CN101108819A - Process for producing vulcanization of rubber accelerant disulfide diisobutyl thiuram - Google Patents
Process for producing vulcanization of rubber accelerant disulfide diisobutyl thiuram Download PDFInfo
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- CN101108819A CN101108819A CNA2007100549644A CN200710054964A CN101108819A CN 101108819 A CN101108819 A CN 101108819A CN A2007100549644 A CNA2007100549644 A CN A2007100549644A CN 200710054964 A CN200710054964 A CN 200710054964A CN 101108819 A CN101108819 A CN 101108819A
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Abstract
A production method of the diisobutylthiuram disulfide-accelerant of the vulcanization of rubber is provided, which is the production method of the accelerant of the vulcanization of rubber. The method overcomes the defects existing when others produce the product. The raw materials and the mixture ratio of the invention are diisobutylamine : carbon disulfide : oxidant equals to 1 : 1-1.3 : 0.35-0.55; the production method is that enamel reaction axe with volume of 2000L is added with the diisobutylamine, alcohols or water and phase transfer catalyst with specified amount in turns; the cooling water is turned on with temperature reduced to the preferential temperature and is added with carbon disulfide liquid measured accurately by drops, and the time is controlled; after added by drops, the pH value of the reaction liquid is measured to the specialized range; after the pH value is stable, the preferential temperature is controlled and the oxidant is added by drops to carry out oxidation reaction. After the oxidation reaction, the insulation temperature is kept for 1h and solid-liquid separation is conducted to abandon the liquid and dry, crush, sieve and pack the solid.
Description
One, technical field:
The present invention relates to a kind of thiofide, especially the production method of vulcanization of rubber accelerant disulfide diisobutyl thiuram.
Two, background technology:
In recent years, along with the fast development of Rubber processing industry, the fast development of domestic automobile industry, communication industry drives the Rubber processing industry and increases fast, unprecedented good opportunity is provided for the development of Rubber Chemicals Industries.Since the entry to WTO,, compared, still have very big gap at aspects such as product inner quality and " green " green technologies with developed country in the world though the production of China's rubber accelerator product is improved largely.China's Auxiliaries Industry will enlarge the market share green, nontoxic auxiliary agent product, cut down significantly to contain the sulfenamide type accelerators that can produce carcinogenic substance in nitrosamine, the reprocessing process.To advancing cleaner production, the green auxiliary agent of development to give great attention, particularly eliminate the understanding that produces nitrosamine carcinogens product gradually and be rooted in the hearts of the people, and obtain first-stage success.Vulcanization of rubber accelerant disulfide diisobutyl thiuram (TiBTD) is exactly a kind of green environmental protection thiofide, is widely used in the sulfuration processing of natural rubber, polyisoprene rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, terpolymer EP rubber and paracril etc.
The production technology of vulcanization of rubber accelerant disulfide diisobutyl thiuram (TiBTD), the domestic soda acid method that generally adopts is at present produced, these technologies are aborning except that producing a large amount of inorganic salt waste water, even more serious is because of using severe corrosive raw materials such as a large amount of acid, alkali, cause that production safety hidden danger is big, energy consumption is high, bring very big difficulty to environment protection treating, do not meet national environmental protection policy and energy-conservation production requirement.And the product fusing point is low, and the outward appearance Huang is difficult to satisfy the high-end requirement of domestic and international selling market.
The production method of the vulcanization of rubber accelerant disulfide diisobutyl thiuram of my company research be with alcohols or water be medium as solvent, under the phase-transfer catalyst effect, utilize green oxidation agent " hydrogen peroxide " or " clorox " single stage method synthetic.This method is with short production cycle, safety coefficient is high, almost do not have discharge of wastewater, and product fusing point height, outward appearance are white, obviously are better than other production method, and comprehensive cost is low, can satisfy market demands.
Three, summary of the invention:
The purpose of this invention is to provide a kind of production method of producing vulcanization of rubber accelerant disulfide diisobutyl thiuram, improve the quality of products, energy-saving and cost-reducing, reduce " three wastes " and pollute.
1, the present invention is raw materials used
1.1, diisobutylamine: a kind of colourless liquid, the smell of ammonia is arranged, fusing point :-70 ℃, boiling point: 139.5 ℃ are not volatile, vapour pressure: 1.33kPa/30.6 ℃, flash-point: 29 ℃ are alkalescence, relative density (water=1) 0.74; Relative density (air=1) 4.46 is deposited color for a long time and can be increased the weight of in air.
1.2, hydrogen peroxide: have another name called hydrogen peroxide, a kind of colourless transparent liquid, relative density 1.4067 (25 ℃), water-soluble, pure, ether are insoluble to sherwood oil, and is extremely unstable, meet light, heat, uneven surface, heavy metal and other impurity and can cause decomposition, emit oxygen and heat simultaneously.Have stronger oxidation capacity, be strong oxidizer.More stable under acidic conditions.
