CN101973919A - Method for preparing zinc diphenyl dithiocarbamate - Google Patents
Method for preparing zinc diphenyl dithiocarbamate Download PDFInfo
- Publication number
- CN101973919A CN101973919A CN2010105005658A CN201010500565A CN101973919A CN 101973919 A CN101973919 A CN 101973919A CN 2010105005658 A CN2010105005658 A CN 2010105005658A CN 201010500565 A CN201010500565 A CN 201010500565A CN 101973919 A CN101973919 A CN 101973919A
- Authority
- CN
- China
- Prior art keywords
- phenylbenzene
- sodium hydroxide
- preparation
- zinc
- pentanoic
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing zinc diphenyl dithiocarbamate, belonging to the technical field of chemical synthesis. The method comprises the steps of: firstly, reacting carbon disulfide with diphenylamine under the condition that water is used as solvent and sodium hydroxide is used as a catalyst, and then carrying out replacement reaction with zinc chloride. The synthesis can be finished in two steps in the reaction process and is free of complicated processing processes, three wastes are not generated basically, and products have high purity and good color. The invention has the advantages that the sodium hydroxide is cheap and common and is easy to purchase, the method has short production cycle and high safety coefficient, basically no waste gas is discharged, the products have high melting point and white appearance, the total product yield is 80-92% and the comprehensive cost is low.
Description
Technical field
The present invention relates to the novel process of the synthetic phenylbenzene zinc dithiocarbamate of a kind of pentanoic, concrete will be the manufacture method that a kind of pentanoic and dithiocarbonic anhydride, zinc chloride synthesize the phenylbenzene zinc dithiocarbamate, belong to chemosynthesis technical field.
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, subdue 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 and 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.Thiofide phenylbenzene zinc dithiocarbamate (ZDPC) 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.In modern green tire sizing material, can be used for substituting products such as producing the carcinogenic ZDBC of nitrosamine, ZDEC, ZDMC, PZ.Phenylbenzene zinc dithiocarbamate (ZDPC) is a dithiocarbamatetype accelerator, be difficult for producing carcinogenic nitrosamine, the sulfurate activity temperature is lower, operate safer, it is the good activator of thiazole accelerator, can be used for substituting promotor ZDMC (ziram), ZDEC (zinc diethyldithiocarbamate) etc., as the primary accelerator and the secondary accelerator of natural rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, terpolymer EP rubber, natural emulsion and synthetic latex.These product have good anti-coke burning performance, have good anti-scorching performance in as sizing material, can directly add sizing material during use, also can be made into predispersion and add in the latex.
The production method of thiofide phenylbenzene zinc dithiocarbamate (ZDPC), domestic do not have bibliographical information at present, and the main quality index of product of external report is fusing point (178 ℃) on the low side just.The preparation method of a kind of monoalkyl or single aryl dithiocar-bamate is disclosed among the Chinese patent publication number CN1485319A, it is that raw material reacts gained between 0～70 ℃ with R～NH2, CS2, MOH, but described method can not be used for the preparation of phenylbenzene zinc dithiocarbamate.
Summary of the invention
The objective of the invention is to seek a kind of novel process of synthetic rubber vulcanization accelerator phenylbenzene zinc dithiocarbamate of efficient, cleaning.
The present invention includes following steps:
1) under the katalysis of sodium hydroxide, dithiocarbonic anhydride and pentanoic are reacted, through press filtration, obtain the phenylbenzene nabam; When feeding intake, the mass ratio of described dithiocarbonic anhydride and pentanoic is 1: 1.2～2.8, and the mass ratio of described sodium hydroxide and pentanoic is 1: 1.5～5.2;
2) with after phenylbenzene nabam and the solder(ing)acid reaction,, obtain the phenylbenzene zinc dithiocarbamate through centrifuging; When feeding intake, the mass ratio of described zinc chloride and phenylbenzene nabam is 1: 2～4.5.
The present invention elder generation dithiocarbonic anhydride and pentanoic are that solvent, sodium hydroxide react under as the catalyzer condition at water, carry out replacement(metathesis)reaction with zinc chloride again.Two steps of reaction process are synthetic, need not through complicated treating processes, and almost do not have the three wastes and produce, and the purity height of product, color is good.Sodium hydroxide is cheap and common being easy to bought, and 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, and total yield of products is 80～92%, and comprehensive cost is low.Have the following advantages with its corresponding product contrast:
1, do not produce waste gas and waste residue 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, particle diameter is thin, and is loose.
3, the first fusing point 〉=180 ℃ of product, purity 〉=more than 98%.
4, shelf life of products is long, and is more stable at ambient temperature.
5, in vulcanization of rubber test: curing time is short, and time of scorch is long, shows superior curability than like product.
