CN108148018A - The preparation method of thiofide DPTT-6 - Google Patents
The preparation method of thiofide DPTT-6 Download PDFInfo
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- CN108148018A CN108148018A CN201711389928.3A CN201711389928A CN108148018A CN 108148018 A CN108148018 A CN 108148018A CN 201711389928 A CN201711389928 A CN 201711389928A CN 108148018 A CN108148018 A CN 108148018A
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- thiofide
- dptt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/21—Radicals derived from sulfur analogues of carbonic acid
Abstract
The present invention provides a kind of preparation methods of thiofide DPTT 6, it is related to thiofide technical field, sulphur, hexahydropyridine and surfactant are added to mixing in low-carbon alcoholic solvent by preparation method of the present invention, then, carbon disulfide and hydrogen peroxide and temperature reaction are added dropwise successively, thiofide DPTT 6 is made.Above-mentioned preparation method makees solvent using low-carbon alcohols that are less toxic, cheap, being easily recycled and apply mechanically, oxidation through peroxide hydrogen peroxide at a lower temperature, six vulcanization di-penta methylene thiuram of synthesis, the preparation method has the advantages that simple for process, product yield is high, purity is high, product yield >=97.0% obtained, just fusing point >=115.0 DEG C, purity >=98.0%；Meanwhile discharged in preparation process of the present invention without " three wastes ", solvent whole recovery, non-environmental-pollution realizes zero emission.
Description
Technical field
The present invention relates to thiofide technical field, more particularly, to a kind of thiofide DPTT-6's
Preparation method.
Background technology
Pollution has become Chinese society economy with the limited contradiction of Ecological Environment Capacity caused by China's industrial development at present
The Vital Strategic Problems of urgent need to resolve in development.Following Rubber Accelerator Industry development must adhere to low-carbon economy, green economy reason
It reads, to continually develop cleaning low-carbon process route as main development model.Only in this way, can really run business big and strong China rubber
Glue auxiliary agent industry.Therefore, the clean and effective technology exploitation of some principal items becomes the key of industry development with application.
Six vulcanization di-penta methylene thiurams (DPTT-6) are used as a kind of thiofide, are now widely used for making day
In the synthesis of T PNR, synthetic rubber and latex, free sulphur can be decomposited when being heated due to DPTT-6, therefore also is used as vulcanizing
Agent, during as vulcanizing agent, relatively safety at the operational, vulcanizate is heat-resisting, ageing-resistant performance is excellent.This product is gathered in chlorosulfonation
Primary accelerator can be done in ethylene rubber, butadiene-styrene rubber, butyl rubber, when with thiazole accelerator and used time especially suitable for butyronitrile
Glue.Six vulcanization di-penta methylene thiurams (DPTT-6) are easily dispersed in dry rubber substance, are also easily dispersed in water, are not polluted, general to use
In manufacture heat resistant article, cable etc..
The synthetic technology of domestic DPTT-6 at present is generally acted on using hexahydropyridine and carbon disulfide in sodium hydroxide
Product is precipitated under the conditions of nitration mixture dropwise addition in lower condensation synthesis sodium pentamethylene dithiocarbamate, sodium salt, synthetic method production
The raw sodium sulfate wastewater for being largely difficult to biochemical treatment, causes environment larger pollution；Dioxygen oxidation method is to add in six at room temperature
Pyridinium hydroxide, triethylamine and Cosan add in metal salt catalyst after carbon disulfide condensation is added dropwise, heat up 50 DEG C, be passed through oxygen extremely
Pressure is set, reaction 1h no longer changes to pressure as reaction end, and since reaction is carried out under band pressure condition, this technique exists
Since reaction is carried out under band pressure condition in production, the reactant in reaction kettle is gaseous material, is easily exploded, thus
In process of production there are great security risk, while production process high energy consumption.
