CN105503677B - A kind of environmental protection, high performance vulcanization crosslinking agent 1,6 2（The sulphur of N, N dibenzyl amino formyl two）The preparation method of hexane - Google Patents
A kind of environmental protection, high performance vulcanization crosslinking agent 1,6 2（The sulphur of N, N dibenzyl amino formyl two）The preparation method of hexane Download PDFInfo
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- CN105503677B CN105503677B CN201510891653.8A CN201510891653A CN105503677B CN 105503677 B CN105503677 B CN 105503677B CN 201510891653 A CN201510891653 A CN 201510891653A CN 105503677 B CN105503677 B CN 105503677B
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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
- C07C333/16—Salts of dithiocarbamic acids
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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
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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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
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/24—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to carbon atoms of six-membered aromatic rings
Abstract
A kind of preparation method step the present invention relates to environmental protection, high performance vulcanization crosslinking agent 1,6 2 (sulphur of N, N dibenzyl amino formyl two) hexane includes：Synthesize dibenzyl aminodithioformic acid sodium first, then with 1, the reaction of 6 dichloro hexanes, 1,6 two (sulphur of N, N dibenzyl amino formyl one) hexanes of generation, the synthetic generates product 1,6 two (sulphur of N, N dibenzyl thiocarbamoyl two) hexane with sulfur reaction.Product prepared by the present invention is few containing inorganic salts, and purity is high, and the present invention provide preparation method is simple and easy to apply, environmental protection, the waste water generated in preparation process is few, reduces the pollution to environment.
Description
Technical field
The present invention relates to a kind of environmentally friendly, high performance vulcanization crosslinking agent 1,6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane
Preparation method, belongs to rubber chemicals synthesis technique field.
Background technology
Natural rubber has recovery phenomenon in high temperature or long-time sulfidation, and recovery can reduce vulcanizate
Crosslink density, and then reduce vulcanizate mechanical property and dynamic property.(N, N- the dibenzyl thiocarbamoyls of 1,6- bis-
Two sulphur) hexane is a kind of new and effective multiple crosslinking agent, the both effect with vulcanization accelerator, and the work with anti-recovery
With, its cross-bond for being formed has the stability of monosulfidic bond and cystine linkage, while there is the compliance of similar polysulfide crosslink bond again,
The cross-linked network of stabilization can be formed in sulfidation, the anti-reversion behaviour of sizing material is improved.
In the synthetic method of current this product mainly with the double sodothiol dihydrates of hexa-methylene -1,6- and
Dibenzyl aminodithioformic acid sodium is Material synthesis.Wherein Germany is being reaction bar containing formaldehyde, toluene and weakly alkaline environment
Part, with water as solvent, sintetics, but the preparation method has the disadvantage that：1. can produce substantial amounts of containing formaldehyde, containing a small amount of toluene
Waste water, and have unpleasant toxic odor, it is more difficult to process；2. the reaction speed it is relatively slow, it is necessary to reaction time it is more long.In addition,
China, with the alkane of dioxy six, dichloromethane and toluene etc. as solvent, has the following disadvantages in sintetics, but the preparation method：Two
Kind of raw material is all the salt for being insoluble in organic solvent, in heterogeneous system, so this metathesis reaction it is more difficult carry out, it is necessary to
Reaction time is long.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of environmental protection, high performance vulcanization crosslinking agent 1, (N, the N- dibenzyl of 6- bis-
The sulphur of carbamyl two) hexane preparation method, the synthetic method prepare product purity it is high, required time is short, generation it is poisonous
Waste water is few, and industrialization low cost.
