CN105732451B - Thiofide PZ is produced without waste water - Google Patents
Thiofide PZ is produced without waste water Download PDFInfo
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- CN105732451B CN105732451B CN201610068593.4A CN201610068593A CN105732451B CN 105732451 B CN105732451 B CN 105732451B CN 201610068593 A CN201610068593 A CN 201610068593A CN 105732451 B CN105732451 B CN 105732451B
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- 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
- C07C333/16—Salts of dithiocarbamic acids
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Abstract
The invention discloses a kind of method of no waste water production thiofide PZ, using ethanol as solvent, using dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide as raw material, dimethylamine, carbon disulfide, nonionic surfactant, the weight ratio of zinc oxide and ethanol are 1.0:1.05‑1.15:0.01‑0.015:0.50‑0.55:5.05‑5.5.System of the present invention is anhydrous to be brought into, non-wastewater discharge, solvent is made with ethanol, shortens the reaction time, and the use of ethanol is not polluted to environment, recyclable recycling, has reached the effect of energy-saving, green doulbe-sides' victory, realizes the clean manufacturing of product；Excellent product quality, just fusing point >=245 DEG C, purity >=99.5%；Technique is simple, and reaction condition is gentle, not harsh to equipment requirement, product yield >=96%.
Description
Technical field
The present invention relates to thiofide, refers specifically to a kind of without waste water production thiofide DMDS
For carbaminate.
Background technology
Recently as the development of rubber industry, research and the production of vulcanization accelerator are increasingly taken seriously.This product
It is natural gum and rubber polymer ultras and latex beneficial agents in general, its butyl rubber small especially suitable for compression
Glue and the excellent nitrile rubber of ageing-resistant performance is required, be also applied for the very low ethylene propylene diene rubber of curing temperature.Due to its is nontoxic,
It is tasteless, do not pollute, be non-discolouring, therefore be also applied for adhesive plaster, food and druggist rubber sundrier.
Thiofide PZ (PZ) belongs to inorganic dithiocarbamates and surpassed
Fast accelerator is extensive in the industry to use.In the prior art, with two-step method synthesization of dimethyl disulfide for carbaminate.It is first
Sodium hydroxide solution and carbon disulfide are first added in the reactor, and dimethylamine, reaction temperature control are then added dropwise under agitation
System is below 30 DEG C, and dimethylamine continues to react 30min after being added dropwise, and intermediate product is in faint yellow, and it is molten that zinc chloride is finally added dropwise
Liquid, after reaction terminates, product is filtered, wash and is drying to obtain product.But this production technology product fusing point is low, yield is low,
Outward appearance is dark, can produce substantial amounts of waste water, and brought in waste water containing the salt for being largely difficult to direct biochemical treatment to environment protection treating
Very big difficulty, it is difficult to realize " cleaning green " production, do not meet national environmental protection policy and domestic and international market in this approach
High-end requirement.The method that Publication No. CN102295592A Chinese invention patent discloses zinc oxide one-step synthesis method PZ, should
The process of method is：Dimethylamine, the non-ionic surface of ormal weight are sequentially added into the reactor for filling pure water, under stirring
Activating agent, zinc oxide, after stirring be added dropwise carbon disulfide liquid, finally carry out separation of solid and liquid, liquid is given up, solid drying, crush,
Sieving, obtains PZ products.But the method accelerator PZ yield is up to 95.4%.Also, the solvent of above-mentioned process
All it is to use water, last separation of solid and liquid, liquid is given up, and can produce substantial amounts of waste water, and environment is caused seriously to pollute.
Therefore, Improvement is carried out to its synthetic method, research and development one kind makes product yield higher, and can be in production process
In the method for energy-saving, green no waste water production thiofide PZ seem
It is necessary.
The content of the invention
The technical problems to be solved by the invention seek to provide one kind without waste water production thiofide dimethyl
The method of zinc dithiocarbamate, the clean manufacturing of product can be realized by this method.