The production method of di-penta methylene thiuram tetrasulfide as rubber vulcanizing accelerator in CN200610107367.9, raw material and
It matches and is:Hexahydropyridine:Carbon disulfide:Sulphur:Hydrogen peroxide=1:1-1.3:1.8-2.5:0.4-0.7.Without molten in reaction process
Agent adjusts reactiveness by pH value.Reaction is difficult to carry out, it is impossible to realize preferable production status；CN200810183220.7
Introduce a kind of preparation method of di-penta methylene thiuram tetrasulfide as rubber vulcanizing accelerator, wherein the method using water as solvent,
Used raw material and its molar ratio are:Hexahydropyridine:Carbon disulfide:Sulphur:Hydrogen peroxide=1:1-1.3:1.8-2.5:0.4-
0.7, the specific embodiment of this method is：Under normal pressure, six are sequentially added into the reaction kettle for fill water under stirring
Pyridinium hydroxide and sulphur control temperature in the range of 20-30 DEG C after addition, carbon disulfide liquid, control drop is then added dropwise
2-3 hours between added-time, the pH value of reaction solution is measured after being added dropwise, treats that the pH value of reaction solution is stablized in the range of 6.5-7.5
Afterwards, the temperature of reaction solution is controlled at 30 DEG C -40 DEG C, starts that hydrogen peroxide progress oxidation reaction is added dropwise, the time of oxidation reaction is 3-4
Hour, it is to be oxidized after reaction, then insulation reaction 1 hour carries out separation of solid and liquid and obtains product later.But due to reaction
Using water as solvent, waste water is difficult to handle, and brings very big environmental protection pressure.
Therefore, research and develop it is a kind of it is simple for process, product yield is high, purity is high, meanwhile, reaction dissolvent is not aqueous and can
Six vulcanization di-penta methylene thiuram (DPTT-6) preparation methods of recycling, to alleviate the production process energy of DPTT-6 in the prior art
Consumption is high, the problem of generating a large amount of waste water, very big difficulty is brought to environment protection treating, becomes very necessary and urgent.
In view of this, it is special to propose the present invention.
Invention content
The first object of the present invention is to provide a kind of preparation method of thiofide DPTT-6, the preparation side
Method has that simple for process, product yield is high, purity is high, meanwhile, the advantages that reaction dissolvent is not aqueous and recyclable.
The preparation method of thiofide DPTT-6 provided by the invention a kind of, the preparation method include following step
Suddenly：
Sulphur, hexahydropyridine and surfactant are added to mixing in low-carbon alcoholic solvent, then, curing is added dropwise successively
Thiofide DPTT-6 is made in carbon and hydrogen peroxide and temperature reaction.
Further, the low-carbon alcoholic solvent is any one in methanol, ethyl alcohol, isopropanol or n-butanol.
Further, the mass ratio of the low-carbon alcoholic solvent and hexahydropyridine is 10.0~15.0:1.
Further, the molar ratio of the hexahydropyridine, carbon disulfide, sulphur and hydrogen peroxide is 1:1.0~1.2:1.9~
2.3:0.5~0.8.
Further, the surfactant is three ethylene oxide alkyl phenylates, trimethyloctadecyl ammonium chloride, dodecane
Any one in base benzene sulfonic acid sodium salt or diisobutyl sodium naphthalene sulfonate.
Further, the mass ratio of the hexahydropyridine and surfactant is 20.0~25.0:1.
Further, the time for adding of the carbon disulfide is 1.2~1.8h, and dropping temperature is 16~18 DEG C.
Further, the time for adding of the hydrogen peroxide is 3.5~4.5h, and dropping temperature is 20~25 DEG C.
Further, the preparation method further includes the thiofide DPTT-6 that will be obtained and crushing is dried
Step.
Preferably, the temperature of the drying is 70~80 DEG C.
Further, the preparation method specifically includes following steps：
Sulphur is added in low-carbon alcoholic solvent first and is stirred 20~30min, hexahydropyridine is then added in and surface is lived
Property agent be stirred, then adjust the temperature to 16~18 DEG C of dropwise addition carbon disulfide, after carbon disulfide completion of dropwise addition, constant temperature stirring is anti-
Answer 0.5~1.0h；It is warming up to 20~25 DEG C later, hydrogen peroxide, constant temperature after hydrogen peroxide completion of dropwise addition are added dropwise under conditions of constant temperature
React 0.5~1.0h；70~80 DEG C of 0.5~1.0h of reaction are finally warming up to, thiofide DPTT-6 is made.
