CN102731355A - Preparation process for rubber vulcanization accelerator tetrabenzylthiuram disulfide - Google Patents
Preparation process for rubber vulcanization accelerator tetrabenzylthiuram disulfide Download PDFInfo
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- CN102731355A CN102731355A CN2012102218416A CN201210221841A CN102731355A CN 102731355 A CN102731355 A CN 102731355A CN 2012102218416 A CN2012102218416 A CN 2012102218416A CN 201210221841 A CN201210221841 A CN 201210221841A CN 102731355 A CN102731355 A CN 102731355A
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Abstract
The invention relates to a preparation process for the rubber vulcanization accelerator tetrabenzylthiuram disulfide. A raw material mol ratio of dibenzylamine to carbon disulfide to hydrogen peroxide is 0.9-1: 1.25-1.3: 1.45-1.5. The process comprises the following steps: sequentially adding a specified amount of dibenzylamine, carbon disulfide and an emulsifier into a reaction vessel filled with toluene and water under agitation, stirring the above-mentioned substances for a reaction for 1 h, then adding hydrogen peroxide drop by drop for an oxidation reaction, controlling the temperature to be 10 to 50 DEG C, continuing stirring for 0.5 to 3 h after dropwise addition of hydrogen peroxide has finished 0.5 to 3 h before, cooling an obtained solution to a low temperature for solid-liquid separation, carrying out washing with a small amount of toluene and pumping out a solid under vacuum so as to obtain tetrabenzylthiuram disulfide. The preparation process provided in the invention poses no pollution to the environment; toluene and water in mother liquor can be recycled through distillation; production cost is reduced; and the obtained product has good quality.
Description
Technical field
The invention belongs to the thiofide technical field, relate to a kind of reparation technology of tetra benzyl thiuram disulfide as rubber vulcanizing accelerator.
Background technology
Along with industrial expansion; It is important that environment protection more seems in Chemical Manufacture from now on; In recent years; In the world some promotor is prone to produce the problem pay attention to day by day of harmful NSC 223080 in the Rubber processing process, calendar year 2001, Chinese rubber auxiliary agent Professional Committee brought forward the carcinogenic problem of NSC 223080 that solves in " carrying forward vigorously the cleaner production of China's rubber industry " suggestion.Research shows, the N-NSC 223080 is by secondary amine and reaction of nitrogen oxides and generate.In the sulfidation of sizing material, be that basic vulcanization accelerator decomposes the reaction of nitrogen oxides generation N-NSC 223080 that the back produces Synergist S-421 95 in secondary amine and the air with secondary amine, the NSC 223080 of generation has the DNA alkylation to bring out carcinogenic possibility most.
Environment-friendly type accelerant disulfide tetra-benzyl thiram (TBzTD) is a kind of safe secondary amine promotor, no NSC 223080 harm.Its high molecular weight is incomparable with the thiuram that to be used to make the resulting promotor performance of benzylamine that this molecule uses be low relative molecular mass.Mainly be to be used for replacing thiuram auxiliary agent TMTD.Tetra-benzyl thiram disulfide (TBzTD) can be used as quick primary accelerator or secondary accelerator in the application of NR, SBR and NBR.
The method for preparing accelerant disulfide tetra-benzyl thiram (TBzTD) has a variety of, and for example: use dibenzyl amine, CS2 is in organic solvent, in the presence of catalyzer (like neutralized verdigris), with the method for O2 oxidation.Document has: GB10293029; CN1341097, reaction conditions needs pressure in these class methods, and is quite high to the requirement of equipment; Use dibenzyl amine, CS2, alkali (NaOH, LiOH) to process the dibenzyl aminodithioformic acid an alkali metal salt in addition, carry out oxidation then, oxygenant is like H2O2, CL2, NaCLO etc.Document has: CN1827596 (H2O2+H2SO4); DE19930625 (LiOH replaces NaOH) is easy to generate great amount of wastewater, abraum salt with these class methods, and water treatment has been brought difficulty.The aforesaid method energy consumption is high, is difficult to realize that " cleaning is green " produces.And reparation technology of the present invention, the problem of having avoided aforesaid method to occur, non-wastewater discharge, non-environmental-pollution, and toluene, water can recycles, and energy-saving and cost-reducing, good product quality.
Summary of the invention
A kind of reparation technology that the purpose of this invention is to provide the vulcanization of rubber accelerant disulfide tetrabenzyl.
L, the present invention are raw materials used
Dibenzyl amine: a kind of colourless or flaxen transparent oily liquid, micro-bitter almond odor is arranged, not volatile, be alkalescence, in air, deposit color for a long time and can increase the weight of.
Hydrogen peroxide: have another name called ydrogen peroxide 50, a kind of colourless transparent liquid, specific density 1. 4067
(25 ℃), water-soluble, pure, ether are insoluble to sherwood oil, and is extremely unstable, meets light, heat, uneven surface, heavy metal and other impurity and can cause decomposition, emits oxygen and heat simultaneously.Have stronger oxidation capacity, be strong oxidizer.More stable under acidic conditions.
