CN103073521B - Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) - Google Patents
Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) Download PDFInfo
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Abstract
The invention provides a preparation method of a rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS). A specific process as below: adding 30-60ml of ammonia; weighing 33.25g of Dithio-dibenzo thiazole, 0.10-0.25g of a copper ammonia catalyst and a surface active agent under oxygen pressure of 0.2-0.8MPa, and adding into a reaction kettle; slowly injecting 15.36-19.02g of tert-butylamine by a metering pump to generate a target product at a reasonable reaction temperature; and conducting centrifugation, washing and drying to obtain the product NS. The method provided by the invention can effectively reduce the treatment amount of organic wastewater, reduce comprehensive cost, and has advantages of few raw material varieties, high reaction selectivity, high yield and short cycle; and the method is better than a current production method, and can well meet the demand of high-end market.
Description
First, technical field
The invention belongs to the preparing technical field of thiofide, particularly to a kind of thiofide uncle N-
The preparation method of butyl -2-[4-morpholinodithio sulfenamide (NS).
2nd, background technology
In recent years, the toxicity being also easy to produce nitrosamine that can be carcinogenic during rubber processing to vulcanization accelerator in the world is asked
Topic pay attention to day by day.It has been investigated that, the generation of nitrosamine be due to when rubber product is processed using the rush containing secondary amine group
Enter agent, belong to this kind of accelerator and common are N- oxygen diethylidene benzothiazole -2- sulfenamide (NOBS), N, N- diisopropyl
Base -2-[4-morpholinodithio sulfenamide (DIBS) and N, N- dicyclohexyl -2-[4-morpholinodithio sulfenamide (DZ) etc., this be due to
Prepare such accelerator all using secondary amine group raw material such as morpholine, diisopropylamine etc., these contain the accelerator meeting of secondary amine group
There is nitrosation reaction in atmosphere, generate nitrosamine compound.In this regard, multinomial restricted regulation is put into effect in succession.Thus, make
For replacement products of new generation, the greenization preparation of rubber vulcanization accelerator NS is particularly important.
Existing NS preparation method in current industrial mainly has sodium hypochlorite oxidization and hydrogen peroxide oxidation method.Sodium hypochlorite
Oxidizing process is first chlorine to be passed through sodium hydroxide solution preparing sodium hypochlorite, then puts into 2- benzothiazolyl mercaptan and tert-butylamine
Condensation oxidation is obtained NS.This method is there is problems that complex process, auxiliary material large usage quantity, and reactant chlorine are corrosivity
Hypertoxic gas, sodium hydroxide again be highly basic, not only higher to equipment requirements, environment be will also result in quite serious pollution,
Production cost is higher, simultaneously it is difficult to avoid product over oxidation phenomenon, causes reaction selectivity reduction, product yield and quality
Low.Have part producing enterprise at present both at home and abroad to have selected hydrogen peroxide oxidation method replacement sodium hypochlorite oxidization to synthesize rush
Enter agent NS, in reactor, put into tert-butylamine, 2- benzothiazolyl mercaptan and solvent, and Deca hydrogen peroxide brings it about oxidation
Reaction is obtained NS.This kind of method raw material variety in synthesis is few, equipment is simple, however required quantity of solvent is big, high expensive, reaction
Selectivity is not high, and the discharge capacity of organic wastewater is larger.
3rd, content of the invention
For overcoming defect present in the various methods preparing NS in prior art, the present invention provides a kind of greenization preparation
The method of rubber accelerator NS, this method compensate for prior art deficiency in process of production, more cleaning, efficient and energy-conservation ground
Produce rubber vulcanization accelerator NS.The preparation technology of the NS of the present invention is achieved by the following scheme：Put into 30～60ml ammonia,
0.2～0.8MPa oxygen is depressed, and weighs 33.25g dithio-bis-benzothiazole and 0.10～0.25g cuprammonium catalyst puts into reaction bulb
In, it is slowly injected into 15.36～19.02g tert-butylamine using dosing pump, generate target product under rational reaction temperature, by
The operations such as centrifugation, washing, drying, obtain required product NS.Its purity >=99%, just fusing point >=106.0 DEG C, outward appearance is in off-white color.
This preparation method reduces treatment of Organic Wastewater amount because replacing hydrogen peroxide from cheap high pure oxygen as reaction oxidant, comprehensive
Synthesize this reduction, this method has that raw material variety is few, reaction selectivity is high concurrently simultaneously, the advantage of high income, cycle is short is hence it is evident that better than existing
The production method of row, can admirably meet the demand of high-end market.
1st, the present invention is raw materials used
1.1st, dithio-bis-benzothiazole：Off-white color crystallizes, relative density 1.45～1.54g/cm3, nontoxic slight bitter.Fusing point
More than 175 DEG C.Dissolve in chloroform, be partially soluble in benzene, ethanol and carbon tetrachloride, water insoluble, gasoline and ethyl acetate.