Compared with prior art, beneficial effects of the present invention are：
The preparation method of thiofide DPTT-6 provided by the invention, by sulphur, hexahydropyridine and surface-active
Agent is added to mixing in low-carbon alcoholic solvent, then, carbon disulfide and hydrogen peroxide and temperature reaction is added dropwise successively, the vulcanization of rubber is made
Diphenylguanidine PTT-6.Above-mentioned preparation method makees solvent using low-carbon alcohols that are less toxic, cheap, being easily recycled and apply mechanically, compared with
Oxidation through peroxide hydrogen peroxide under low temperature, six vulcanization di-penta methylene thiuram (DPTT-6) of synthesis.The preparation side
Method has the advantages that simple for process, product yield is high, purity is high, product yield >=97.0% obtained, just fusing point >=115.0
DEG C, purity >=98.0%；Meanwhile discharged in preparation process of the present invention without " three wastes ", solvent whole recovery, no environment is dirty
Dye, realizes zero emission.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution of the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is the chemical structural formula of thiofide DPTT-6 in embodiment of the present invention；
Fig. 2 is the chromatogram of thiofide DPTT-6 that the embodiment of the present invention 1 is prepared；
Fig. 3 is the chromatogram of thiofide DPTT-6 that the embodiment of the present invention 2 is prepared；
Fig. 4 is the chromatogram of thiofide DPTT-6 that the embodiment of the present invention 3 is prepared；
Fig. 5 is the chromatogram of thiofide DPTT-6 that the embodiment of the present invention 4 is prepared；
Fig. 6 is the chromatogram of thiofide DPTT-6 that the embodiment of the present invention 5 is prepared.
Specific embodiment
Technical scheme of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's all other embodiments obtained without making creative work, shall fall within the protection scope of the present invention.
According to an aspect of the present invention, a kind of preparation method of thiofide DPTT-6, the preparation method
Include the following steps：Sulphur, hexahydropyridine and surfactant are added to mixing in low-carbon alcoholic solvent, then, are added dropwise successively
Thiofide DPTT-6 is made in carbon disulfide and hydrogen peroxide and temperature reaction.
Sulphur, hexahydropyridine and surfactant are added to by the preparation method of thiofide DPTT-6 of the present invention
Mixing in low-carbon alcoholic solvent then, is added dropwise carbon disulfide and hydrogen peroxide and temperature reaction, thiofide is made successively
DPTT-6.Above-mentioned preparation method makees solvent using low-carbon alcohols that are less toxic, cheap, being easily recycled and apply mechanically, in lower temperature
The lower oxidation through peroxide hydrogen peroxide has synthesized six vulcanization di-penta methylene thiurams (DPTT-6).The preparation method has
There is the advantages of simple for process, product yield is high, purity is high, product yield >=97.0% obtained, just fusing point >=115.0 DEG C are pure
Degree >=98.0%；Meanwhile discharged in preparation process of the present invention without " three wastes ", solvent whole recovery, non-environmental-pollution, it realizes
Zero emission.
The chemical structural formula of thiofide DPTT-6 of the present invention is as shown in Figure 1.
The preparation reaction of thiofide DPTT-6 of the present invention includes the following raw material：
Hexahydropyridine refers generally to piperidines.Colourless liquid.There is the smell as pepper.It is water-miscible, be dissolved in ethyl alcohol, ether,
Acetone and benzene.Relative vapor density (air=1)：3.0, saturated vapour pressure (kPa)：5.33 (29.2 DEG C), the combustion heat (kJ/
mol)：3455.2.The azeotropic aqueous solution boiling point of 35% piperidines is 92.8 DEG C；pKa11.1；Alkalinity is slightly better than pyridine.With acid into salt,
A kind of chemical property strong organic base similar to fatty primary secondary amine acts on generation salt with inorganic acid.It can volatilize together with steam.For making
Medicine, mainly piperidine hydrochloride and nitric acid piperidines (flat crystal, 110 DEG C of fusing point).Other organic syntheses are also used for, and as epoxy
Curing agent of resin etc..It is hydrogenated and obtained by pyridine.With stronger reproducibility.
Carbon disulfide, colourless or light yellow transparent liquid, sterling have ether taste.Fusing point：- 111.9 DEG C, density 1.26g/
Cm3, relative vapor density (air=1) 2.64,46.2 DEG C of boiling point.It is not soluble in water, it is most organic molten to be dissolved in ethyl alcohol, ether etc.
Agent.The pure carbon disulfide of use for laboratory has fragrant sweet taste, but usually impure industrial goods are because being mixed with other sulfide
It is yellowish, and have rotten radish taste beastly.