Dithiocarbonic anhydride: colourless or little yellow volatility transparent liquid, specific density 1. 265,
Pure article have aromatising flavour, and 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/100ml) be dissolved in pure and mild ether, high refractivity is arranged, be prone to 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.
Toluene: toluene is organic cpds, is liquid at normal temperatures, and is colourless, inflammable.Its boiling point is 110.8 ℃, and zero pour is-95 ℃, and density is 0.866 gram per centimeter
3Toluene insoluble is in water, but good solvent is gone up in industry.
2, reparation technology process of the present invention:
A kind of reparation technology of tetra benzyl thiuram disulfide as rubber vulcanizing accelerator, starting material stoichiometry mol ratio:
Its technological process is: in the reaction kettle that fills toluene and water; The dibenzyl amine that adds specified amount under the whipped state successively; Dithiocarbonic anhydride, and emulsifying agent (X 2073) stirring reaction simultaneously after reacting one hour, begin to drip ydrogen peroxide 50 and carry out oxidizing reaction; Controlled temperature is at 10-50 ℃, drip time of 0.5～3 hour after; Continue to stir 0.5～3 hour, reaction finishes.Reduce to low temperature and carry out solid-liquid separation, with the small amount of toluene washing, the solid vacuum is drained dithio tetra-benzyl thiram promptly.
(1) proportioning raw materials:
Dibenzyl amine: dithiocarbonic anhydride: ydrogen peroxide 50=0.9～1:1.25～1.3:1.45～1.5mol
(2) solvent: adding entry is to be used for dissolved emulsifier, and adding toluene is speed of reaction and the reaction yield that is used for improving step of reaction, selects the amount of toluene, generally is 2-10 times of dibenzyl amine weight, and proper is 2-5 times; The weight ratio of toluene and water is 4:1;
3, the advantage of product of the present invention:
(l), non-wastewater discharge in the process of producing product, non-environmental-pollution.
(2), solvent toluene and water can recycles, greatly reduce cost.
(3), the first fusing point >=130 ℃ of product, purity >=more than 98%.
(4), in sulfuration, use, do not produce carcinogenic NSC 223080.
(5), in vulcanization of rubber experiment: have longer time of scorch, process safer.
(6), with short production cycle; Energy-conservation, consumption reduction.
Embodiment
Instance 1
In the four-hole boiling flask of 500ml, add 200g toluene, the dibenzyl amine of 39.5g, 15g dithiocarbonic anhydride, 0.1g emulsifying agent and 50g water.In 20-35 ℃, stirring reaction 1 hour.The ydrogen peroxide 50 that drips 10g35% afterwards begins to carry out oxidizing reaction, and temperature is controlled at 10-50 ℃; Dropwise reaction 1.5 hours.After dropwising, stir 30min, reduce to low temperature and carry out solid-liquid separation, use the 20ml toluene wash, the dry product TBzTD that gets.Yield 95.1%, fusing point 132-135 ℃, purity is 99.5%.
Instance 2
In the four-hole boiling flask of 500ml, add 210g toluene, the dibenzyl amine of 39.5g, 15g dithiocarbonic anhydride, 0.08g emulsifying agent and 52g water.In 20-35 ℃, stirring reaction 1 hour.The ydrogen peroxide 50 that drips 10g35% afterwards begins to carry out oxidizing reaction, and temperature is controlled at 10-50 ℃; Dropwise reaction 2 hours.After dropwising, stir 45min, reduce to low temperature and carry out solid-liquid separation, use the 30ml toluene wash, the dry product TBzTD that gets.Yield 95.7%, fusing point 132-135 ℃, purity is 99.5%.
Instance 3
In the four-hole boiling flask of 500ml, add 200g toluene, the dibenzyl amine of 39.5g, 15g dithiocarbonic anhydride, 0.03g emulsifying agent and 50g water.In 20-35 ℃, stirring reaction 1 hour.The ydrogen peroxide 50 that drips 10g35% afterwards begins to carry out oxidizing reaction, and temperature is controlled at 10-50 ℃; Dropwise reaction 2.5 hours.After dropwising, stir 60min, reduce to low temperature and carry out solid-liquid separation, use the 20ml toluene wash, the dry product TBzTD that gets.Yield 96.1%, fusing point 132-135 ℃, purity is 99.5%.
Claims (6)
1. the reparation technology of a tetra benzyl thiuram disulfide as rubber vulcanizing accelerator; It is characterized in that: in the reaction kettle that fills toluene and water; Add dibenzyl amine, dithiocarbonic anhydride and emulsifying agent under the whipped state successively; After reacting 1 hour, begin to drip ydrogen peroxide 50 and carry out oxidizing reaction, controlled temperature is at 10-50 ℃; Drip after 0.5-3 hour; Continue to stir 0.5-3 hour, reduce to low temperature then and carry out solid-liquid separation, the dry dithio tetra-benzyl thiram that gets.