1.2nd, tert-butylamine：Colourless flammable liquid, relative density 0.70g/cm when 25 DEG C3, 44.5 DEG C of boiling point, can with water,
Ethanol, acetone etc. are miscible.Irritant ammonia odor.
1.3rd, oxygen：Colourless under room temperature, odorless, tasteless, density is 1.43g/L at standard conditions, less soluble under normal pressure
Yu Shui, can dissolve 30ml oxygen in standard atmosphere pressure 1L water.
1.4th, ammonia：25% aqueous solution.When 20 DEG C, density is 0.91g/cm3, have strong sharp aroma, can dissolve numerous
Organic compound.
1.5th, cuprammonium catalyst：Four ammino copper complexs being obtained with ammonia by cupric oxalate.
1.6、TW-20：Nonionic surfactant.Relative density 1.01g/cm3, 321 DEG C of boiling point, contain more in molecule
Hydrophilic radical, can be miscible with water, methanol, ethanol and ethyl acetate, insoluble in paraffin, expressed oi and V.M.. naphtha.Have good
The effect such as emulsifying well, diffusion, solubilising.
2nd, the factory formula of the present invention：
Dibenzothiazyl disulfide (mol): ammonia (1)=1.0: (0.3～0.6)
Dibenzothiazyl disulfide (mol): tert-butylamine (mol)=1.0: (1.05～1.30)
Dibenzothiazyl disulfide (mol): oxygen (mol)=1.0: (0.55～0.80)
Dibenzothiazyl disulfide (g): cuprammonium catalyst (g)=1.0: (0.003～0.007)
Dibenzothiazyl disulfide (g): surfactant (g)=1.0: (0.00015～0.00025)
3rd, the production process of the present invention：
Add 30～60ml ammonia in the 1L autoclave have temperature, pressure-detecting device and permanent magnetic stirrer,
Reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyst 0.10～0.25g and pole is put under strong agitation
A small amount of surfactant TW-20, to 10～25 DEG C, being passed through oxygen and making pressure is 0.2～0.8MPa to temperature control, in 1.5～3.5h
Add the tert-butylamine of 15.36～19.02g, now temperature in the kettle raises, control 30～42 DEG C of temperature, react 1～2h, oxygen uptake is very
When few, terminal is arrived in reaction, stops stirring.White precipitate is through washing, being dehydrated, be drying to obtain product.
4th, the advantage of synthesis technique involved in the present invention：
4.1st, inorganic acid and highly basic are not used in synthesis technique flow process, to production equipment no aggressive；
4.2nd, process is simple, one-step method can synthesize target product, with short production cycle；
4.3rd, materials kind is few, and oxidant is high pure oxygen, low production cost；
4.4th, no waste gas, waste sludge discharge in building-up process, wastewater treatment capacity substantially reduces, and has substantially accomplished clean manufacturing；
4.5th, the like product producing compared to other methods, product appearance is white, and just fusing point is higher than 106 DEG C, purity >=
99%；
4.6th, in rubber applications test, show that cure time is short, scorch safety is good, heat resistance is excellent and resistance to revert
The advantages of property.The product producing compared to other methods, then show the vulcanization of rubber application performance of brilliance.
4th, brief description：
Fig. 1 is the work of the preparation method of rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide of the present invention
Skill flow chart.
5th, specific embodiment
Raw materials used in the preparation method of the rubber vulcanization accelerator N-tertiary butyl of the present invention -2-[4-morpholinodithio sulfenamide
For dibenzothiazyl disulfide, tert-butylamine, oxygen, ammonia, cuprammonium catalyst and surfactant；Its formula proportion is as follows：
Dibenzothiazyl disulfide (mol): ammonia (1)=1.0: (0.3～0.6)
Dibenzothiazyl disulfide (mol): tert-butylamine (mol)=1.0: (1.05～1.30)
Dibenzothiazyl disulfide (mol): oxygen (mol)=1.0: (0.55～0.80)
Dibenzothiazyl disulfide (g): cuprammonium catalyst (g)=1.0: (0.003～0.007)
Dibenzothiazyl disulfide (g): surfactant (g)=1.0: (0.00015～0.00025)
Embodiment one：
Add 35ml ammonia in the 1L autoclave have temperature, pressure-detecting device and permanent magnetic stirrer, strongly
Stirring is lower to put into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyst 0.12g and surfactant TW-
20 0.005g, to 20 DEG C, being passed through oxygen and making pressure is 0.4MPa to temperature control, adds the tert-butylamine of 16.09g, now kettle in 2.5h
Interior temperature raises, and controls 40 DEG C of temperature, reacts 1.5h, and when oxygen uptake is little, terminal is arrived in reaction, stops stirring.White precipitate warp
Wash, be dehydrated, be drying to obtain product.Its outward appearance is in canescence, and after measured, reaction yield is 96.2%, obtains product after reaction
Just fusing point be 106.3 DEG C, purity be 98.6%.
