CN105541683A - Method for preparing tetrathioperoxydicarbamic acid - Google Patents
Method for preparing tetrathioperoxydicarbamic acid Download PDFInfo
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- CN105541683A CN105541683A CN201610097445.5A CN201610097445A CN105541683A CN 105541683 A CN105541683 A CN 105541683A CN 201610097445 A CN201610097445 A CN 201610097445A CN 105541683 A CN105541683 A CN 105541683A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/30—Dithiocarbamic acids; Derivatives thereof having sulfur atoms of dithiocarbamic groups bound to other sulfur atoms
- C07C333/32—Thiuramsulfides; Thiurampolysulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
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Abstract
The invention discloses a method for preparing tetrathioperoxydicarbamic acid. The method includes the steps that diisobutylamine is added to solvent, then carbon disulfide is dropwise added to the mixture, a reaction is conducted for 0.5-1 hour after the carbon disulfide is completely added dropwise, and diisobutyl aminodithioformic acid reaction liquid is obtained; 2, the diisobutyl aminodithioformic acid reaction liquid obtained in step 1 is slowly added to a hydrogen peroxide solution dropwise, after the diisobutyl aminodithioformic acid reaction liquid is completely added dropwise, the temperature is raised for an oxidizing reaction, after the reaction is conducted, reaction liquid is filtered, the obtained sediment is washed and dried, and the tetrathioperoxydicarbamic acid is obtained. The preparation process is simple, strong acid and strong base are not needed any more by controlling the solvent, the dropwise adding speed, the dropwise adding sequence and other conditions, production cost is reduced, the potential safety hazard of the process is lowered, pollution is small, energy is saved, the environment is protected, an obtained product is good in quality, the yield is high, and the method is adapted to the policy requirement for national green chemical engineering.
Description
Technical field
The present invention relates to a kind of disulfide diisobutyl thiuram and low-cost environmental-protecting preparation method thereof, belong to field of fine chemical.
Background technology
Rubber accelerator disulfide diisobutyl thiuram (TiBTD) is a kind of thiuram type accelerator of novel, safety and environmental protection, and structural formula is
.Disulfide diisobutyl thiuram can be widely used in natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR) etc., be alternative Vulcanization accelerator TMTD, TETD, TMTM, TRA etc. one class produce the green product of N-nitrosamine auxiliary agent.
At present, the main at home production method of TiBTD is acid-base method, and step is: diisobutylamine, dithiocarbonic anhydride and sodium hydroxide carry out condensation reaction, obtains the sodium salt of diisobutylamine, then it is acid for adjusting system with sulfuric acid, under the effect of hydrogen peroxide, the sodium salt of diisobutylamine is oxidized to TiBTD.Reaction equation is:
Acid-base method is aborning except producing a large amount of inorganic salt waste water, the production technique of strong acid, highly basic is also serious to equipment corrosion, there is a large amount of potential safety hazards, very large difficulty is brought to environment protection treating, be difficult to realize " cleaning " production, " green " production, do not conform to the policy requirements of the national national environmental protection policy of symbol and energy-saving and emission-reduction.Meanwhile, existing production technique reaction yield is low, and obtained product fusing point is low, purity is low, outward appearance is yellow, is difficult to the high-end requirement meeting domestic and international market.Therefore, imperative to the improvement of disulfide diisobutyl thiuram technique.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of disulfide diisobutyl thiuram, the method does not use strong acid and strong base, a large amount of by product can not be produced, environmental protection, safety, cost are low, and products obtained therefrom outward appearance is white, and fusing point is high, purity is high, is a kind of clean, green preparation method.
The concrete technical scheme of the present invention is as follows:
A preparation method for disulfide diisobutyl thiuram, the method comprises the following steps:
(1) diisobutylamine is added in solvent, then drip dithiocarbonic anhydride wherein, drip off rear reaction 0.5 ~ 1h, obtain diisobutyl dithiocarbamic acid reaction solution;
(2) be slowly added drop-wise in superoxol by the diisobutyl dithiocarbamic acid reaction solution of step (1), drip off rear intensification and carry out oxidizing reaction, filtering reacting liquid after reaction, gained washing of precipitate, drying, obtain disulfide diisobutyl thiuram.