2. reparation technology according to claim 1 is characterized in that: the mother liquor after the solid-liquid separation is distilled, and overhead product divides two phases (toluene and water), drops into cycling and reutilization in the next batch reaction kettle.
3. reparation technology according to claim 1 is characterized in that: the mol ratio of dibenzyl amine, dithiocarbonic anhydride and ydrogen peroxide 50 is 0.9～1:1.25～1.3:1.45～1.5.
4. according to claim 1 and 2 described reparation technologies, it is characterized in that: described emulsifying agent is an X 2073.
5. reparation technology according to claim 1 is characterized in that: the amount of toluene is 2-10 a times of dibenzyl amine weight, and proper is 2-5 times; The weight ratio of toluene and water is 4:1.
6. reparation technology according to claim 1 is characterized in that: described drying is that vacuum is drained.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739534A (en) * | 2013-12-24 | 2014-04-23 | 武汉径河化工有限公司 | Synthetic method of rubber accelerator tetrabenzylthiuram disulfide |
| CN104326956A (en) * | 2014-10-21 | 2015-02-04 | 山东斯递尔化工科技有限公司 | Preparation method of tetrabutylthiuram disulfide used as rubber vulcanization accelerator |
| CN104829509A (en) * | 2015-05-12 | 2015-08-12 | 苏州市湘园特种精细化工有限公司 | Preparation method of rubber vulcanization accelerator |
| CN106316905A (en) * | 2016-08-23 | 2017-01-11 | 山东阳谷华泰化工股份有限公司 | Sulfide tetrabenzyl thiuram and preparation method and application thereof |
| CN108863874A (en) * | 2018-06-05 | 2018-11-23 | 蔚林新材料科技股份有限公司 | A kind of method of continuous synthesis dibenzyl aminodithioformic acid sodium |
| 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 |
| CN111018761A (en) * | 2019-12-27 | 2020-04-17 | 鹤壁元昊化工有限公司 | Synthesis process of tetrabenzylthiuram disulfide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008055A1 (en) * | 1978-08-10 | 1980-02-20 | Bayer Ag | Process for the preparation of dimethyldiphenylthiuram disulphide |
| JP2004244406A (en) * | 2003-02-14 | 2004-09-02 | Kawaguchi Kagaku Kogyo Kk | Method for producing tetrabenzylthiuram disulfide |
| CN1962627A (en) * | 2006-11-21 | 2007-05-16 | 陕西科技大学 | Process for preparing tetraalkyl thiram |
-
2012
- 2012-07-01 CN CN2012102218416A patent/CN102731355A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008055A1 (en) * | 1978-08-10 | 1980-02-20 | Bayer Ag | Process for the preparation of dimethyldiphenylthiuram disulphide |
| JP2004244406A (en) * | 2003-02-14 | 2004-09-02 | Kawaguchi Kagaku Kogyo Kk | Method for producing tetrabenzylthiuram disulfide |
| CN1962627A (en) * | 2006-11-21 | 2007-05-16 | 陕西科技大学 | Process for preparing tetraalkyl thiram |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739534A (en) * | 2013-12-24 | 2014-04-23 | 武汉径河化工有限公司 | Synthetic method of rubber accelerator tetrabenzylthiuram disulfide |
| CN103739534B (en) * | 2013-12-24 | 2016-04-27 | 武汉径河化工（潜江)有限公司 | The synthetic method of rubber accelerator tetrabenzylthiuram disulfide |
| CN104326956A (en) * | 2014-10-21 | 2015-02-04 | 山东斯递尔化工科技有限公司 | Preparation method of tetrabutylthiuram disulfide used as rubber vulcanization accelerator |
| CN104326956B (en) * | 2014-10-21 | 2015-10-28 | 山东斯递尔化工科技有限公司 | A kind of preparation method of tetra benzyl thiuram disulfide as rubber vulcanizing accelerator |
| CN104829509A (en) * | 2015-05-12 | 2015-08-12 | 苏州市湘园特种精细化工有限公司 | Preparation method of rubber vulcanization accelerator |
| CN106316905A (en) * | 2016-08-23 | 2017-01-11 | 山东阳谷华泰化工股份有限公司 | Sulfide tetrabenzyl thiuram and preparation method and application thereof |
| CN108863874A (en) * | 2018-06-05 | 2018-11-23 | 蔚林新材料科技股份有限公司 | A kind of method of continuous synthesis dibenzyl aminodithioformic acid sodium |
| 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 |
| CN111018761A (en) * | 2019-12-27 | 2020-04-17 | 鹤壁元昊化工有限公司 | Synthesis process of tetrabenzylthiuram disulfide |
| CN111018761B (en) * | 2019-12-27 | 2021-05-07 | 鹤壁元昊化工有限公司 | Synthesis process of tetrabenzylthiuram disulfide |
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Application publication date: 20121017 |