What the present invention was achieved through the following technical solutions：
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
It is as follows including step：
(1) with dibenzylamine, NaOH and carbon disulfide as raw material, it is added in solvent, after the completion of reaction, obtains containing two
The solution of benzyl nabam；
(2) to added in the obtained solution containing dibenzyl aminodithioformic acid sodium of step (1) 1,6- dichloro hexanes and
Catalyst, reacts at reflux, and after completion of the reaction, suction filtration, filter cake washing removes side product chlorinated sodium, is taken out again after washing
Filter, 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane is obtained after filter cake drying；
(3) obtained (sulphur of N, the N- dibenzyl amino formyl one) hexanes of 1,6- bis- are added in organic solvent with sulphur,
Reacted at 70-100 DEG C of temperature, after completion of the reaction, remove organic solvent, obtain (N, N- the dibenzyl amino formyls two of 1,6- bis-
Sulphur) hexane product.
Currently preferred, solvent described in step (1) is methyl alcohol, ethanol or isopropanol.
Currently preferred, the mol ratio of dibenzylamine, NaOH and carbon disulfide is 1 in step (1):(1.0~
1.3):(1.1~1.3), dibenzylamine is 1 with the mass ratio of solvent:(5~8).
Currently preferred, carbon disulfide is added in reaction system so that mode is added dropwise in step (1), is added dropwise in 30min
Finish, reaction temperature is 0-50 DEG C in step (1), the reaction time is 3-5 hours, it is preferred that reaction temperature is 10-35 DEG C, instead
It is 4-5 hours between seasonable.
It is currently preferred, the addition of 1,6- dichloro hexanes and sodium containing dibenzyl aminodithioformic acid in step (2)
The mol ratio of dibenzyl aminodithioformic acid sodium is 1.0 in solution：(2.1~2.3), wherein, dibenzyl dithio amino first
The yield of sour sodium is calculated with 95%.
Currently preferred, the catalyst in step (2) is KI or KBr, and the addition of catalyst is dibenzyl dithio
The 0.1~0.5% of carbamic acid sodium quality.
Currently preferred, the reaction temperature in step (2) is 70-85 DEG C, and the reaction time is 3-5 hours.The step
Reaction temperature depends on the boiling point of solvent for use.
Currently preferred, in step (2) after completion of the reaction, suction filtration washes filter cake, removes side product chlorinated sodium, water
Suction filtration again after washing, obtains 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane after filter cake drying, solvent is repeatable to be utilized.
Currently preferred, organic solvent described in step (3) is toluene, dimethylbenzene or 120# solvent naphthas.
It is currently preferred, in step (3) (sulphur of N, the N- dibenzyl amino formyl one) hexanes of 1,6- bis- and sulphur mole
Than being 1:(2.0~2.2), 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane is 1 with the mass ratio of organic solvent：(5~
8)。
Currently preferred, step (3) reaction temperature is 80-95 DEG C, and the reaction time is 5-7 hours.
Currently preferred, step (3) organic solvent is removed using vacuum distillation mode.
Synthetic route of the invention is as follows：
Beneficial effects of the present invention are as follows：
Preparation method of the invention, dibenzyl aminodithioformic acid sodium need not be extracted in a solvent, directly used and contained
The reaction of the solution and 1,6- dichloro hexane of dibenzyl aminodithioformic acid sodium, can effectively ensure production safety, can keep away again
Exempt from the potential pollution that personnel cause to intermediate production process.Meanwhile, simplify production operation, the discharge of waste liquid is reduced, in reduction
Energy consumption in mesosome extraction process；And dibenzyl aminodithioformic acid sodium is dissolved in solvent of the invention, 1,6- bis- (N, N-
The sulphur of dibenzyl amino formyl one) hexane and byproduct sodium chloride do not dissolve in solvent, and the unreacted dibenzyl of very small amount can be removed after suction filtration
Base nabam and 1,6- dichloro hexane, after further filter cake is washed, remove side product chlorinated sodium, so as to get
1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane purity is improved；1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane
Organic solvent of the invention can be dissolved in building-up process with sulphur, homogeneous system, reaction is easily carried out, substantially reduced anti-
Between seasonable.Side reaction is few in the synthetic reaction, and the product purity for obtaining is high, yield is high, and can only produce a small amount of sodium chloride-containing
Waste water, without other wastes produce, be really achieved the production process of green non-pollution.
