CN101121684A - Method for producing rubber vulcanization accelerant zinc dibutyl dithiocarbamate - Google Patents
Method for producing rubber vulcanization accelerant zinc dibutyl dithiocarbamate Download PDFInfo
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- CN101121684A CN101121684A CNA200710189605XA CN200710189605A CN101121684A CN 101121684 A CN101121684 A CN 101121684A CN A200710189605X A CNA200710189605X A CN A200710189605XA CN 200710189605 A CN200710189605 A CN 200710189605A CN 101121684 A CN101121684 A CN 101121684A
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Abstract
The invention is a production method for the rubber vulcanization accelerator diethyl dithiocarbamate zinc, solving the problems in the other methods. The ratio of the raw materials is diethylamine to carbon bisulfide to sodium hydroxide to zinc chloride is equal to 1 to from 0.90 to 1.25 to from 0.98 to 1.30 to from 0.50 to 0.65. The technological process is: in the reaction kettle filler with the purified water, the diethylamine and sodium hydroxide of the prescribed quantity are stired and added in order; the temperature to controlled be 10 to 35 Celsius system; the method is begin to drop the carbon bisulfide liquid of the prescribed quantity; the operation is controlled for 5 to 7 hours; after the dropping, the method is to stir for a certain period of time; the proper temperature is controlled and the zinc chloride solution for the double decomposition reaction is dropped; after the reaction, the pH value of the reaction solution with the sulfuric acid is adjusted to be in the proper scope; thus the reaction is finished; the material is stirred for 2 hours and the solid and liquid are separated; the liquid is dropped, and after being dried, smashed, screened and packed, the product is made.
Description
One, technical field: the present invention relates to a kind of thiofide, especially the production method of rubber vulcanization accelerant zinc dibutyl dithiocarbamate.
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 countries 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 promotor 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.Rubber vulcanization accelerant zinc dibutyl dithiocarbamate (EZ) 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 method of rubber vulcanization accelerant zinc dibutyl dithiocarbamate (EZ), the domestic two-step approach that generally adopts is at present produced, mostly be to be starting material, earlier through condensation reaction synthetic intermediate Thiocarb with diethylamine, dithiocarbonic anhydride, liquid caustic soda and zinc sulfate.Then, carry out replacement Treatment with Thiocarb and zinc sulfate again, last synthetic rubber vulcanization accelerator zinc diethyldithiocarbamate (EZ).These technologies exist synthesis step many aborning, and operation is difficult for, and the waste gas, the wastewater flow rate that produce in the production process are big, and be serious to equipment corrosion, shortcomings such as energy consumption height.Even more serious is that production safety hidden danger is big, brings very big difficulty to environment protection treating, is difficult to realize that " cleaning is green " produces, and does not meet national environmental protection policy and energy-conservation production requirement.And the product fusing point is low, and outward appearance is dark, and yield is low, is difficult to satisfy the high-end requirement of domestic and international selling market.
Three, summary of the invention: the purpose of this invention is to provide a kind ofly improve the quality of products, save energy and reduce the cost, the production method of the rubber vulcanization accelerant zinc dibutyl dithiocarbamate of green rubber ingredients, it has overcome the shortcoming that other technology exists, the object of the present invention is achieved like this, the production method of rubber vulcanization accelerant zinc dibutyl dithiocarbamate " single stage method ", be as solvent with water, under the phase-transfer catalyst effect, utilizing " zinc chloride " is displacer, the novel method of one-step synthesis rubber vulcanization accelerant zinc dibutyl dithiocarbamate.Half-finished generation link in the middle of having reduced has reduced production cost, reduces environmental pollution.This method is with short production cycle, safety coefficient is high, almost do not have exhaust gas emission, and product fusing point height, outward appearance are white, obviously are better than other production method, and comprehensive cost is low, can satisfy the high-end market requirement.
1, the present invention is raw materials used
1.1, diethylamine: the colourless liquid volatile, that the ammonia smell is arranged.Water-soluble, ethanol and ether.Be used for pharmacy thing, dyestuff, vulcanizer and sterilant etc.Vapour pressure: 25901Pa/20 ℃, flash-point-26 ℃, 55.5 ℃ of boiling points, fusing point-48 ℃.Good stability.
1.2, 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.
1.3, sodium hydroxide: have another name called sheet alkali, a kind of white plates solid.Density 2.130g/cm
3318.4 ℃ of fusing points.1390 ℃ of boiling points.Industrial goods contain a spot of sodium-chlor and yellow soda ash, are the solids of White-opalescent, and dilution property is strong, reveal when putting in the air, easily absorb airborne moisture deliquescence gradually, and last full one-tenth solution easily absorbs airborne CO
2Be transformed into soda ash, the aqueous solution is strong basicity, is dissolved in glycerine and ethanol, is not dissolved in acetone, and severe corrosive is arranged.
1.4, sulfuric acid: pure product are colourless, odorless, transparent colourless liquid, the acidity of flaunting the superiority.Commercially available industrial sulphuric acid is colourless to little yellow, even reddish-brown.Relative density: 98% sulfuric acid is 1.8365 (20 ℃), and 93% sulfuric acid is 1.8276 (20 ℃), and fusing point is 10.35 ℃, and boiling point is 338 ℃.Very strong adsorptive power is arranged, can mix by different ratios with water, and emit a large amount of heat, be inorganic acid, corrodibility is very strong, very alive group of chemical property.Almost can generate salt with all metals and oxide compound thereof, light oxide compound reaction, can also with the salt effect of other mineral acid.When dilute sulphuric acid, can only annotate sour entry, the sour accident of spray of blasting in case the acid solution surface local is overheated.Concentration is lower than 76% sulfuric acid and metal reaction meeting releasing hydrogen gas.