The present invention passes through the cooperation of the selection of solvent and the dropping order of raw material and rate of addition, namely can obtain the measured disulfide diisobutyl thiuram product of matter when not using strong acid and highly basic.During preparation, first diisobutylamine and dithiocarbonic anhydride are reacted in a solvent and generate intermediate diisobutyl dithiocarbamic acid (reaction 1), then this intermediate is slowly added drop-wise in superoxol, oxidation product disulfide diisobutyl thiuram (reaction 2).Returned the method for dropping by intermediate, a small amount of intermediate is joined in a large amount of oxygenants, oxidation is formed fast, improves rate of oxidation, and make quality product obtain larger lifting.Reaction equation is as follows:
In above-mentioned preparation method, described solvent is water, or volume fraction is the isopropanol water solution of 15-25%.Research finds, the selection of solvent can affect the process of reaction, affects the purity of product.
In above-mentioned preparation method, dithiocarbonic anhydride instills in the mixture of diisobutylamine and solvent at normal temperatures, after dripping, then reacts 0.5-1h.
In above-mentioned preparation method, in step (1), dithiocarbonic anhydride is added drop-wise in the mixture of diisobutylamine and solvent according to the rate of addition of 9-15ml/min.
In above-mentioned preparation method, in step (2), diisobutyl dithiocarbamic acid reaction solution is added drop-wise in superoxol according to the rate of addition of 1-5ml/min.
In above-mentioned preparation method, in step (2), after dripping, be warming up to 50 ~ 60 DEG C and react, be preferably warming up to 53 ~ 57 DEG C and react.
In above-mentioned preparation method, in step (2), after dripping, General reactions 4 ~ 6h, preferred reaction 4.5 ~ 5.5h.
In above-mentioned preparation method, the concentration of superoxol can choose at random, when the concentration of superoxol is 30wt%, each raw material as follows with magnitude relation: diisobutylamine 100 ~ 120 weight part, dithiocarbonic anhydride 70 ~ 84 weight part, 30wt% superoxol 50 ~ 60 weight part, solvent 400 ~ 700 weight part.
In above-mentioned preparation method, when the concentration of superoxol is 30wt%, each raw material preferably uses following magnitude relation: diisobutylamine 100 weight part, dithiocarbonic anhydride 72 ~ 75 weight part, 30wt% superoxol 50 ~ 55 weight part, solvent 400 ~ 700 weight part.
In above-mentioned preparation method, when the concentration of superoxol is 30wt%, each raw material most preferably uses following magnitude relation: diisobutylamine 100 weight part, dithiocarbonic anhydride 73 weight part, 30wt% superoxol 52 weight part, solvent 500 weight part.
Gained disulfide diisobutyl thiuram fusing point of the present invention is 69 ~ 71 DEG C, purity can reach 98%, outward appearance is white, meets the high-end requirement of domestic and international market.Disulfide diisobutyl thiuram effectively can reduce curing time when being used as vulcanization accelerator, enhances productivity, and reduces production cost; Do not produce N-nitrosamine when cure scorch, environment-protecting asepsis, the coke burning performance of sizing material can be improved, extend time of scorch, increase work efficiency, improve the security in the course of processing, can as rubber accelerator for the preparation of cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR) etc.
The present invention, by research, optimization, improves the preparation method of disulfide diisobutyl thiuram, achieves good effect, specific as follows:
1, preparation technology of the present invention is simple, by controlling the conditions such as solvent, rate of addition and dropping order, no longer adds strong acid and highly basic, reduce production cost, reduce process safety hidden danger, less pollution, energy-conserving and environment-protective, and product yield is higher, has adapted to the policy requirements of national green chemical industry.
2, gained disulfide diisobutyl thiuram purity of the present invention is high, fusing point is high, outward appearance is white, may be used for physicals and the chemical property of improving sizing material in rubber process.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited thereto.
Diisobutylamine of the present invention, dithiocarbonic anhydride, 30% superoxol are existing commercial products, can buy in market.Wherein: diisobutylamine is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and dithiocarbonic anhydride is purchased from Tianjin great Mao chemical reagent factory, and 30wt% superoxol is purchased from Shanghai Habo Chemical Technology Co., Ltd..