Brief description of the drawings
Fig. 1 is 1,6- bis- obtained in the embodiment of the present invention 1 (sulphur of N, N- dibenzyl amino formyl two) hexane product infrared light
Spectrogram.
Specific embodiment
The present invention is further elaborated with reference to embodiment, but institute's protection domain not limited to this of the present invention.
Embodiment 1
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
Step is as follows：
(1) to 39.4g dibenzylamine, 8.4g NaOH and 190g ethanol is put into 1000mL there-necked flasks, stirred at 20 DEG C
20min is mixed, 16g carbon disulfide is weighed in constant pressure funnel, carbon disulfide is added drop-wise in the there-necked flask in 30min,
Continue to stir 3 hours at 20 DEG C, the ethanol solution containing dibenzyl aminodithioformic acid sodium is obtained after the completion of reaction.
(2) 14.7g 1 is weighed, 6- dichloro hexanes and 0.2gKI are added in the flask, connects condenser pipe, use electric jacket liter
Temperature is stirred 4 hours to system backflow under reflux state, after reaction terminates, is cooled to room temperature, and suction filtration obtains white filter cake, will filter
Cake adds about 150g water as in 500mL beakers, stirs 10min, and suction filtration, filter cake drying obtains 61g white solids 1,6- bis-
(sulphur of N, N- dibenzyl amino formyl one) hexane, gross production rate is 91.8%.
(3) weigh (sulphur of N, N- dibenzyl amino formyl one) hexane, 2.56g Sulfurs and the 160g toluene of 26.6g 1,6- bis- in
In 500mL there-necked flasks, condenser pipe is connected, opens condensed water, 80 DEG C are warming up to electric jacket, stirred 5 hours at this temperature,
After reaction terminates, toluene is rotated out, obtain 1,6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane product that content is 98%
27.6g, yield is 94.6%, and the fusing point of end product is 91 DEG C, and (750 DEG C/2h) of ash content is 0.2%.
Embodiment 2
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
With embodiment 1, difference is：
Step (1) reaction temperature is 30 DEG C, obtains the ethanol solution containing dibenzyl aminodithioformic acid sodium.
Step (2) filter cake is dried, and obtains 60.5g white solids 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane,
Gross production rate is 91%.
Step (3) obtains 1,6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane product 27.4g that content is 97%, produces
Rate is 94%, and the fusing point of end product is 90 DEG C, and (750 DEG C/2h) of ash content is 0.1%.
Embodiment 3
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
With embodiment 1, difference is：
Step (1) reaction temperature is 10 DEG C, obtains the ethanol solution containing dibenzyl aminodithioformic acid sodium.
Step (2) filter cake is dried, and obtains 60g white solids 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane, always
Yield is 90.2%.
Step (3) obtains 1,6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane product 27.5g that content is 97%, produces
Rate is 94.3%, and the fusing point of end product is 90 DEG C, and (750 DEG C/2h) of ash content is 0.1%.
Embodiment 4
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
With embodiment 1, difference is：
Step (1) solvent for use is isopropanol, obtains the aqueous isopropanol containing dibenzyl aminodithioformic acid sodium.
Step (2) filter cake is dried, and obtains 59.7g white solids 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane,
Gross production rate is 89.9%.
Step (3) obtains 1,6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane product 27.2g that content is 96%, produces
Rate is 93.3%, and the fusing point of end product is 90 DEG C, and (750 DEG C/2h) of ash content is 0.1%.
Embodiment 5
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
With embodiment 1, difference is：
Step (2) weighs 14.7g 1, and 6- dichloro hexanes and 0.2gKBr are added in the flask, connects condenser pipe, electricity consumption
Hot jacket is warming up to system backflow, is stirred 4 hours under reflux state, after reaction terminates, is cooled to room temperature, and suction filtration obtains white filter
Cake, by filter cake as in 500mL beakers, adds about 150g water, stirs 10min, and suction filtration, filter cake drying obtains 59.8g whites solid
Body 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane, gross production rate is 90.1%.
