CN105399652A - Preparation method of rubber vulcanization accelerator of dimethyldithiocarbamate selenium - Google Patents
Preparation method of rubber vulcanization accelerator of dimethyldithiocarbamate selenium Download PDFInfo
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- CN105399652A CN105399652A CN201410436972.5A CN201410436972A CN105399652A CN 105399652 A CN105399652 A CN 105399652A CN 201410436972 A CN201410436972 A CN 201410436972A CN 105399652 A CN105399652 A CN 105399652A
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Abstract
The invention discloses a preparation method of a rubber vulcanization accelerator of dimethyldithiocarbamate selenium. The preparation method comprises the following steps: (1) solution preparation, in which, a selenium-containing solution and a dimethyldithiocarbamate solution are prepared; (2) synthesis of dimethyldithiocarbamate selenium, in which the prepared selenium-containing solution reacts with the dimethyldithiocarbamate solution under a reaction condition of a pH value being 7-9 and the temperature in a range of 0-90 DEG C; and (3) separation of dimethyldithiocarbamate selenium, in which, a final product of dimethyldithiocarbamate selenium is obtained.
Description
Technical field
The present invention relates to thiofide field, exactly refer to a kind of preparation method of thiofide Selenium dimethyl dithiocarbamate.
Background technology
Dithiocarbamate(s) compound is mainly used as the ultra fast accelerator in Vulcanization Process of Rubber.Compared with the vulcanization accelerator of other type, dithiocarbamatetype accelerator has that vulcanization rate is very fast, curing temperature is low, dispersing property good, degree of crosslinking is high, low toxin, but easily incipient scorch, sulfuration flatness are poor.Use thiocarbamate class promotor can obtain the larger vulcanized rubber of tensile stress, but tensile strength and tensile yield ratio use sulfenamide type accelerators low.
Research shows, when two kinds of ultra-rapid vulcanization accelerator combinations, can produce synergistic effect, easily miscible when its reason may be accelerator combination, defines the salt-forming compound that solubleness is comparatively large and chemically reactive is larger in rubber.Generally adopt the vulcanization system of two or more accelerator combinations in current Rubber processing industry, when having bibliographical information xanthogenate/zinc diethyldithiocarbamate accelerator combination sulfurized natural rubber, there is positive synergistic effect.
Selenium dimethyl dithiocarbamate is as the one in thiocarbamate class, its Main Function is presented as with thiazoles and for NR, IIR, SBR, nondiscoloration in light color article, more effective in the heat-resisting formula of low-sulfur, it also can also use as vulcanizing agent.
At present, also do not have the synthetic method of document or the open Selenium dimethyl dithiocarbamate of data, need to make up this sheet blank.
Summary of the invention
For above-mentioned defect, the technical problem that the present invention solves is the preparation method providing a kind of thiofide Selenium dimethyl dithiocarbamate.
In order to solve above technical problem, the preparation method of thiofide Selenium dimethyl dithiocarbamate provided by the invention, comprises the steps:
(1) obtain solution
Preparation Se solution: by selenium oxide alkali lye or water dissolution, forms the solution containing selenium; Or by selenite water dissolution, obtain the solution containing selenium;
Preparation dimethyl dithiocarbamate solution: dimethyl dithiocarbamate is soluble in water, forms dimethyl dithiocarbamate solution;
(2) synthesization of dimethyl disulfide is for carboxylamine selenium
The Se solution configured and dimethyl dithiocarbamate solution are reacted, reaction conditions is as follows:
PH value is 7-9, and temperature is 0-90 DEG C;
(3) Selenium dimethyl dithiocarbamate is separated.
Preferably, in step (1), in Se solution, the concentration of selenium is 0.25-1mol/L.
3 preferably, and in step (1), the concentration of alkali lye is concentration 1-3 times of Se solution.
Preferably, in step (1), alkali lye reacts to selenium oxide and generates corresponding selenite.
Preferably, in step (1), alkali lye is formulated by one or more materials in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus.
Preferably, in step (1), the concentration of dimethyl dithiocarbamate solution is 10-40wt%.
Preferably, in step (2), regulate reaction conditions pH value to be 7-9 with acid solution, acid solution is formulated by one or more of hydrochloric acid, acetic acid or nitric acid.
Preferably, the concentration of acid solution is 0.5-2mol/L.
Preferably, in step (2), the Se solution configured and dimethyl dithiocarbamate solution are reacted, the endpoint pH of reaction is at 6-7.