In following embodiment, the account form of yield is: products obtained therefrom quality/product Theoretical Mass.
Embodiment 1
A preparation method for disulfide diisobutyl thiuram, step is as follows:
1, each raw material is taken: diisobutylamine 100g, dithiocarbonic anhydride 73g, 30% superoxol 52g, water 500g;
2, by proportioning, diisobutylamine is added to the water, drips dithiocarbonic anhydride according to the speed of 9ml/min under normal temperature, drip off rear reaction 0.5h, obtain reaction solution;
3, the reaction solution of step 2 is added drop-wise in the superoxol of 30wt% according to the speed of 1ml/min, temperature of reaction when controlling to drip and after dripping is 55 DEG C, reacts 5h again, the solid suction filtration be obtained by reacting, washing after dripping off, dry under vacuum, obtain disulfide diisobutyl thiuram 149.6g.Products obtained therefrom outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 70.1 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 98.0%, and yield is 95.2%.
Embodiment 2
1, each raw material is taken: with embodiment 1;
2, by proportioning, diisobutylamine is added to the water, drips dithiocarbonic anhydride according to the speed of 15ml/min under normal temperature, drip off rear reaction 0.5h, obtain reaction solution;
3, the reaction solution of step 2 is added drop-wise in the superoxol of 30wt% according to the speed of 5ml/min, temperature of reaction when controlling to drip and after dripping is 55 DEG C, reacts 5h again, the solid suction filtration be obtained by reacting, washing after dripping off, dry under vacuum, obtain disulfide diisobutyl thiuram 148.4g.Products obtained therefrom outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 69.6 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 97.5%, and yield is 94.5%.
Embodiment 3
1, each raw material is taken: diisobutylamine 100g, dithiocarbonic anhydride 70g, 30% superoxol 50g, the isopropanol water solution 500g of volume fraction 15%;
2, by proportioning, diisobutylamine is joined in the isopropanol water solution of volume fraction 15%, drip dithiocarbonic anhydride according to the speed of 9ml/min under normal temperature, drip off rear reaction 0.5h, obtain reaction solution;
3, the reaction solution of step 2 is added drop-wise in the superoxol of 30wt% according to the speed of 1ml/min, temperature of reaction when controlling to drip and after dripping is 55 DEG C, reacts 5h again, the solid suction filtration be obtained by reacting, washing after dripping off, dry under vacuum, obtain disulfide diisobutyl thiuram 155.0g.Products obtained therefrom outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 70.3 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 98.8%, and yield is 98.7%.
Embodiment 4
Disulfide diisobutyl thiuram is prepared according to the method for embodiment 3, unlike: each raw material dosage is: diisobutylamine 120g, dithiocarbonic anhydride 84g, 30wt% superoxol 60g, the isopropanol water solution 500g of volume fraction 25%.Products obtained therefrom is 186.6g, and outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 70.2 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 98.5%, and yield is 98.4%.
Embodiment 5
1, each raw material is taken: diisobutylamine 110g, dithiocarbonic anhydride 77g, 30wt% superoxol 55g, the isopropanol water solution 500g of volume fraction 20%;
2, by proportioning, diisobutylamine is added to the water, drips dithiocarbonic anhydride according to the speed of 9ml/min under normal temperature, drip off rear reaction 0.5h, obtain reaction solution;
3, the reaction solution of step 2 is added drop-wise in the superoxol of 30wt% according to the speed of 1ml/min, temperature of reaction when controlling to drip and after dripping is 50 DEG C, reacts 6h again, the solid suction filtration be obtained by reacting, washing after dripping off, dry under vacuum, obtain disulfide diisobutyl thiuram 171.2g.Outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 70.5 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 99.0%, and yield is 98.7%.
Embodiment 6
Disulfide diisobutyl thiuram is prepared according to the method for embodiment 3, unlike: each raw material dosage is: diisobutylamine 110g, dithiocarbonic anhydride 84g, 30% superoxol 55g, the isopropanol water solution 500g of volume fraction 25%.Products obtained therefrom is 170.1g, and outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 70.2 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 98.3%, and yield is 98.1%.