Hydrogen peroxide (chemical formula：H2O2), can arbitrary proportion and water dissolution, be a kind of strong oxidizer, aqueous solution is commonly called as dioxygen
Water is colourless transparent liquid.Its aqueous solution is suitable for medical wound disinfection and environment disinfected.It can slowly decompose under normal circumstances
Cheng Shui and oxygen, but decomposition rate is extremely slow.Aqueous hydrogen peroxide solution is colourless transparent liquid, water, alcohol is dissolved in, insoluble in oil
Ether.Pure hydrogen peroxide is nattier blue thick liquid, -0.43 DEG C of fusing point, 150.2 DEG C of boiling point, its molecule structure of pure hydrogen peroxide
Type can change, so molten boiling point can also change.Density of solid is 1.71g/cm during solidification point3, density with temperature raising and
Reduce.Its associating intensity compares H2O is big, so its boiling point is higher than water.
Sulphur alias sulphur, colloid sulphur.Appearance is crystallized for faint yellow brittleness or powder, there is off-odor.Molecular weight is
32.06, vapour pressure is 0.13kPa, and fusing point is 119 DEG C, and boiling point is 444.6 DEG C, and relative density (water=1) is 2.0.Sulphur is insoluble
Yu Shui is slightly soluble in ethyl alcohol, ether, is soluble in carbon disulfide.As inflammable solid, sulphur is mainly for the manufacture of dyestuff, pesticide, fire
Bavin, gunpowder, rubber, artificial silk etc..Commodity sulphur is yellow solid or powder, has apparent smell, can volatilize.Sulphur aqueous suspensions are in
Subacidity, it is not soluble in water, generation polysulfide is reacted with alkali.Cyan flame is sent out during sulfur burning, dioxy is generated with burning
Change sulphur gas.Sulphur is often processed into colloidal suspending agent for preventing pest and disease damage in production, it is not easy to make to make produce to people, animal safety
Crude drug is done harm to.
In the present invention, the low-carbon alcoholic solvent refers to the solution of the low-carbon alcohols containing 1~4 carbon atom.
In the preferred embodiment of the present invention, the low-carbon alcoholic solvent is methanol, ethyl alcohol, isopropanol or n-butanol
In any one.
As a preferred embodiment, above-mentioned low-carbon alcoholic solvent is appointing in methanol, ethyl alcohol, isopropanol or n-butanol
Meaning is a kind of, above-mentioned solvent have the advantages that it is less toxic, cheap, be easily recycled and apply mechanically, it is of the invention to use low-carbon alcoholic solvent,
Oxidation through peroxide hydrogen peroxide under lower temperature has synthesized six vulcanization di-penta methylene thiurams, nothing in preparation process
" three wastes " discharge, and solvent whole recovery, non-environmental-pollution realizes zero emission.
In above-mentioned preferred embodiment, the mass ratio of the low-carbon alcoholic solvent and hexahydropyridine is 10~15:1.
Preferably, the mass ratio of above-mentioned low-carbon alcoholic solvent and hexahydropyridine is 12:1.
In the preferred embodiment of the present invention, mole of the hexahydropyridine, carbon disulfide, sulphur and hydrogen peroxide
Than being 1:1.0~1.2:1.9~2.3:0.5~0.8.
As a preferred embodiment, above-mentioned hexahydropyridine, carbon disulfide, sulphur and hydrogen peroxide molar ratio be 1:
1.0~1.2:1.9~2.3:0.5~0.8.Under conditions of above-mentioned molal weight ratio, the present invention can be made to prepare the anti-of reaction
It should avoid the waste of reaction raw materials more completely.
In the preferred embodiment of the present invention, the surfactant is three ethylene oxide alkyl phenylates, trimethyl
Any one in octadecyl ammonium chloride, neopelex or diisobutyl sodium naphthalene sulfonate.
As a preferred embodiment, above-mentioned surfactant, which is added in reaction system, can make reaction raw materials
The mixing being more uniformly distributed in organic solvent, into but reaction it is more efficient, meanwhile, also accelerate the speed of reaction.
In above-mentioned preferred embodiment, the mass ratio of the hexahydropyridine and surfactant is 20~25:1.
In the preferred embodiment of the present invention, the time for adding of the carbon disulfide is 1.2~1.8h.