In the step 1) of the present invention, earlier with aqueous sodium hydroxide solution with after pentanoic mixes, the temperature of maintenance reaction system is 25～45 ℃, the dropping dithiocarbonic anhydride aqueous solution.
The mass content of sodium hydroxide is 3.25～8% in the described aqueous sodium hydroxide solution.
The mass content of dithiocarbonic anhydride is 35～80% in the described dithiocarbonic anhydride aqueous solution.
Step 2 of the present invention) in, the phenylbenzene nabam is placed reactor earlier, agitation condition adds solder(ing)acid down.
The mass content of zinc chloride is 5～20% in the described solder(ing)acid; The mass content of zinc chloride is 10% in the preferable solder(ing)acid.
Embodiment
Embodiment 1
With adding the 49.7g pentanoic after 10.1g sodium hydroxide and the 300g water adding reactor stirring and dissolving, stir even; Begin to drip 40% dithiocarbonic anhydride solution 83g, and controlled temperature is at 40 ℃, drips and finish the back and stir 1h, the pH=9 of reaction product phenylbenzene nabam; Filter, phenylbenzene nabam after filtering is put in the metathesis reactor, stir that to add weight concentration down be that to be mixed with concentration be that weight concentration is 10% liquor zinci chloridi for 98% zinc chloride 17.5g, restir 3 hours, centrifuging, wash the phenylbenzene zinc dithiocarbamate, productive rate is 96%, purity 〉=98%.
Embodiment 2
With adding the 61g pentanoic after 25g sodium hydroxide and the 300g water adding reactor stirring and dissolving, stir; Begin to drip 80% dithiocarbonic anhydride solution 27.2g, and controlled temperature is at 30 ℃, drips and finish the back and stir 3h, the pH=8.8 of reaction product phenylbenzene nabam; Filter, phenylbenzene nabam after filtering is put in the metathesis reactor, stir that to add weight concentration down be that to be mixed with weight concentration be 10% liquor zinci chloridi for 98% zinc chloride 21.5g, restir 2 hours, centrifuging, wash the phenylbenzene zinc dithiocarbamate, productive rate is 97%, purity 〉=98%.
Gained thiofide phenylbenzene zinc dithiocarbamate of the present invention has following structure:
Can again product be crushed to, sieve, pack and to obtain finished product less than 60 orders.
The final product quality characteristic:
Fusing point 〉=180 ℃, weight loss on heating≤0.5%, ash content≤0.3%, outward appearance is white powder or solid particulate, purity 98.5～99%.
Claims (7)
1. a kind of preparation method of phenylbenzene zinc dithiocarbamate is characterized in that may further comprise the steps:
1) under the katalysis of sodium hydroxide, dithiocarbonic anhydride and pentanoic are reacted, through press filtration, obtain the phenylbenzene nabam; When feeding intake, the mass ratio of described dithiocarbonic anhydride and pentanoic is 1: 1.2～2.8, and the mass ratio of described sodium hydroxide and pentanoic is 1: 1.5～5.2;
2) with after phenylbenzene nabam and the solder(ing)acid reaction,, obtain the phenylbenzene zinc dithiocarbamate through centrifuging; When feeding intake, the mass ratio of described zinc chloride and phenylbenzene nabam is 1: 2～4.5.
2. according to a kind of preparation method of the described phenylbenzene zinc dithiocarbamate of claim 1, it is characterized in that in the described step 1), earlier with aqueous sodium hydroxide solution with after pentanoic mixes, the temperature of maintenance reaction system is 25～45 ℃, the dropping dithiocarbonic anhydride aqueous solution.
3. according to a kind of preparation method of the described phenylbenzene zinc dithiocarbamate of claim 2, the mass content that it is characterized in that sodium hydroxide in the described aqueous sodium hydroxide solution is 3.25～8%.
4. according to a kind of preparation method of the described phenylbenzene zinc dithiocarbamate of claim 2, the mass content that it is characterized in that dithiocarbonic anhydride in the described dithiocarbonic anhydride aqueous solution is 35～80%.
5. according to a kind of preparation method of claim 1 or 2 described phenylbenzene zinc dithiocarbamates, it is characterized in that described step 2) in, the phenylbenzene nabam is placed reactor earlier, agitation condition adds solder(ing)acid down.
6. according to a kind of preparation method of claim 1 or 2 described phenylbenzene zinc dithiocarbamates, the mass content that it is characterized in that zinc chloride in the described solder(ing)acid is 5～20%.
