
Embodiment 1
120 gram SULPHUR POWDER (industrial top grade, content 99.9%) are placed reactor, use N
2Replaced 10 minutes, the intensification polymerization when temperature reaches 280 ℃, from reactor bottom blowing, enters the slightly acidic quenching aqueous solution that contains Virahol (0.1%) immediately and (contains HNO
3, pH5.5) in.Place 65-70 ℃ of baking oven to solidify 2.5 hours resulting elastomeric polymer.Ground 100 mesh sieves after the taking-up.Extract with dithiocarbonic anhydride.One package stabilizer A-stearic acid tin (0.01%, to insoluble sulfur) and one package stabilizer B-p-methylstyrene (1.2%, to insoluble sulfur) are joined in the mixture of insoluble sulfur and dithiocarbonic anhydride, and mixed at room temperature stirred after 1.5 hours, filtered.60 ℃ of filter cake heating 1 hour, through pulverizing, promptly obtaining insoluble sulfur content is 97.3%; At 110 ℃, 15 minutes, thermal stability rate was 86.5% insoluble sulfur.The insoluble sulfur once through yield is 38.5%.
Embodiment 2
120 gram SULPHUR POWDER (industrial top grade, content 99.9%) are placed reactor, use N
2Replaced 10 minutes, the intensification polymerization when temperature reaches 280 ℃, from reactor bottom blowing, enters immediately in the slightly acidic quenching aqueous solution that contains tetramethylolmethane (concentration 0.1%) and (contains HNO
3, pH6.0).With resulting elastomeric polymer, place 60-65 ℃ baking oven to solidify 4.5 hours.Ground 100 mesh sieves after the taking-up.Extract with dithiocarbonic anhydride.One package stabilizer A-barium stearate and lithium stearate (0.013%, to insoluble sulfur) and one package stabilizer B-propenylbenzene (1.2%, to insoluble sulfur) join in the mixture of insoluble sulfur and dithiocarbonic anhydride.Mixed at room temperature stirred after 1 hour, filtered.55 ℃ of filter cake heating 1.25 hours are through pulverizing.Promptly obtaining content is 98.1%; 110 ℃, 15 minutes, thermal stability rate was 88.4% insoluble sulfur.The insoluble sulfur once through yield is 39.2%.
Embodiment 3
120 gram SULPHUR POWDER (industrial top grade, content 99.9%) are placed reactor, use N
2Replaced 10 minutes, the intensification polymerization when temperature reaches 300 ℃, from reactor bottom blowing, enters immediately in the slightly acidic quenching aqueous solution and (contains HNO
3, pH6.5).Resulting elastomeric polymer is placed 65-70 ℃ baking oven, solidified 4.5 hours.Ground 100 mesh sieves after the taking-up.Extract with dithiocarbonic anhydride.One package stabilizer A-lead stearate (0.015%, to insoluble sulfur) and one package stabilizer B-alpha-methyl styrene (0.8%, to insoluble sulfur) join in the mixture of insoluble sulfur and dithiocarbonic anhydride, mixed at room temperature stirred after 1.5 hours, and decompression removes dithiocarbonic anhydride.70 ℃ of heat drying residues 2.5 hours, through pulverizing, promptly obtaining content is 97.8%; 110 ℃, 15 minutes, thermal stability rate was 87.3% insoluble sulfur.The insoluble sulfur once through yield is 38.7%.
Embodiment 4
120 gram SULPHUR POWDER (industrial top grade, content 99.9%) are placed reactor, use N
2Replaced 10 minutes, the intensification polymerization when temperature reaches 300 ℃, from reactor bottom blowing, enters immediately in the slightly acidic quenching aqueous solution and (contains HNO
3, pH6.5).Place 65-70 ℃ baking oven to solidify 4 hours resulting elastomeric polymer.Ground 100 mesh sieves after the taking-up.Extract with dithiocarbonic anhydride.One package stabilizer A-Magnesium Stearate (0.012%, to insoluble sulfur) and one package stabilizer B-terpenes (0.9%, to insoluble sulfur) join in the mixture of insoluble sulfur and dithiocarbonic anhydride, mixed at room temperature stirred after 1.5 hours, decompression removes dithiocarbonic anhydride, 80 ℃ of heat drying residues 0.5 hour, through pulverizing, promptly obtaining content is 97.7% insoluble sulfur.This insoluble sulfur charges into RUBBER PROCESS OIL (oil-filled amount 20%), 110 ℃ of its oil-filled insoluble sulfurs, and 15 minutes, thermal stability rate was 89.4%.The insoluble sulfur once through yield is 40.0%.