In the preferred embodiment of the present invention, the time for adding of the hydrogen peroxide is 3.5~4.5h.
As a preferred embodiment, the time for adding of above-mentioned hydrogen peroxide is 3.5~4.5h, the present invention can be controlled
The intensity of reaction avoids reaction from excessively causing unnecessary security risk strongly.
In the preferred embodiment of the present invention, the preparation method further includes the thiofide that will be obtained
The step of crushing is dried in DPTT-6.
In above-mentioned preferred embodiment, the temperature of the drying is 70~80 DEG C.
Preferably, the temperature of the drying is 80 DEG C.
In the preferred embodiment of the present invention, the preparation method specifically includes following steps：
Sulphur is added in low-carbon alcoholic solvent first and is stirred 20~30min, hexahydropyridine is then added in and surface is lived
Property agent be stirred, then adjust the temperature to 16~18 DEG C of dropwise addition carbon disulfide, after carbon disulfide completion of dropwise addition, constant temperature stirring is anti-
Answer 0.5~1.0h；It is warming up to 20~25 DEG C later, hydrogen peroxide, constant temperature after hydrogen peroxide completion of dropwise addition are added dropwise under conditions of constant temperature
React 0.5~1.0h；70~80 DEG C of 0.5~1.0h of reaction are finally warming up to, thiofide DPTT-6 is made.
Embodiment 1
A kind of preparation method of thiofide DPTT-6, the preparation method include the following steps：
First, it will be stirred in 250ml ethyl alcohol and 14.0g sulphur addition 1000ml four-hole bottles in atmospheric conditions mixed
It closes, is stirred the time as 30min；Then 19.6g hexahydropyridines and 0.98g trimethyloctadecyl ammonium chlorides, control are added in
18 DEG C of temperature starts that 17.87g carbon disulfide is added dropwise, and temperature control is 18 DEG C during dropwise addition, time for adding 1.5h；It is added dropwise
After, controlled at 18 DEG C of reaction 1.0h；
Then, 22 DEG C are warming up to, starts that the mixed solution of 17.07g hydrogen peroxide and 108.17ml ethyl alcohol is added dropwise, control is added dropwise
Speed makes reaction temperature be 22 DEG C, time for adding 3.5h；Then insulation reaction 0.5h；
Finally, gained reaction solution is warming up to 75 DEG C, then insulation reaction 0.5h.35 DEG C are cooled to, is then filtered, 80 DEG C
Dry, crushing, obtains thiofide DPTT-6.
By made from the present embodiment thiofide DPTT-6 carry out chromatography detection, profiling results as shown in Fig. 2,
Data results are as shown in the table：
By upper table analysis it is found that being detected through chromatography, product yield 98.6%, 116.2 DEG C of just fusing point, purity 99.65%.
Embodiment 2
A kind of preparation method of thiofide DPTT-6, the preparation method include the following steps：
First, it will be stirred in 250ml ethyl alcohol and 14.0g sulphur addition 1000ml four-hole bottles in atmospheric conditions mixed
It closes, is stirred the time as 30min；Then 22.5g hexahydropyridines and 0.98g trimethyloctadecyl ammonium chlorides, control are added in
18 DEG C of temperature starts that 19.87g carbon disulfide is added dropwise, and temperature control is 18 DEG C during dropwise addition, time for adding 1.5h；It is added dropwise
After, controlled at 18 DEG C of reaction 1.0h；
Then, 22 DEG C are warming up to, starts that the mixed solution of 17.07g hydrogen peroxide and 108.17ml ethyl alcohol is added dropwise, control is added dropwise
Speed makes reaction temperature be 22 DEG C, time for adding 3.5h；Then insulation reaction 0.5h；
Finally, gained reaction solution is warming up to 75 DEG C, then insulation reaction 0.5h.35 DEG C are cooled to, is then filtered, 80 DEG C
Dry, crushing, obtains thiofide DPTT-6.
By made from the present embodiment thiofide DPTT-6 carry out chromatography detection, profiling results as shown in figure 3,
Data results are as shown in the table：
By upper table analysis it is found that being detected through chromatography, product yield 99.2%, 116.5 DEG C of just fusing point, purity 99.02%.