1.3, dithiocarbonic anhydride: colourless or little yellow volatility transparent liquid, relative density 1.265, pure product have aromatising flavour, raw product is because of containing sulphur and other impurity is faint yellow, and foul smelling.Boiling point: 46.3 ℃, lightning :-30 ℃.Be slightly soluble in water (22 ℃, 0.22g/100ml; 50 ℃, 0.14g/ml) be dissolved in pure and mild ether, high refractivity is arranged, easily flow severe toxicity.Has very strong dissolving power, solubilized fat, wax, resin, untreated rubber, sulphur, phosphorus etc.Its steam and air mixed are easy to catch fire and explode, threshold concentration 30mg/ml.
1.4, ethanol: the pungent flavour of smells of wine and stimulation is arranged, the volatile and inflammable liquid of water white transparency.Fusing point :-114.1 ℃, boiling point: 78.3 ℃; Vapour pressure: 5.33kPa/19 ℃, flash-point: 12 ℃.Relative density (water=1) 0.79, relative density (air=1) 1.59.Miscible with water, can be miscible of many uses in most organic solvents such as ether, chloroform, glycerine, be a kind of important solvent, be used for to coating, dyestuff, medicine, synthetic rubber, washing composition etc.
2, production formula of the present invention:
Raw-material stoichiometry mol ratio:
Diisobutylamine: dithiocarbonic anhydride: oxygenant (hydrogen peroxide or clorox)=1: 1-1.3: 0.35-0.55
3, production process of the present invention:
In the 2000L enamel reaction still, add diisobutylamine, alcohols or water, the phase-transfer catalyst of specified amount under the whipped state successively.Open water coolant, be cooled to optimal temperature, begin to drip the accurately dithiocarbonic anhydride liquid of metering, the period.After dropwising, measured reaction liquid pH value is to specialized range, treat that pH value is stable after, the control optimal temperature, beginning dropping oxidizing agent (hydrogen peroxide or clorox) is carried out oxidizing reaction.After oxidation finished, insulation reaction was 1 hour again, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
4, the advantage of product of the present invention:
This products production has the following advantages with domestic corresponding product contrast:
(1), in the process of producing product because of not using inorganic acid alkali, so low to production unit corrodibility, the safety coefficient height, environmental pollution is little.The inorganic salt wastewater flow rate that produces is few, with short production cycle; Energy-conservation, consumption reduction.
(2), product appearance is white than other similar product color, the grain warp is thin.
(3), because of not using inorganic acid alkali in the production process, the inorganic impurity of generation is few, good to the organic impurity solvability because of using alcoholic medium simultaneously, so just fusing point is greater than 65 ℃ for product, purity can be big more than 98%.
(4), shelf life of products is long, more stable at ambient temperature.
(5), in vulcanization of rubber experiment: curing time is short, and time of scorch is long, and good heat resistance has more no foaminess, shows superior curability than similar product.
(6), reduce investment in fixed assets, reduction noise, safety coefficient height.
Four, description of drawings:
Fig. 1 is the process flow sheet of the production method of vulcanization of rubber accelerant disulfide diisobutyl thiuram, and its technological process is: in the 2000L enamel reaction still, add diisobutylamine, alcohols or water, the phase-transfer catalyst of specified amount under the whipped state successively.Open water coolant, be cooled to optimal temperature, begin to drip the accurately dithiocarbonic anhydride liquid of metering, the period.After dropwising, measured reaction liquid pH value is to specialized range, treat that pH value is stable after, the control optimal temperature, beginning dropping oxidizing agent (hydrogen peroxide or clorox) is carried out oxidizing reaction.After oxidation finished, insulation reaction was 1 hour again, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
Five, embodiment:
Raw materials used and the proportioning of the present invention is:
Diisobutylamine: dithiocarbonic anhydride: oxygenant=1: 1-1.3: 0.35-0.55
Its technological process is: in the 2000L enamel reaction still, add diisobutylamine, alcohols or water, the phase-transfer catalyst of specified amount under the whipped state successively.Open water coolant, be cooled to optimal temperature, begin to drip the accurately dithiocarbonic anhydride liquid of metering, the period.After dropwising, measured reaction liquid pH value is to specialized range, treat that pH value is stable after, the control optimal temperature, beginning dropping oxidizing agent (hydrogen peroxide or clorox) is carried out oxidizing reaction.After oxidation finished, insulation reaction was 1 hour again, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
Claims (3)