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.05-1.15:0.01-0.015:0.50-0.55:5.05-5.5.
Preferably, the weight ratio of dimethylamine, carbon disulfide, nonionic surfactant, zinc oxide and ethanol is 1.0:
1.1-1.15:0.012-0.015:0.53-0.55:5.35-5.45。
Further, the weight ratio of dimethylamine, carbon disulfide, nonionic surfactant, zinc oxide and ethanol is 1.0:
1.13:0.014:0.53:5.40。
Further, nonionic surfactant be Tween-20, OPEO, polyoxyethylene carboxylate,
One or more of mixtures in sorbitan ester.
Further, nonionic surfactant be Tween-20, OPEO, polyoxyethylene carboxylate,
Sorbitan ester is 4 by weight:2:1:1 composition.
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 20-30min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1-1.5h to control time for adding, and it is 20-30 to control temperature
℃；After being added dropwise to complete, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Further, in step 2), it is 20min to control mixing time.
Further, in step 3), it is 1.3h to control time for adding, and it is 20 DEG C to control temperature.
Dimethylamine is anhydrous dimethyl amine.
Advantages of the present invention is mainly reflected in following several respects：
Brought into first, system of the present invention is anhydrous, non-wastewater discharge, solvent is made with ethanol, shorten the reaction time, ethanol
Do not polluted using to environment, recyclable recycling, reached the effect of energy-saving, green doulbe-sides' victory, realized product
Clean manufacturing, meet environmental protection concept at this stage；
Second, the thiofide PZ that the present invention synthesizes is best in quality, incipient melting
Point >=245 DEG C, purity >=99.5%；
Third, present invention process is simple, reaction condition is gentle, not harsh to equipment requirement, product yield >=96%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but the embodiment should not be construed pair
The limitation of the present invention.
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.05-1.15:0.01-0.015:0.50-0.55:5.05-5.5.
Preferably, the weight ratio of dimethylamine, carbon disulfide, nonionic surfactant, zinc oxide and ethanol is 1.0:
1.1-1.15:0.012-0.015:0.53-0.55:5.35-5.45。
Further, the weight ratio of dimethylamine, carbon disulfide, nonionic surfactant, zinc oxide and ethanol is 1.0:
1.13:0.014:0.53:5.40。
Further, nonionic surfactant be Tween-20, OPEO, polyoxyethylene carboxylate,
One or more of mixtures in sorbitan ester.
Further, nonionic surfactant be Tween-20, OPEO, polyoxyethylene carboxylate,
Sorbitan ester is 4 by weight:2:1:1 composition.
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 20-30min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1-1.5h to control time for adding, and it is 20-30 to control temperature
℃；After being added dropwise to complete, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Further, in step 2), it is 20min to control mixing time.
Further, in step 3), it is 1.3h to control time for adding, and it is 20 DEG C to control temperature.
Embodiment 1
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.13:0.014:0.53:5.40.Wherein, nonionic surfactant is to tell
Temperature -20, OPEO, polyoxyethylene carboxylate, sorbitan ester are 4 by weight:2:1:1 composition.
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 20min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1.3h to control time for adding, and it is 20 DEG C to control temperature；It is added dropwise
After the completion of, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Products obtained therefrom yield is 99.1%, product purity 99.8%.
Embodiment 2
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.1:0.015:0.52:5.05.Wherein, nonionic surfactant be tween-
20。
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 30min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1.5h to control time for adding, and it is 25 DEG C to control temperature；It is added dropwise
After the completion of, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Products obtained therefrom yield is 98.3%, product purity 99.6%.
Embodiment 3
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.15:0.012:0.55:5.45.Wherein, nonionic surfactant is to tell
Temperature -20, polyoxyethylene carboxylate are 2 by weight:1 composition.
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 23min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1h to control time for adding, and it is 21 DEG C to control temperature；Drip
Cheng Hou, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Products obtained therefrom yield is 97.5%, product purity 99.6%.