Embodiment 5
120 gram SULPHUR POWDER (industrial top grade, content 99.9%) are placed reactor, use N
2Replaced 10 minutes, the intensification polymerization when temperature reaches 320 ℃, from the Polycondensation Reactor and Esterification Reactor blowing, enters immediately in the slightly acidic quenching aqueous solution and (contains HNO
3, pH6.5).Resulting elastomeric polymer is placed 65-70 ℃ baking oven, solidified 5 hours.Ground 100 mesh sieves after the taking-up.Extract with dithiocarbonic anhydride.One package stabilizer A-Zinic stearas (0.01%, to insoluble sulfur) and one package stabilizer B-propenylbenzene (1.35%, to insoluble sulfur) join in the mixture of insoluble sulfur and dithiocarbonic anhydride, mix and stir after 2 hours, decompression removes dithiocarbonic anhydride, heat 60 ℃ 2 hours, through pulverizing, promptly obtaining content is 98.3% insoluble sulfur.This insoluble sulfur charges into RUBBER PROCESS OIL (oil-filled amount 20%), 110 ℃ of its oil-filled insoluble sulfurs, and 15 minutes, thermal stability rate was 90.1%.The insoluble sulfur once through yield is 39.7%.
Embodiment 6
120 gram SULPHUR POWDER (industrial top grade, content 99.9%) are placed reactor, use N
2Replaced 10 minutes, the intensification polymerization when temperature reaches 320 ℃, from the Polycondensation Reactor and Esterification Reactor blowing, enters immediately in the slightly acidic quenching aqueous solution that contains sorbyl alcohol (0.5%) and (contains HNO
3, pH6.5).Resulting elastomeric polymer is placed 65-70 ℃ baking oven, solidified 6 hours.Ground 100 mesh sieves after the taking-up.Extract with dithiocarbonic anhydride.One package stabilizer A-lead stearate (0.012%, to insoluble sulfur) and one package stabilizer B-dodecylene-1 (1.2%, to insoluble sulfur) join in the mixture of insoluble sulfur and dithiocarbonic anhydride, mix and stir after 1.5 hours, decompression removes dithiocarbonic anhydride, heat 70 ℃ 1.5 hours, through pulverizing, promptly obtaining content is 97.4% insoluble sulfur.This insoluble sulfur charges into RUBBER PROCESS OIL (oil-filled amount 20%), 110 ℃ of its oil-filled insoluble sulfurs, and 15 minutes, thermal stability rate was 90.1%.The insoluble sulfur once through yield is 38.7%.
Embodiment 7
120 gram SULPHUR POWDER (technical grade, content 99.9%) are placed reactor, use N
2Replaced 10 minutes, the intensification polymerization when temperature reaches 350 ℃, from the Polycondensation Reactor and Esterification Reactor blowing, enters immediately in the slightly acidic quenching aqueous solution and (contains HNO
3, pH6.5).Resulting elastomeric polymer is placed 65-70 ℃ baking oven, solidified 5 hours.Ground 100 mesh sieves after the taking-up.Extract with dithiocarbonic anhydride.One package stabilizer A-barium stearate (0.015%, to insoluble sulfur) and one package stabilizer B-benzo cyclopropylene (0.9%, to insoluble sulfur) join in the mixture of insoluble sulfur and dithiocarbonic anhydride, mix and stir after 1 hour, decompression removes dithiocarbonic anhydride, heat 65 ℃ 1.3 hours, through pulverizing, promptly obtaining content is 98.3% insoluble sulfur.This insoluble sulfur charges into RUBBER PROCESS OIL (oil-filled amount 20%), 110 ℃ of its oil-filled insoluble sulfurs, and 15 minutes, thermal stability rate was 89.4%.The insoluble sulfur once through yield is 40.1%.
