CN105367469A - Tetrabenzylthiuramdisulfide synthesis method - Google Patents
Tetrabenzylthiuramdisulfide synthesis method Download PDFInfo
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- CN105367469A CN105367469A CN201410411007.2A CN201410411007A CN105367469A CN 105367469 A CN105367469 A CN 105367469A CN 201410411007 A CN201410411007 A CN 201410411007A CN 105367469 A CN105367469 A CN 105367469A
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Abstract
The present invention relates to a synthesis method of a rubber vulcanization accelerator tetrabenzylthiuramdisulfide. The synthesis method is characterized in that dibenzylamine, carbon disulfide, sodium hydroxide and hydrogen peroxide are adopted as base raw materials, and in the presence of a phase transfer catalyst, the mixture obtained from the reaction is subjected to acid neutralization, filtration, washing and drying to obtain the tetrabenzylthiuramdisulfide. According to the present invention, the method is different from the previous method using the organic solvent as the reaction system or carrying out the catalysis reaction under the pressure condition, and has characteristics of simpleness, easy operation, convenient reaction product separation and washing, high product yield, and high product purity.
Description
Technical field
The present invention relates to a kind of thiofide, i.e. the synthetic method of tetra-benzyl thiram disulfide.
Background technology
Nowadays along with industrial expansion, environment is more and more important in Chemical Manufacture from now on; Meanwhile, buyer more and more focuses on its use value and the hazardness brought when selecting product.Therefore, in Rubber processing industry, whether the use more paying close attention to promotor both at home and abroad can produce nitrosamine carcinogens.At present, for generation nitroso compound problem, in the research field of rubber accelerator, the very big concern of vast scientific research person is also received.Simultaneously, relevant restricted regulation has also been promulgated in the whole world, as controlled content of nitrosamines as far back as nineteen eighty-two German just promulgation relevant laws and regulations, afterwards the U.S., Japan, France, Britain also energetically input research exploitation do not produce the Novel vulcanization accelerator of nitrosamine, and in succession stop using the vulcanization accelerator producing nitrosamine.There is due to thiuram accelerator the advantages such as critical temperature is low, vulcanization rate is fast, sulphidity is high, nondiscoloration, and the thiuram type accelerators such as TMTM, TMTD, TETD, TBTD can produce carcinogenic substance nitrosamine, therefore, promotor TBzTD, namely tetra-benzyl thiram disulfide is that one has plastic new variety.
Tetra-benzyl thiram disulfide (TBzTD) is a kind of safe, green secondary amine promotor, and as a kind of quick acting accelerator or secondary accelerator, TBZTD has numerous premium properties, is widely used in all sizing materials such as butadiene-styrene rubber, natural gum, butadiene-acrylonitrile rubber; Do not produce can be carcinogenic nitrosamine, molecular weight is large, and not volatile, vulcanization rate is high, and scorch safety is good, makes sizing material thermotolerance excellent, and as non-polar molecule, in Vulcanization Process of Rubber, without bloom phenomenon, burning-point is high, not easily decomposes, reducing resistance.
The structural formula of tetra-benzyl thiram disulfide is as follows:
cN1962627Apatent describes a kind of universal synthesis method of tetraalkyl thiram, it uses persulphate as the oxygenant of reaction, and aqueous ethanolic solution is as reaction medium, and in example, the highest yield is 82%.
cN1827596Apatent describes a kind of solventless synthesis synthetic method, the highest yield 95% in example, product purity is 97%.
cN1341097Apatent describes a kind of no-solvent synthesis process, its reaction employs manganous acetate catalyzer, and is react at reduced pressure conditions.
cN102731355Athe synthetic method of patent Introduction, adds toluene as solvent in its reaction system.
Summary of the invention
The object of the present invention is to provide a kind of thiofide, i.e. the synthetic method of tetra-benzyl thiram disulfide.
The synthetic method of tetra-benzyl thiram disulfide, it is characterized in that with dibenzylamine, dithiocarbonic anhydride, sodium hydroxide, hydrogen peroxide for basic raw material, under phase-transfer catalyst existence condition, the mixture be obtained by reacting, through peracid neutralization, filtration, washing, drying treatment, obtains tetra-benzyl thiram disulfide.
For reaching above object, the technical scheme that the present invention takes is as follows:
The synthetic method of N-secondary octyl-N'-diphenyl-para-phenylene diamine, its feature comprises the following steps:
A certain proportion of caustic soda, dibenzylamine, phase-transfer catalyst are joined and fill in the reactor of distilled water, stirs and make it dissolve; At a certain temperature, drip dithiocarbonic anhydride, after the reaction regular hour, continue the insulation regular hour; Start at a certain temperature to drip hydrogen peroxide, then drip sulfuric acid after reacting the regular hour, regulate PH, make it aobvious acid, discharging after the insulation regular hour, suction filtration, by washing with alcohol; Filter cake is put into drying baker, under certain temperature and time, carries out drying, can product be drawn.
Selected phase-transfer catalyst is conventional quaternary ammonium salt phase transfer catalyst, as benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride etc.
The mol ratio dibenzylamine of raw material: dithiocarbonic anhydride: sodium hydroxide: hydrogen peroxide is 1:1.1 ~ 1.3:1.1 ~ 1.3:0.5 ~ 0.7; Phase-transfer catalyst consumption is 5 ~ 10mol% of dibenzylamine.