Step (3) weighs 26.6g 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane, 2.56g Sulfurs and 160g first
Benzene connects condenser pipe in 500mL there-necked flasks, opens condensed water, and 80 DEG C are warming up to electric jacket, and 5 are stirred at this temperature
Hour, after reaction terminates, toluene is rotated out, obtain 1,6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane that content is 96%
Product 27g, yield is 92.6%, and the fusing point of end product is 90 DEG C, and (750 DEG C/2h) of ash content is 0.3%.
Embodiment 6
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
, with embodiment 1, difference is for step (1) and (2)：
Step (3) weighs 26.6g 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane, 2.56g Sulfurs and 160g first
Benzene connects condenser pipe in 500mL there-necked flasks, opens condensed water, and 80 DEG C are warming up to electric jacket, and 5 are stirred at this temperature
Hour, after reaction terminates, toluene is rotated out, obtain 1,6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane that content is 95%
Product 27.8g, yield is 95.3%, and the fusing point of end product is 91 DEG C, and (750 DEG C/2h) of ash content is 0.2%.
Embodiment 7
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
, with embodiment 1, difference is for step (1) and (2)：
Step (3) weighs 6.6g 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane, 2.56g Sulfurs and 160g bis-
Toluene connects condenser pipe in 500mL there-necked flasks, opens condensed water, and 80 DEG C are warming up to electric jacket, stirs at this temperature
5 hours, after reaction terminates, dimethylbenzene is rotated out, obtain 1, the 6- bis- (sulphur of N, N- dibenzyl amino formyl two) that content is 95%
Hexane product 27.2g, yield is 94%, and the fusing point of end product is 91 DEG C, and (750 DEG C/2h) of ash content is 0.2%.
Embodiment 8
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
, with embodiment 1, difference is for step (1) and (2)：
Step (3) weighs 26.6g 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane, 2.56g Sulfurs and 160g
120# solvent naphthas connect condenser pipe in 500mL there-necked flasks, open condensed water, 80 DEG C are warming up to electric jacket, in this temperature
Lower stirring 5 hours, after reaction terminates, rotates out solvent naphtha, obtains (N, N- the dibenzyl amino formyls of 1,6- bis- that content is 96%
Two sulphur) hexane product 27.2g, yield is 93.3%, and the fusing point of end product is 91 DEG C, and (750 DEG C/2h) of ash content is 0.2%.
Embodiment 9
A kind of environmental protection, high performance vulcanization crosslinking agent 1, the preparation method of 6- bis- (sulphur of N, N- dibenzyl amino formyl two) hexane,
, with embodiment 1, difference is for step (1) and (2)：
Step (3) weighs 26.6g 1,6- bis- (sulphur of N, N- dibenzyl amino formyl one) hexane, 2.56g Sulfurs and 160g first
Benzene connects condenser pipe in 500mL there-necked flasks, opens condensed water, and 90 DEG C are warming up to electric jacket, and 5 are stirred at this temperature
Hour, after reaction terminates, rotate out solvent naphtha, obtain 1,6- bis- (sulphur of N, N- dibenzyl amino formyl two) that content is 95% oneself
Alkane product 27.0g, yield is 92.6%, and the fusing point of end product is 91 DEG C, and (750 DEG C/2h) of ash content is 0.2%.
Claims (8)
1. a kind of vulcanization crosslinking agent 1,6- bis-（The sulphur of N, N- dibenzyl amino formyl two）The preparation method of hexane, including step is such as
Under：
（1）With dibenzylamine, NaOH and carbon disulfide as raw material, it is added in solvent, after the completion of reaction, obtains containing dibenzyl
The solution of nabam, the solvent is methyl alcohol, ethanol or isopropanol；
（2）To step（1）1,6- dichloro hexanes and catalysis are added in the obtained solution containing dibenzyl aminodithioformic acid sodium
Agent, reacts at reflux, and after completion of the reaction, suction filtration, filter cake washing removes side product chlorinated sodium, suction filtration, filter again after washing
1,6- bis- is obtained after cake drying（The sulphur of N, N- dibenzyl amino formyl one）Hexane；The catalyst be KI or KBr, catalyst plus
It is the 0.1~0.5% of dibenzyl aminodithioformic acid sodium quality to enter amount；
（3）Will obtained 1,6- bis-（The sulphur of N, N- dibenzyl amino formyl one）Hexane is added in organic solvent with sulphur, described
Organic solvent is toluene, dimethylbenzene or 120# solvent naphthas, is reacted at 70-100 DEG C of temperature, after completion of the reaction, is removed organic molten
Agent, obtains 1,6- bis-（The sulphur of N, N- dibenzyl amino formyl two）Hexane product.