Claims (4)
1. the preparation method of an insoluble sulfur, with the method for melt polymerization, through CS2 quenching, curing, extraction, one package stabilizer stabilizing step, it is characterized in that: melt polymerization carries out under lower temperature, and the melt polymerization temperature is at 250-350 ℃; Quenching liquid is neutrality, slightly acidic or the aqueous solution that contains organic stablizer, and wherein organic stabilizer is Virahol, tetramethylolmethane or sorbyl alcohol; Be solidificated in 55-75 ℃, finish in 2.5-6.5 hour; Through extraction, resulting insoluble sulfur adopts one package stabilizer A and one package stabilizer B, and stablizes in 0.5-3.0 hour 50-80 ℃ of heating, obtains insoluble sulfur; Wherein one package stabilizer A is the organic metal salt that contains metal ion Pb, Ba, Mg, Li, Zn, Al, Sn; One package stabilizer B is one or more in dodecylene-1, vaccenic acid-1, benzo cyclopropylene, propenylbenzene, a-vinyl toluene, p-methylstyrene, turps, Vinylstyrene, the terpenes.
2. according to the described preparation method of claim 1, it is characterized in that: described quenching liquid is neutrality or weakly acidic water solution, wherein weakly acidic water solution HNO
3Regulate pH4.5-6.
3. according to the described preparation method of claim 1, it is characterized in that: the dosage of described one package stabilizer A is counted between the 0.01%-0.015% with insoluble sulfur; The dosage of one package stabilizer B is counted between the 0.5%-1.8% with insoluble sulfur.
4. according to the described preparation method of claim 1, it is characterized in that: described one package stabilizer A is 1 with the weight consumption ratio of one package stabilizer B: 20-180.
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| CN 02122115 CN1193928C (en) | 2002-05-30 | 2002-05-30 | Method for preparing high quality insoluble sulphur |
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| CN 02122115 CN1193928C (en) | 2002-05-30 | 2002-05-30 | Method for preparing high quality insoluble sulphur |
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| CN1193928C true CN1193928C (en) | 2005-03-23 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323026C (en) * | 2004-10-28 | 2007-06-27 | 王桃仙 | Insoluble sulfur preparation method |
| CN100427386C (en) * | 2005-12-22 | 2008-10-22 | 南化集团研究院 | Medium grade insoluble sulphur preparing process and producing apparatus |
| CN101066753B (en) * | 2007-05-29 | 2010-06-02 | 江西恒兴源化工有限公司 | Continuous one-step process for producing insoluble sulphur |
| CN102897718B (en) * | 2012-09-14 | 2014-10-08 | 河南省开仑化工有限责任公司 | Production method for high-fineness sulfur |
| CN106633937B (en) * | 2015-11-02 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of modified high softening point bitumen particle, preparation method and application |
| CN105694095A (en) * | 2016-01-22 | 2016-06-22 | 上海京海（安徽）化工有限公司 | High-quality and wear-resisting insoluble sulfur for rubber and production process of high-quality and wear-resisting insoluble sulfur |
| CN108129693B (en) * | 2017-12-22 | 2020-10-30 | 蔚林新材料科技股份有限公司 | Oil-extended insoluble sulfur and preparation method and application thereof |
| CN109650839A (en) * | 2019-02-26 | 2019-04-19 | 中国人民解放军陆军勤务学院 | A kind of sulphur concrete and preparation method thereof of anti-distillation corrosion |
| CN114436221B (en) * | 2022-01-12 | 2023-03-10 | 嘉兴学院 | Stabilizer for preparing insoluble sulfur and preparation method thereof |
| CN114348969A (en) * | 2022-01-12 | 2022-04-15 | 嘉兴学院 | Preparation method of insoluble sulfur |
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