Embodiment 7
Disulfide diisobutyl thiuram is prepared according to the method for embodiment 3, unlike: each raw material dosage is: diisobutylamine 120g, dithiocarbonic anhydride 70g, 30% superoxol 65g, the isopropanol water solution 500g of volume fraction 20%.Products obtained therefrom is 186.0g, and outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 70.1 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 98.4%, and yield is 98.1%.
Embodiment 8
Disulfide diisobutyl thiuram is prepared according to the method for embodiment 1, unlike: each parts by weight of raw materials consumption is: diisobutylamine 120 parts, dithiocarbonic anhydride 77 parts, 30% superoxol 65g, water 500g.Products obtained therefrom is 179g, and outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 69.5 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 98.0%, and yield is 94.3%.
Embodiment 9
1, each raw material is taken: diisobutylamine 100g, dithiocarbonic anhydride 70g, 30% superoxol 50g, the isopropanol water solution 500g of volume fraction 20%;
2, by proportioning, diisobutylamine is added to the water, drips dithiocarbonic anhydride according to the speed of 11ml/min under normal temperature, drip off rear reaction 0.5h, obtain reaction solution;
3, the reaction solution of step 2 is added drop-wise in the superoxol of 30wt% according to the speed of 2ml/min, temperature of reaction when controlling to drip and after dripping is 57 DEG C, 4h is reacted again after dripping off, the solid suction filtration be obtained by reacting, washing, dry under vacuum, obtain disulfide diisobutyl thiuram 154.2g, outward appearance is white, recording fusing point through automatic capillary melting point apparatus is 70.3 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 98.5%, and yield is 98.2%.
Embodiment 10
Disulfide diisobutyl thiuram is prepared according to the method for embodiment 1, unlike: each raw material weight g consumption is: diisobutylamine 100g, dithiocarbonic anhydride 73g, 30% superoxol 52g, water 700g.Products obtained therefrom is 150.3g, and outward appearance is white, and recording fusing point through automatic capillary melting point apparatus is 69.5 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 97.4%, and yield is 95.7%.
Comparative example 1
A preparation method for disulfide diisobutyl thiuram, step is as follows:
1, each raw material is taken: diisobutylamine 120g, dithiocarbonic anhydride 84g, sodium hydrate solid 40g, 98% vitriol oil 50g, 30% superoxol 65g, water 500g;
2, step: diisobutylamine is added drop-wise in water by proportioning, drip the sodium salt of dithiocarbonic anhydride and sodium hydroxide condensation generation diisobutylamine under normal temperature simultaneously, drip the vitriol oil of 98% again, drip the sodium salt of hydrogen peroxide oxidation diisobutylamine in acid condition, be obtained by reacting solid suction filtration, washing, dry under vacuum, obtain disulfide diisobutyl thiuram 173.5g.Products obtained therefrom outward appearance is yellow, and recording fusing point through automatic capillary melting point apparatus is 65.2 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 95.8%, and yield is 91.5%.
Comparative example 2
A preparation method for disulfide diisobutyl thiuram, step is as follows:
1, each raw material is taken: diisobutylamine 100g, dithiocarbonic anhydride 73g, 30% superoxol 52g, water 500g;
2, step: be added to the water by diisobutylamine by proportioning, drips dithiocarbonic anhydride according to the speed of 18ml/min under normal temperature, drips off rear reaction 0.5h, obtain reaction solution;
3, the superoxol of 30wt% is added drop-wise in the reaction solution of step 2 according to the speed of 10ml/min, temperature of reaction when controlling to drip and after dripping is 55 DEG C, 5h is reacted again after dripping off, the solid suction filtration be obtained by reacting, washing, dry under vacuum, obtain disulfide diisobutyl thiuram 140.2g.Products obtained therefrom outward appearance is yellow, and recording fusing point through automatic capillary melting point apparatus is 67.2 DEG C, and recording purity through efficient liquid phase chromatographic analysis instrument is 90.5%, and yield is 89.2%.