Embodiment 3
A kind of preparation method of thiofide DPTT-6, the preparation method include the following steps：
First, 245ml isopropanols and 12.07g sulphur are added in 1000ml four-hole bottles in atmospheric conditions and are stirred
Mixing is stirred the time as 40min；Then 16.04g hexahydropyridines and 0.73g neopelexes, control temperature are added in
17 DEG C of degree starts that 17.55g carbon disulfide is added dropwise, and temperature control is 17 DEG C during dropwise addition, time for adding 1.2h；Knot is added dropwise
Shu Hou, controlled at 17 DEG C of reaction 0.5h；
Then, 24 DEG C are warming up to, starts that the mixed solution of 16.3g hydrogen peroxide and 145.26ml isopropanols, control drop is added dropwise
Acceleration makes reaction temperature be 24 DEG C, time for adding 4.0h；Then insulation reaction 0.5h；
Finally, gained reaction solution is warming up to 70 DEG C, then insulation reaction 0.5h.Be cooled to 36 DEG C, start filtering, 80 DEG C
Dry, crushing, obtains thiofide DPTT-6.
By made from the present embodiment thiofide DPTT-6 carry out chromatography detection, profiling results as shown in figure 4,
Data results are as shown in the table：
By upper table analysis it is found that being detected through chromatography, product yield 97.3%, 115.8 DEG C of just fusing point, purity 99.42%.
Embodiment 4
A kind of preparation method of thiofide DPTT-6, the preparation method include the following steps：
First, 245ml isopropanols and 12.07g sulphur are added in 1000ml four-hole bottles in atmospheric conditions and are stirred
Mixing is stirred the time as 40min；Then 16.04g hexahydropyridines and 0.73g neopelexes, control temperature are added in
17 DEG C of degree starts that 17.55g carbon disulfide is added dropwise, and temperature control is 17 DEG C during dropwise addition, time for adding 1.2h；Knot is added dropwise
Shu Hou, controlled at 17 DEG C of reaction 0.5h；
Then, 24 DEG C are warming up to, starts that the mixed solution of 16.3g hydrogen peroxide and 145.26ml isopropanols, control drop is added dropwise
Acceleration makes reaction temperature be 24 DEG C, time for adding 4.5h；Then insulation reaction 0.5h；
Finally, gained reaction solution is warming up to 70 DEG C, then insulation reaction 0.5h, is cooled to 36 DEG C, start filtering, 80 DEG C
Dry, crushing, obtains thiofide DPTT-6.
By made from the present embodiment thiofide DPTT-6 carry out chromatography detection, profiling results as shown in figure 5,
Data results are as shown in the table：
| Peak | Retention time | Peak area | Concentration % |
| 1 | 1.173 | 30369 | 0.2376 |
| 2 | 1.934 | 2142 | 0.01674 |
| 3 | 2.800 | 3145 | 0.02458 |
| 4 | 4.117 | 31974 | 0.2499 |
| 5 | 5.437 | 12716998 | 99.41 |
| 6 | 10.064 | 1418 | 0.01108 |
| 7 | 11.026 | 1630 | 0.01274 |
| 8 | 12.118 | 2197 | 0.01717 |
| 9 | 12.743 | 1686 | 0.01318 |
| 10 | 13.651 | 1337 | 0.01045 |
| It amounts to | 12792923 | 100 |
By upper table analysis it is found that being detected through chromatography, product yield 98.8%, 116.4 DEG C of just fusing point, purity 99.41%.
Embodiment 5
A kind of preparation method of thiofide DPTT-6, the preparation method include the following steps：
First, it will be stirred in 260ml methanol and 14.21g sulphur addition 1000ml four-hole bottles in atmospheric conditions mixed
It closes, is stirred the time as 35min；Then 17.16g hexahydropyridines and 0.69g diisobutyl sodium naphthalene sulfonates are added in, controls temperature
16 DEG C, start that 18.77g carbon disulfide is added dropwise, temperature control is 16 DEG C during dropwise addition, time for adding 1.0h；Completion of dropwise addition
Afterwards, controlled at 16 DEG C of reaction 0.5h；
Then, 25 DEG C are warming up to, starts that the mixed solution of 17.44g hydrogen peroxide and 87.2ml methanol is added dropwise, speed is added dropwise in control
Degree makes reaction temperature be 25 DEG C, time for adding 3.5h；Then insulation reaction 0.5h；After heat preservation,
Finally, gained reaction solution is warming up to 80 DEG C, then insulation reaction 0.5h.35 DEG C are cooled to, starts to filter, do
Dry, crushing, obtains thiofide DPTT-6.