1. the production method of vulcanization of rubber accelerant disulfide diisobutyl thiuram, it is characterized in that: raw materials used and proportioning is: diisobutylamine: dithiocarbonic anhydride: oxygenant=1: 1-1.3: 0.35-0.55; Its production method is: in the 2000L enamel reaction still, add diisobutylamine, alcohols or water, the phase-transfer catalyst of specified amount under the whipped state successively; Open water coolant, be cooled to optimal temperature, begin to drip the accurately dithiocarbonic anhydride liquid of metering, the period; After dropwising, measured reaction liquid pH value is to specialized range, treat that pH value is stable after, the control optimal temperature, the beginning dropping oxidizing agent is carried out oxidizing reaction; After oxidation finished, insulation reaction was 1 hour again, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
2. the production method of vulcanization of rubber accelerant disulfide diisobutyl thiuram according to claim 1, it is characterized in that: raw materials used and proportioning is: diisobutylamine: dithiocarbonic anhydride: hydrogen peroxide=1: 1-1.3: 0.35-0.55; Its production method is: in the 2000L enamel reaction still, add diisobutylamine, ethanol, the phase-transfer catalyst of specified amount under the whipped state successively; Open water coolant, be cooled to optimal temperature, begin to drip the accurately dithiocarbonic anhydride liquid of metering, the period; After dropwising, measured reaction liquid pH value is to specialized range, treat that pH value is stable after, the control optimal temperature begins to drip hydrogen peroxide, carries out oxidizing reaction; After oxidation finished, insulation reaction was 1 hour again, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
3. the production method of vulcanization of rubber accelerant disulfide diisobutyl thiuram according to claim 1, it is characterized in that: raw materials used and proportioning is: diisobutylamine: dithiocarbonic anhydride: clorox=1: 1-1.3: 0.35-0.55; Its production method is: in the 2000L enamel reaction still, add diisobutylamine, water, the phase-transfer catalyst of specified amount under the whipped state successively; Open water coolant, be cooled to optimal temperature, begin to drip the accurately dithiocarbonic anhydride liquid of metering, the period; After dropwising, measured reaction liquid pH value is to specialized range, treat that pH value is stable after, the control optimal temperature begins to drip clorox, carries out oxidizing reaction; After oxidation finished, insulation reaction was 1 hour again, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948417A (en) * | 2010-04-29 | 2011-01-19 | 濮阳蔚林化工股份有限公司 | Preparation method of rubber vulcanization accelerator tetra(isobutyl)thioperoxydicarbamic acid (TiBTD) |
| CN102030694A (en) * | 2010-11-23 | 2011-04-27 | 濮阳蔚林化工股份有限公司 | Preparation method of thiofide TiBTM (Tetraisobutylethiuram Monosulfide) |
| CN105541683A (en) * | 2016-02-23 | 2016-05-04 | 山东阳谷华泰化工股份有限公司 | Method for preparing tetrathioperoxydicarbamic acid |
| CN108129517A (en) * | 2017-12-30 | 2018-06-08 | 西北有色金属研究院 | A kind of preparation method of organic three core molybdenum additives |
| CN109608375A (en) * | 2018-12-29 | 2019-04-12 | 蔚林新材料科技股份有限公司 | A kind of clean preparation method of thiofide TOT-N |
| CN110950790A (en) * | 2019-12-31 | 2020-04-03 | 蔚林新材料科技股份有限公司 | Tetrabutylthiuram disulfide and preparation method and application thereof |
| CN114702462A (en) * | 2022-05-07 | 2022-07-05 | 鹤壁元昊化工有限公司 | Preparation method of secondary amyl thiuram hexasulfide |
-
2007
- 2007-08-15 CN CNA2007100549644A patent/CN101108819A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948417A (en) * | 2010-04-29 | 2011-01-19 | 濮阳蔚林化工股份有限公司 | Preparation method of rubber vulcanization accelerator tetra(isobutyl)thioperoxydicarbamic acid (TiBTD) |
| CN101948417B (en) * | 2010-04-29 | 2011-11-09 | 濮阳蔚林化工股份有限公司 | Preparation method of rubber vulcanization accelerator tetra(isobutyl)thioperoxydicarbamic acid (TiBTD) |
| CN102030694A (en) * | 2010-11-23 | 2011-04-27 | 濮阳蔚林化工股份有限公司 | Preparation method of thiofide TiBTM (Tetraisobutylethiuram Monosulfide) |
| CN102030694B (en) * | 2010-11-23 | 2013-06-05 | 濮阳蔚林化工股份有限公司 | Preparation method of thiofide TiBTM (Tetraisobutylethiuram Monosulfide) |
| CN105541683A (en) * | 2016-02-23 | 2016-05-04 | 山东阳谷华泰化工股份有限公司 | Method for preparing tetrathioperoxydicarbamic acid |
| CN108129517A (en) * | 2017-12-30 | 2018-06-08 | 西北有色金属研究院 | A kind of preparation method of organic three core molybdenum additives |
| CN109608375A (en) * | 2018-12-29 | 2019-04-12 | 蔚林新材料科技股份有限公司 | A kind of clean preparation method of thiofide TOT-N |
| CN110950790A (en) * | 2019-12-31 | 2020-04-03 | 蔚林新材料科技股份有限公司 | Tetrabutylthiuram disulfide and preparation method and application thereof |
| CN114702462A (en) * | 2022-05-07 | 2022-07-05 | 鹤壁元昊化工有限公司 | Preparation method of secondary amyl thiuram hexasulfide |
| CN114702462B (en) * | 2022-05-07 | 2023-01-10 | 鹤壁元昊化工有限公司 | Preparation method of secondary amyl thiuram hexasulfide |
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