Preferably, in step (3), be separated Selenium dimethyl dithiocarbamate:
Conventional filtration, washing, drying, breaking method is adopted to process Selenium dimethyl dithiocarbamate product, thus obtain the finished product Selenium dimethyl dithiocarbamate.
Compared with prior art, the preparation method of thiofide Selenium dimethyl dithiocarbamate of the present invention, has the following advantages:
1, do not produce waste gas and waste residue in process of producing product, environmental pollution is little;
2, product purity is high, can reach more than 99%;
3, productive rate is large, can reach more than 95%.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of thiofide Selenium dimethyl dithiocarbamate in the embodiment of the present invention, and wherein, SeDMC is Selenium dimethyl dithiocarbamate.
Embodiment
In order to those skilled in the art can understand technical scheme provided by the present invention better, set forth below in conjunction with specific embodiment.
Refer to Fig. 1, this figure is the schema of the preparation method of thiofide Selenium dimethyl dithiocarbamate in the embodiment of the present invention, and wherein, SeDMC is Selenium dimethyl dithiocarbamate.
Of the present inventionly to comprise the steps:
(1) obtain solution
Preparation Se solution: by selenium oxide alkali lye or water dissolution, forms the solution containing selenium; Or by selenite water dissolution, obtain the solution containing selenium;
Preparation dimethyl dithiocarbamate solution: dimethyl dithiocarbamate is soluble in water, forms dimethyl dithiocarbamate solution;
(2) synthesization of dimethyl disulfide is for carboxylamine selenium
The Se solution configured and dimethyl dithiocarbamate solution are reacted, reaction conditions is as follows:
PH value is 7-9, and temperature is 0-90 DEG C;
Reaction conditions pH value is regulated with acid solution;
(3) Selenium dimethyl dithiocarbamate is separated
Conventional filtration, washing, drying, breaking method is adopted to process Selenium dimethyl dithiocarbamate product, thus obtain the finished product Selenium dimethyl dithiocarbamate.
Embodiment 1
The preparation method of the thiofide Selenium dimethyl dithiocarbamate that the embodiment of the present invention provides, the dimethyl dithiocarbamate of 62.5g is dissolved in the water of 94g, be warming up to 80 DEG C, until completely dissolved, the selenous acid of 100ml0.5mol/L is added reaction system, stir after 30min, in 1h, the hydrochloric acid of 1mol/L is slowly added under agitation reaction system to system pH to 6-7 between.The pale yellow precipitate occurred in adjust ph process is Selenium dimethyl dithiocarbamate.Product, through washing and filtering, 90 DEG C of dryings, obtains the Selenium dimethyl dithiocarbamate product of 26.7g, wherein selenium content 14.5%, fusing point 256-265 DEG C.
Embodiment 2
The preparation method of the thiofide Selenium dimethyl dithiocarbamate that the embodiment of the present invention provides, the dimethyl dithiocarbamate of 62.5g is dissolved in the water of 146g, temperature of reaction 5-10 DEG C is controlled with ice-water bath, until completely dissolved, the selenous acid of 100ml0.5mol/L is added reaction system, stir after 30min, in 1h, the hydrochloric acid of 1mol/L is slowly added under agitation reaction system to system pH to 6-7 between.The pale yellow precipitate occurred in adjust ph process is Selenium dimethyl dithiocarbamate.Product, through washing and filtering, 90 DEG C of dryings, obtains the Selenium dimethyl dithiocarbamate product of 27.3g, wherein selenium content 14.3%, fusing point 249-262 DEG C.
Embodiment 3
The preparation method of the thiofide Selenium dimethyl dithiocarbamate that the embodiment of the present invention provides, the dimethyl dithiocarbamate of 62.5g is dissolved in the water of 146g, temperature of reaction 5-10 DEG C is controlled with ice-water bath, until completely dissolved, the selenous acid of 100ml0.5mol/L is added reaction system, stir after 30min, in 1h, the hydrochloric acid of 1mol/L is slowly added under agitation reaction system to system pH to 6-7 between.The pale yellow precipitate occurred in adjust ph process is Selenium dimethyl dithiocarbamate.Product, through washing and filtering, 90 DEG C of dryings, obtains the Selenium dimethyl dithiocarbamate product of 27.3g, wherein selenium content 14.3%, fusing point 249-262 DEG C.