2. vulcanization crosslinking agent 1,6- bis- according to claim 1（The sulphur of N, N- dibenzyl amino formyl two）The preparation side of hexane
Method, it is characterised in that step（1）The mol ratio of middle dibenzylamine, NaOH and carbon disulfide is 1:（1.0~1.3）:（1.1~
1.3）, dibenzylamine is 1 with the mass ratio of solvent:（5~8）.
3. vulcanization crosslinking agent 1,6- bis- according to claim 1（The sulphur of N, N- dibenzyl amino formyl two）The preparation side of hexane
Method, it is characterised in that step（1）Middle carbon disulfide is added in reaction system so that mode is added dropwise, completion of dropping in 30min, step
Suddenly（1）Middle reaction temperature is 0-50 DEG C, and the reaction time is 3-5 hours.
4. vulcanization crosslinking agent 1,6- bis- according to claim 3（The sulphur of N, N- dibenzyl amino formyl two）The preparation side of hexane
Method, it is characterised in that reaction temperature is 10-35 DEG C, the reaction time is 4-5 hours.
5. vulcanization crosslinking agent 1,6- bis- according to claim 1（The sulphur of N, N- dibenzyl amino formyl two）The preparation side of hexane
Method, it is characterised in that step（2）Two in the addition and sodium solution containing dibenzyl aminodithioformic acid of middle 1,6- dichloro hexanes
The mol ratio of benzyl nabam is 1.0：（2.1~2.3）, wherein, the receipts of dibenzyl aminodithioformic acid sodium
Rate is calculated with 95%.
6. it is according to claim 1 environmental protection, high performance vulcanization crosslinking agent 1,6- bis-（The sulphur of N, N- dibenzyl amino formyl two）Oneself
The preparation method of alkane, it is characterised in that step（2）In reaction temperature be 70-85 DEG C, the reaction time be 3-5 hours.
7. it is according to claim 1 environmental protection, high performance vulcanization crosslinking agent 1,6- bis-（The sulphur of N, N- dibenzyl amino formyl two）Oneself
The preparation method of alkane, it is characterised in that step（3）Middle 1,6- bis-（The sulphur of N, N- dibenzyl amino formyl one）Hexane rubs with sulphur
You are than being 1:（2.0~2.2）, 1,6- bis-（The sulphur of N, N- dibenzyl amino formyl one）Hexane is 1 with the mass ratio of organic solvent：（5
~8）.
8. it is according to claim 1 environmental protection, high performance vulcanization crosslinking agent 1,6- bis-（The sulphur of N, N- dibenzyl amino formyl two）Oneself
The preparation method of alkane, it is characterised in that step（3）Reaction temperature is 80-95 DEG C, and the reaction time is 5-7 hours, and organic solvent is adopted
Removed with vacuum distillation mode.
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| CN110551047A (en) * | 2019-07-30 | 2019-12-10 | 上海裕诚化工有限公司 | Preparation method of dialkyl dithiocarbamate |
| CN111187193B (en) * | 2019-08-06 | 2022-04-15 | 山东阳谷华泰化工股份有限公司 | Preparation method of rubber additive 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane |
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| JP2012153785A (en) * | 2011-01-25 | 2012-08-16 | Sumitomo Rubber Ind Ltd | Rubber composition for tire, and pneumatic tire |
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