7. according to a kind of preparation method of the described phenylbenzene zinc dithiocarbamate of claim 6, the mass content that it is characterized in that zinc chloride in the described solder(ing)acid is 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105005658A CN101973919A (en) | 2010-09-28 | 2010-09-28 | Method for preparing zinc diphenyl dithiocarbamate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105005658A CN101973919A (en) | 2010-09-28 | 2010-09-28 | Method for preparing zinc diphenyl dithiocarbamate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101973919A true CN101973919A (en) | 2011-02-16 |
Family
ID=43573837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105005658A Pending CN101973919A (en) | 2010-09-28 | 2010-09-28 | Method for preparing zinc diphenyl dithiocarbamate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101973919A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267931A (en) * | 2011-07-18 | 2011-12-07 | 利民化工股份有限公司 | Metham production process |
| CN107488273A (en) * | 2016-06-13 | 2017-12-19 | 上海顿美新材料科技有限公司 | A kind of accelerator ZDEC mixtures and its rubber compound composition |
| CN112661685A (en) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | One-step synthesis method of dithiocarbamate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827622A (en) * | 2006-04-11 | 2006-09-06 | 浙江超微细化工有限公司 | Process for preparing dibenzyl dithio carbaminate |
| CN101215249A (en) * | 2008-01-22 | 2008-07-09 | 濮阳蔚林化工股份有限公司 | Method for producing rubber vulcanization accelerant zinc ethylphenyl dithiocarbamate |
| CN101249324A (en) * | 2007-11-16 | 2008-08-27 | 广州机械科学研究院 | Food EPT rubber filter-pressing plate and method for preparing same |
-
2010
- 2010-09-28 CN CN2010105005658A patent/CN101973919A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827622A (en) * | 2006-04-11 | 2006-09-06 | 浙江超微细化工有限公司 | Process for preparing dibenzyl dithio carbaminate |
| CN101249324A (en) * | 2007-11-16 | 2008-08-27 | 广州机械科学研究院 | Food EPT rubber filter-pressing plate and method for preparing same |
| CN101215249A (en) * | 2008-01-22 | 2008-07-09 | 濮阳蔚林化工股份有限公司 | Method for producing rubber vulcanization accelerant zinc ethylphenyl dithiocarbamate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267931A (en) * | 2011-07-18 | 2011-12-07 | 利民化工股份有限公司 | Metham production process |
| CN107488273A (en) * | 2016-06-13 | 2017-12-19 | 上海顿美新材料科技有限公司 | A kind of accelerator ZDEC mixtures and its rubber compound composition |
| CN112661685A (en) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | One-step synthesis method of dithiocarbamate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101139338B (en) | Preparation of 2,2'-disulfo-dibenzopyrene by oxygen process based on 2-mercaptan benzothiazole ammonia salt | |
| CN101973919A (en) | Method for preparing zinc diphenyl dithiocarbamate | |
| CN101717380A (en) | Clean production method of rubber vulcanizing accelerator TBBS | |
| CN107779603A (en) | A kind of method that ceruse is prepared in the scrap lead from oxidation | |
| CN111019131B (en) | Preparation method of polyaspartic acid zinc salt | |
| CN105037295A (en) | Method for producing sulfenamide rubber vulcanization accelerator | |
| CN104610193A (en) | Preparation method of rubber vulcanizing accelerator TBBS | |
| CN106316906B (en) | A kind of method of synthesis accelerant DPTU | |
| CN102875356A (en) | Calcium stearate production method | |
| CN105732687A (en) | Methyltris(methylethylketoxime)silane preparation method | |
| CN104592161A (en) | Method for producing rubber vulcanization accelerator CBS by crude product MBT | |
| CN87107289A (en) | The production method of polyphenylene oxide | |
| CN108947845A (en) | A kind of production method of 2,4-dinitrophenol sodium | |
| CN102295620B (en) | Co-production synthesizing technology of rubber vulcanization promoter NS | |
| CN105037215B (en) | A kind of environment protection method of high yield dioxygen oxidation method synthesis accelerant DPG | |
| CN101717381A (en) | Method for synthesizing thiofide CZ by taking hydrogen peroxide as oxidant | |
| CN101121683A (en) | Method for producing rubber vulcanization accelerant zinc dibutyl dithiocaarbamate | |
| CN106866468A (en) | A kind of environment-friendly preparation method of 4 ASC | |
| CN101157663A (en) | Method for producing rubber vulcanization accelerator NS | |
| CN101973914B (en) | Method for preparing salt-free 2-amino-1,5-naphthalenedisulfonic acid | |
| CN112427049B (en) | Catalyst for producing vulcanization accelerator TBBS by heterogeneous oxygen method and application method thereof | |
| CN112645900B (en) | Synthesis method of accelerant DCBS | |
| CN101633495A (en) | Method for preparing sulphur black dye and sodium thiosulfate from sulphur dye waste water | |
| CN1827622A (en) | Process for preparing dibenzyl dithio carbaminate | |
| CN101215249A (en) | Method for producing rubber vulcanization accelerant zinc ethylphenyl dithiocarbamate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110216 |