Embodiment 4
The preparation method of the thiofide Selenium dimethyl dithiocarbamate that the embodiment of the present invention provides, the dimethyl dithiocarbamate of 62.5g is dissolved in the sodium hydroxide lye of 178g, temperature of reaction 30-60 DEG C is controlled with ice-water bath, until completely dissolved, the Sodium Selenite of 100ml0.75mol/L is added reaction system, stir after 30min, in 1h, the nitric acid of 1mol/L is slowly added under agitation reaction system to system pH to 6-7 between.The pale yellow precipitate occurred in adjust ph process is Selenium dimethyl dithiocarbamate.Product, through washing and filtering, 90 DEG C of dryings, obtains the Selenium dimethyl dithiocarbamate product of 26.3g, wherein selenium content 13.8%, fusing point 242-261 DEG C.
Compared with prior art, the preparation method of thiofide Selenium dimethyl dithiocarbamate of the present invention, has the following advantages:
1, do not produce waste gas and waste residue in process of producing product, environmental pollution is little;
2, product purity is high, can reach more than 99%;
3, productive rate is large, can reach more than 95%.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for thiofide Selenium dimethyl dithiocarbamate, is characterized in that, comprises the steps:
(1) obtain solution
Preparation Se solution: by selenium oxide alkali lye or water dissolution, forms the solution containing selenium; Or by selenite water dissolution, obtain the solution containing selenium;
Preparation dimethyl dithiocarbamate solution: dimethyl dithiocarbamate is soluble in water, forms dimethyl dithiocarbamate solution;
(2) synthesization of dimethyl disulfide is for carboxylamine selenium
The Se solution configured and dimethyl dithiocarbamate solution are reacted, reaction conditions is as follows:
PH value is 7-9, and temperature is 0-90 DEG C;
(3) Selenium dimethyl dithiocarbamate is separated.
2. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 1, is characterized in that, in step (1), in Se solution, the concentration of selenium is 0.25-1mol/L.
3. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 2, is characterized in that, in step (1), the concentration of alkali lye is concentration 1-3 times of Se solution.
4. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 3, is characterized in that, in step (1), alkali lye reacts to selenium oxide and generates corresponding selenite.
5. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 3, it is characterized in that, in step (1), alkali lye is formulated by one or more materials in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus.
6. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 1, is characterized in that, in step (1), the concentration of dimethyl dithiocarbamate solution is 10-40wt%.
7. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 1, it is characterized in that, in step (2), regulate reaction conditions pH value to be 7-9 with acid solution, acid solution is formulated by one or more of hydrochloric acid, acetic acid or nitric acid.
8. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 7, is characterized in that, the concentration of acid solution is 0.5-2mol/L.
9. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 1, it is characterized in that, in step (2), the Se solution configured and dimethyl dithiocarbamate solution are reacted, the endpoint pH of reaction is at 6-7.
10. the preparation method of thiofide Selenium dimethyl dithiocarbamate according to claim 1, is characterized in that, in step (3), is separated Selenium dimethyl dithiocarbamate:
Conventional filtration, washing, drying, breaking method is adopted to process Selenium dimethyl dithiocarbamate product, thus obtain the finished product Selenium dimethyl dithiocarbamate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2347128A (en) * | 1943-05-25 | 1944-04-18 | Vanderbilt Co R T | Production of dithiocarbamates |
| US5753125A (en) * | 1995-05-19 | 1998-05-19 | Kreisler; Lawrence | Method for recovering and separating metals from waste streams |
| CN1321637A (en) * | 2001-04-09 | 2001-11-14 | 华东理工大学 | Preparation method of tellurium diethyl dithiocarbamate |
| CN103524390A (en) * | 2012-07-05 | 2014-01-22 | 广东先导稀材股份有限公司 | Preparation method of tellurium diethyl dithiocarbamate |
-
2014
- 2014-08-29 CN CN201410436972.5A patent/CN105399652A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2347128A (en) * | 1943-05-25 | 1944-04-18 | Vanderbilt Co R T | Production of dithiocarbamates |
| US5753125A (en) * | 1995-05-19 | 1998-05-19 | Kreisler; Lawrence | Method for recovering and separating metals from waste streams |
| CN1321637A (en) * | 2001-04-09 | 2001-11-14 | 华东理工大学 | Preparation method of tellurium diethyl dithiocarbamate |
| CN103524390A (en) * | 2012-07-05 | 2014-01-22 | 广东先导稀材股份有限公司 | Preparation method of tellurium diethyl dithiocarbamate |
Non-Patent Citations (1)
| Title |
|---|
| 吴世敏 印德麟主编: "《简明精细化工大辞典》", 30 June 1999, 辽宁科学技术出版社 * |
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