The dropping temperature of dithiocarbonic anhydride is 20 ~ 40 DEG C, time for adding 2 ~ 3 hours, maintains 0.5 ~ 1 hour; Hydrogen peroxide dropping temperature is 40 ~ 60 DEG C, time for adding 2 ~ 3 hours; After reconciling, pH is 6 ~ 7, is incubated 0.5 ~ 1 hour; Wash 3 times; Use dehydrated alcohol; Drying temperature 60 ~ 100 DEG C.
Beneficial effect of the present invention:
Use phase-transfer catalyst, effectively disperse reaction system, improve reaction conversion ratio and yield, products obtained therefrom is easy to abstraction and purification process.
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to following embodiment.
Embodiment
The phase-transfer catalyst of 4.4g sodium hydroxide, 3g, the dibenzylamine of 19.7g are put in four-hole boiling flask, adds the distilled water of 400ml, open agitator, make its stirring and dissolving; Afterwards, when temperature is raised to 35 DEG C, starts slowly to drip 9.2g dithiocarbonic anhydride (time controling is at 2.5h), carry out condensation reaction, dropwise, then continue insulation 0.5 hour; When temperature is raised to 40 DEG C, then drip 6g hydrogen peroxide (time controling was at 3 hours); After oxidizing reaction terminates, drip sulfuric acid, regulate pH (6 ~ 7), continue afterwards to stir, insulation 1h; Finally, discharging, suction filtration, by washing with alcohol 3 times; Product at 80 DEG C dry 4 hours.Obtain product 26.8g, yield is 98.5%, and content (HPLC) is greater than 97%, and fusing point 128.2 DEG C is buff powder.
Claims (5)
1. the synthetic method of a tetra-benzyl thiram disulfide, it is characterized in that with dibenzylamine, dithiocarbonic anhydride, sodium hydroxide, hydrogen peroxide for basic raw material, under phase-transfer catalyst existence condition, the mixture be obtained by reacting, through peracid neutralization, filtration, washing, drying treatment, obtains tetra-benzyl thiram disulfide.
2. synthetic method according to claim 1, it is characterized in that selected phase-transfer catalyst is conventional quaternary ammonium salt phase transfer catalyst, be selected from benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
3. synthetic method according to claim 1, its characteristic reaction condition is: phase-transfer catalyst, sodium hydroxide, dibenzylamine add and fill in the container of distilled water, drips dithiocarbonic anhydride, maintains; Drip hydrogen peroxide; Add acid for adjusting pH, insulation maintains; Discharging, filtration washing.
4., with synthetic method according to claim 3, it is characterized in that the mol ratio of raw material: dibenzylamine: dithiocarbonic anhydride: sodium hydroxide: hydrogen peroxide is 1:1.1 ~ 1.3:1.1 ~ 1.3:0.5 ~ 0.7; Phase-transfer catalyst consumption is 5 ~ 10mol% of dibenzylamine.
5., with synthetic method according to claim 3, it is characterized in that the dropping temperature of dithiocarbonic anhydride is 20 ~ 40 DEG C, time for adding 2 ~ 3 hours, maintain 0.5 ~ 1 hour; Hydrogen peroxide dropping temperature is 40 ~ 60 DEG C, time for adding 2 ~ 3 hours; After reconciling, pH is 6 ~ 7, is incubated 0.5 ~ 1 hour; Wash 3 times; Use dehydrated alcohol; Drying temperature 60 ~ 100 DEG C.
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| CN201410411007.2A CN105367469A (en) | 2014-08-20 | 2014-08-20 | Tetrabenzylthiuramdisulfide synthesis method |
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| CN201410411007.2A CN105367469A (en) | 2014-08-20 | 2014-08-20 | Tetrabenzylthiuramdisulfide synthesis method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147986A (en) * | 2017-12-20 | 2018-06-12 | 蔚林新材料科技股份有限公司 | The preparation method of tetraethylthiuram disulfide |
| CN110054598A (en) * | 2019-04-04 | 2019-07-26 | 上海倍裕实业有限公司 | A kind of novel processing step of rubber vulcanization accelerant CZ |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4468526A (en) * | 1981-02-16 | 1984-08-28 | Akzona Incorporated | Process for the preparation of thiuram disulfides |
| CN1944505A (en) * | 2006-10-30 | 2007-04-11 | 濮阳市蔚林化工有限公司 | Production method of rubber vulcanization accelerator tetrabenzylthiuram disulfide |
| CN101462993A (en) * | 2008-12-16 | 2009-06-24 | 濮阳蔚林化工股份有限公司 | Preparation of rubber vulcanization accelerator tetrabenzylthiuram disulfide |
-
2014
- 2014-08-20 CN CN201410411007.2A patent/CN105367469A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4468526A (en) * | 1981-02-16 | 1984-08-28 | Akzona Incorporated | Process for the preparation of thiuram disulfides |
| CN1944505A (en) * | 2006-10-30 | 2007-04-11 | 濮阳市蔚林化工有限公司 | Production method of rubber vulcanization accelerator tetrabenzylthiuram disulfide |
| CN101462993A (en) * | 2008-12-16 | 2009-06-24 | 濮阳蔚林化工股份有限公司 | Preparation of rubber vulcanization accelerator tetrabenzylthiuram disulfide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147986A (en) * | 2017-12-20 | 2018-06-12 | 蔚林新材料科技股份有限公司 | The preparation method of tetraethylthiuram disulfide |
| CN110054598A (en) * | 2019-04-04 | 2019-07-26 | 上海倍裕实业有限公司 | A kind of novel processing step of rubber vulcanization accelerant CZ |
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Application publication date: 20160302 |