Claims (10)
1. a preparation method for disulfide diisobutyl thiuram, is characterized in that comprising the following steps:
(1) diisobutylamine is added in solvent, then drip dithiocarbonic anhydride wherein, drip off rear reaction 0.5 ~ 1h, obtain diisobutyl dithiocarbamic acid reaction solution;
(2) be slowly added drop-wise in superoxol by the diisobutyl dithiocarbamic acid reaction solution of step (1), drip off rear intensification and carry out oxidizing reaction, filtering reacting liquid after reaction, gained washing of precipitate, drying, obtain disulfide diisobutyl thiuram.
2. preparation method according to claim 1, is characterized in that: described solvent is water, or volume fraction is the isopropanol water solution of 15-25%.
3. preparation method according to claim 1 and 2, is characterized in that: dithiocarbonic anhydride is added drop-wise in the mixture of diisobutylamine and solvent according to the rate of addition of 9-15ml/min.
4. the preparation method according to claim 1,2 or 3, is characterized in that: diisobutyl dithiocarbamic acid reaction solution is added drop-wise in superoxol according to the rate of addition of 1-5ml/min.
5. the preparation method according to claim 1 or 3, is characterized in that: dithiocarbonic anhydride instills in the mixture of diisobutylamine and solvent at normal temperatures.
6. the preparation method according to claim 1 or 4, is characterized in that: in step (2), after dripping, and is warming up to 50 ~ 60 DEG C and reacts, and is preferably warming up to 53 ~ 57 DEG C and reacts.
7. preparation method according to claim 1, is characterized in that: in step (2), after dripping, reaction 4 ~ 6h, preferred reaction 4.5 ~ 5.5h.
8. preparation method according to claim 1, it is characterized in that: when the concentration of superoxol is 30wt%, each raw material as follows with magnitude relation: diisobutylamine 100 ~ 120 weight part, dithiocarbonic anhydride 70 ~ 84 weight part, 30wt% superoxol 50 ~ 65 weight part, solvent 400 ~ 700 weight part.
9. preparation method according to claim 8, it is characterized in that: when the concentration of superoxol is 30wt%, each raw material as follows with magnitude relation: diisobutylamine 100 weight part, dithiocarbonic anhydride 72 ~ 75 weight part, 30wt% superoxol 50 ~ 55 weight part, solvent 400 ~ 700 weight part.
10. preparation method according to claim 9, it is characterized in that: when the concentration of superoxol is 30wt%, each raw material as follows with magnitude relation: diisobutylamine 100 weight part, dithiocarbonic anhydride 73 weight part, 30wt% superoxol 52 weight part, solvent 500 weight part.
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Cited By (5)
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| CN106831515A (en) * | 2017-01-13 | 2017-06-13 | 山东斯递尔化工科技有限公司 | The method that tetra-benzyl thiram disulfide is continuously prepared using micro-reaction device |
| 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 |
| CN111018761A (en) * | 2019-12-27 | 2020-04-17 | 鹤壁元昊化工有限公司 | Synthesis process of tetrabenzylthiuram disulfide |
| CN111116440A (en) * | 2019-12-31 | 2020-05-08 | 蔚林新材料科技股份有限公司 | Process for preparing granular diisobutyl thiuram disulfide |
| CN112358428A (en) * | 2020-11-20 | 2021-02-12 | 鹤壁元昊化工有限公司 | Method for preparing thiuram disulfide by photocatalytic oxidation |
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| 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 |
| 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 |
| CN111116440A (en) * | 2019-12-31 | 2020-05-08 | 蔚林新材料科技股份有限公司 | Process for preparing granular diisobutyl thiuram disulfide |
| CN111116440B (en) * | 2019-12-31 | 2022-04-12 | 蔚林新材料科技股份有限公司 | Process for preparing granular diisobutyl thiuram disulfide |
| CN112358428A (en) * | 2020-11-20 | 2021-02-12 | 鹤壁元昊化工有限公司 | Method for preparing thiuram disulfide by photocatalytic oxidation |
| CN112358428B (en) * | 2020-11-20 | 2022-02-15 | 鹤壁元昊化工有限公司 | Method for preparing thiuram disulfide by photocatalytic oxidation |
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Application publication date: 20160504 |