Embodiment 4
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.12:0.013:0.50:5.45.Wherein, nonionic surfactant is to tell
Temperature -20, OPEO, sorbitan ester are 3 by weight:3:1 composition.
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 28min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1.2h to control time for adding, and it is 30 DEG C to control temperature；It is added dropwise
After the completion of, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Products obtained therefrom yield is 96.7%, product purity 99.5%.
Embodiment 5
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.14:0.010:0.54:5.50.Wherein, nonionic surfactant is to tell
Temperature -20, OPEO, polyoxyethylene carboxylate, sorbitan ester are 1 by weight:1:1:1 composition.
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 21min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1.1h to control time for adding, and it is 28 DEG C to control temperature；It is added dropwise
After the completion of, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Products obtained therefrom yield is 97.4%, product purity 99.7%.
Embodiment 6
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.05:0.01:0.5:5.40.Wherein, nonionic surfactant is octyl phenol
APEO, polyoxyethylene carboxylate, sorbitan ester are 2 by weight:1:3 compositions.
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 27min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1.4h to control time for adding, and it is 27 DEG C to control temperature；It is added dropwise
After the completion of, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Products obtained therefrom yield is 98.2%, product purity 99.6%.
Embodiment 7
Method without waste water production thiofide PZ, using ethanol as solvent, with
Dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide are raw material, dimethylamine, carbon disulfide, non-ionic surface active
The weight ratio of agent, zinc oxide and ethanol is 1.0:1.1:0.013:0.55:5.40.Wherein, nonionic surfactant is dehydration
Sorbitol ester.
Method without waste water production thiofide PZ, comprises the following steps：
1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；
2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control stirring
Time is 25min；
3) carbon disulfide and then is by weight slowly added dropwise, it is 1.5h to control time for adding, and it is 26 DEG C to control temperature；It is added dropwise
After the completion of, continue to stir, it is 0.5h to control mixing time；
4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, sieving
Afterwards, thiofide PZ is produced.
Products obtained therefrom yield is 97.6%, product purity 99.6%.
The content not being described in detail in this specification, belong to prior art known to those skilled in the art.
Claims (1)
- A kind of 1. method of no waste water production thiofide PZ, it is characterised in that：With Ethanol is solvent, using dimethylamine, carbon disulfide, nonionic surfactant and zinc oxide as raw material, dimethylamine, carbon disulfide, The weight ratio of nonionic surfactant, zinc oxide and ethanol is 1.0:1.13:0.014:0.53:5.40；The nonionic surfactant is Tween-20, OPEO, polyoxyethylene carboxylate, Sorbitan Alcohol ester is 4 by weight:2:1:1 composition；Comprise the following steps：1) into the reactor for the ethanol for filling parts by weight, dimethylamine is blasted by weight under stirring；2) stirred again by weight nonionic surfactant, zinc oxide are put into reactor successively, control mixing time For 20min；3) carbon disulfide and then is by weight slowly added dropwise, it is 1.3h to control time for adding, and it is 20 DEG C to control temperature；It is added dropwise to complete Afterwards, continue to stir, it is 0.5h to control mixing time；4) separation of solid and liquid is carried out, gained liquid is filtered, rectifying, reclaims ethanol；By the drying of gained solid, crush, after sieving, i.e., Obtain thiofide PZ.
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| CN108003078A (en) * | 2017-12-21 | 2018-05-08 | 蔚林新材料科技股份有限公司 | The preparation method of thiofide EZ |
| CN110483355A (en) * | 2019-07-30 | 2019-11-22 | 上海裕诚化工有限公司 | The synthetic method of dialkyldithiocarbamates zinc salt |
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| CN102295592A (en) * | 2011-06-22 | 2011-12-28 | 濮阳蔚林化工股份有限公司 | Preparation method of rubber vulcanization accelerator zinc dimethyldithiocarbamate |
| CN105061277A (en) * | 2015-07-16 | 2015-11-18 | 山东阳谷华泰化工股份有限公司 | Environment-friendly preparation method of accelerator zinc dibenzyldithiocarbamate |
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