1.5, zinc chloride: pure product are white powder, odorless, easily deliquescence.Fusing point (℃): 365 boiling points (℃): 732, relative density (water=1): 2.91.Water-soluble, ethanol, ether, glycerine are insoluble to liquefied ammonia.Main application:, also be used for industries such as battery, plating, medicine as dewatering agent, condensing agent, mordant, oil scavenging agent.This product has to stimulate and corrosive nature, sucks zinc chloride smog and can cause bronchopneumonia, and high density sucks and can cause death.
2, production formula of the present invention:
Raw-material stoichiometry mol ratio:
Diethylamine: dithiocarbonic anhydride: sodium hydroxide: zinc chloride=1: 0.90-1.25: 0.98-1.30: 0.50-0.65
3, production process of the present invention: in the reactor that fills purified water, add diethylamine, the sodium hydroxide of specified amount under the whipped state successively; Control 10--35 ℃, begin to drip the dithiocarbonic anhydride liquid of specified amount, period 5--7 hour; After dropwising, stir certain hour, the control optimal temperature drips liquor zinci chloridi, carries out replacement(metathesis)reaction; Reaction is an OK range with sulfuric acid conditioned reaction liquid pH value after finishing, i.e. reaction finishes; Stirred 2 hours the back, 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 product has the following advantages with its corresponding product contrast:
(1), the toxic gas quantity discharged is few in the process of producing product, environmental pollution is little.Wastewater flow rate is few, with short production cycle.
(2), product appearance is white than other similar product color, the grain warp is thin, loose.
(3), the first fusing point 〉=178 ℃ of product, purity 〉=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, shows superior curability than similar product.
Four, description of drawings: Fig. 1 is the process flow sheet of the production method of rubber vulcanization accelerant zinc dibutyl dithiocarbamate, and its technological process is: in the reactor that fills purified water, add diethylamine, the sodium hydroxide of specified amount under the whipped state successively.Control 10--35 ℃, begin to drip the dithiocarbonic anhydride liquid of specified amount, period 5-7 hour; After dropwising, stir certain hour, the control optimal temperature drips liquor zinci chloridi, carries out replacement(metathesis)reaction; Reaction is an OK range with sulfuric acid conditioned reaction liquid pH value after finishing, i.e. reaction finishes; Stirred 2 hours the back, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
Five, embodiment: the raw materials used and proportioning of the present invention is:
Diethylamine: dithiocarbonic anhydride: sodium hydroxide: zinc chloride=1: 0.90-1.25: 0.98-1.30: 0.50-0.65
Its technological process is: in the reactor that fills purified water, add diethylamine, the sodium hydroxide of specified amount under the whipped state successively; Control 10--35 ℃, begin to drip the dithiocarbonic anhydride liquid of specified amount, period 5-7 hour; After dropwising, stir certain hour, the control optimal temperature drips liquor zinci chloridi, carries out replacement(metathesis)reaction; Reaction is an OK range with sulfuric acid conditioned reaction liquid pH value after finishing, i.e. reaction finishes; Stirred 2 hours the back, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
Claims (1)
1. the production method of rubber vulcanization accelerant zinc dibutyl dithiocarbamate, it is characterized in that: raw materials used and proportioning is, diethylamine: dithiocarbonic anhydride: sodium hydroxide: zinc chloride=1: 0.90-1.25: 0.98-1.30: 0.50-0.65, its technological process is: in the reactor that fills purified water, add diethylamine, the sodium hydroxide of specified amount under the whipped state successively; Control 10-35 ℃, begin to drip the dithiocarbonic anhydride liquid of specified amount, period 5-7 hour; After dropwising, stir certain hour, the control optimal temperature drips liquor zinci chloridi, carries out replacement(metathesis)reaction; Reaction is an OK range with sulfuric acid conditioned reaction liquid pH value after finishing, i.e. reaction finishes; Stirred 2 hours the back, carries out solid-liquid separation, and liquid is given up, and solid dries, pulverize, sieve, pack and get final product.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA200710189605XA CN101121684A (en) | 2007-09-19 | 2007-09-19 | Method for producing rubber vulcanization accelerant zinc dibutyl dithiocarbamate |
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| CNA200710189605XA CN101121684A (en) | 2007-09-19 | 2007-09-19 | Method for producing rubber vulcanization accelerant zinc dibutyl dithiocarbamate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848477A (en) * | 2020-07-24 | 2020-10-30 | 新乡市瑞丰新材料股份有限公司 | Preparation method of rubber vulcanization accelerator |
| CN114213297A (en) * | 2021-12-01 | 2022-03-22 | 蔚林新材料科技股份有限公司 | Method for continuously synthesizing rubber vulcanization accelerator EZ |
-
2007
- 2007-09-19 CN CNA200710189605XA patent/CN101121684A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848477A (en) * | 2020-07-24 | 2020-10-30 | 新乡市瑞丰新材料股份有限公司 | Preparation method of rubber vulcanization accelerator |
| CN114213297A (en) * | 2021-12-01 | 2022-03-22 | 蔚林新材料科技股份有限公司 | Method for continuously synthesizing rubber vulcanization accelerator EZ |
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Open date: 20080213 |