By made from the present embodiment thiofide DPTT-6 carry out chromatography detection, profiling results as shown in fig. 6,
Data results are as shown in the table：
| Peak | Retention time | Peak area | Concentration % |
| 1 | 1.116 | 0.03058 | 4103 |
| 2 | 1.447 | 0.033 | 4428 |
| 3 | 4.540 | 0.09827 | 13186 |
| 4 | 5.720 | 99.84 | 13396254 |
| It amounts to | 100 | 13417971 |
By upper table analysis it is found that being detected through chromatography, product yield 98.8%, 116.3 DEG C of just fusing point, purity 99.84%.
In conclusion the preparation method of thiofide DPTT-6 provided by the invention, using low toxicity, price just
Preferably, the low-carbon alcohols for being easily recycled and applying mechanically make solvent, at a lower temperature the oxidation through peroxide hydrogen peroxide, synthesis six
Vulcanize di-penta methylene thiuram (DPTT-6).The preparation method has the advantages that simple for process, product yield is high, purity is high, system
Product yield >=97.0% obtained, just fusing point >=115.0 DEG C, purity >=98.0%；Meanwhile without " three in preparation process of the present invention
It is useless " it discharges, solvent whole recovery, non-environmental-pollution realizes zero emission.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution recorded in foregoing embodiments either to which part or all technical features into
Row equivalent replacement；And these modifications or replacement, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of thiofide DPTT-6, which is characterized in that the preparation method includes the following steps：
Sulphur, hexahydropyridine and surfactant are added to mixing in low-carbon alcoholic solvent, then, carbon disulfide and dioxygen are added dropwise successively
Thiofide DPTT-6 is made in water and temperature reaction.
2. the preparation method of thiofide DPTT-6 according to claim 1, which is characterized in that the low-carbon alcohols
Solvent is any one in methanol, ethyl alcohol, isopropanol or n-butanol.
3. the preparation method of thiofide DPTT-6 according to claim 1 or 2, which is characterized in that described low
The mass ratio of carbon alcoholic solvent and hexahydropyridine is 10.0~15.0:1.
4. the preparation method of thiofide DPTT-6 according to claim 1, which is characterized in that the hexahydro pyrrole
Pyridine, carbon disulfide, sulphur and hydrogen peroxide molar ratio be 1:1.0~1.2:1.9~2.3:0.5~0.8.
5. the preparation method of thiofide DPTT-6 according to claim 1, which is characterized in that live on the surface
Property agent be three ethylene oxide alkyl phenylates, trimethyloctadecyl ammonium chloride, neopelex or diisobutyl naphthalene sulfonic acids
Any one in sodium.
6. the preparation method of thiofide DPTT-6 according to claim 1 or 5, which is characterized in that described six
The mass ratio of pyridinium hydroxide and surfactant is 20~25:1.
7. the preparation method of thiofide DPTT-6 according to claim 1, which is characterized in that the curing
The time for adding of carbon is 1.2~1.8h, and dropping temperature is 16~18 DEG C.
8. the preparation method of thiofide DPTT-6 according to claim 1, which is characterized in that the hydrogen peroxide
Time for adding for 3.5~4.5h, dropping temperature is 20~25 DEG C.
9. the preparation method of thiofide DPTT-6 according to claim 1, which is characterized in that the preparation side
Method further includes the step of crushing is dried in the thiofide DPTT-6 that will be obtained；
Preferably, the temperature of the drying is 70~80 DEG C.
10. the preparation method of thiofide DPTT-6 according to claim 1, which is characterized in that the preparation
Method specifically includes following steps：
Sulphur is added in low-carbon alcoholic solvent first and is stirred 20~30min, then adds in hexahydropyridine and surfactant
It is stirred, then adjusts the temperature to 16~18 DEG C of dropwise addition carbon disulfide, after carbon disulfide completion of dropwise addition, constant temperature is stirred to react
0.5~1.0h；It is warming up to 20~25 DEG C later, hydrogen peroxide is added dropwise under conditions of constant temperature, constant temperature is anti-after hydrogen peroxide completion of dropwise addition
Answer 0.5~1.0h；70~80 DEG C of 0.5~1.0h of reaction are finally warming up to, thiofide DPTT-6 is made.
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