Embodiment two：
Add 42ml ammonia in the 1L autoclave have temperature, pressure-detecting device and permanent magnetic stirrer, strongly
Stirring is lower to put into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyst 0.18g and surfactant TW-
20 0.006g, to 16 DEG C, being passed through oxygen and making pressure is 0.6MPa to temperature control, adds the tert-butylamine of 15.36g, now in kettle in 2h
Temperature raises, and controls 38 DEG C of temperature, reacts 1.5h, and when oxygen uptake is little, terminal is arrived in reaction, stops stirring.White precipitate is through water
Wash, be dehydrated, be drying to obtain product.Its outward appearance is in off-white color, and after measured, reaction yield is 95.8%, obtains product after reaction
Fusing point is 106.8 DEG C, and purity is 98.9%.
Embodiment three：
Add 50ml ammonia in the 1L autoclave have temperature, pressure-detecting device and permanent magnetic stirrer, strongly
Stirring is lower to put into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyst 0.20g and surfactant TW-
20 0.008g, to 10 DEG C, being passed through oxygen and making pressure is 0.5MPa to temperature control, adds the tert-butylamine of 17.55g, now kettle in 3.0h
Interior temperature raises, and controls 35 DEG C of temperature, reacts 2h, and when oxygen uptake is little, terminal is arrived in reaction, stops stirring.White precipitate is through water
Wash, be dehydrated, be drying to obtain product.Its white in appearance, after measured, reaction yield is 97.4%, obtains the molten of product after reaction
Point is 107.2 DEG C, and purity is 99.1%.
Example IV：
Add 56ml ammonia in the 1L autoclave have temperature, pressure-detecting device and permanent magnetic stirrer, strongly
Stirring is lower to put into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyst 0.22g and surfactant TW-
200.006g, to 10 DEG C, being passed through oxygen and making pressure is 0.6MPa to temperature control, adds the tert-butylamine of 18.29g, now kettle in 3.0h
Interior temperature raises, and controls 35 DEG C of temperature, reacts 2h, and when oxygen uptake is little, terminal is arrived in reaction, stops stirring.White precipitate is through water
Wash, be dehydrated, be drying to obtain product.Its white in appearance, after measured, reaction yield is 98.0%, obtains the molten of product after reaction
Point is 107.6 DEG C, and purity is 99.5%.
Claims (5)
1. a kind of rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) preparation method it is characterised in that：
In the method raw materials used for dibenzothiazyl disulfide, tert-butylamine, oxygen, ammonia, cuprammonium catalyst and surfactant；Its
Formula proportion is as follows：
Dibenzothiazyl disulfide (mol): ammonia (l)=1.0: (0.3～0.6)
Dibenzothiazyl disulfide (mol): tert-butylamine (mol)=1.0: (1.05～1.30)
Dibenzothiazyl disulfide (mol): oxygen (mol)=1.0: (0.55～0.80)
Dibenzothiazyl disulfide (g): cuprammonium catalyst (g)=1.0: (0.003～0.007)
Dibenzothiazyl disulfide (g): surfactant (g)=1.0: (0.00015～0.00025)
Its production process is：Ammonia is added in the autoclave with temperature, pressure-detecting device and permanent magnetic stirrer
Water, puts into reactant dibenzothiazyl disulfide, cuprammonium catalyst and surfactant TW-20, temperature control to 10 under strong agitation
～25 DEG C, being passed through oxygen and making pressure is 0.2～0.8MPa, adds tert-butylamine in 1.5～3.5h, and now temperature in the kettle raises,
Control temperature to be 30～42 DEG C, react 1～2h, when oxygen uptake is little, terminal arrive in reaction, stops stirring, white precipitate through washing,
It is dehydrated, be drying to obtain product；
Described cuprammonium catalyst is four ammino copper complexs being obtained with ammonia by cupric oxalate.
2. preparation method according to claim 1 it is characterised in that：Its concrete production process is：Have temperature,
Add 35ml ammonia in the 1L autoclave of pressure-detecting device and permanent magnetic stirrer, under strong agitation, put into reactant two sulfur
Change bisbenzothiazole 33.25g (0.1mol), cuprammonium catalyst 0.12g and surfactant TW-20 0.005g, temperature control to 20
DEG C, being passed through oxygen and making pressure is 0.4MPa, adds the tert-butylamine of 16.09g in 2.5h, and now temperature in the kettle raises, and controls temperature
40 DEG C of degree, reacts 1.5h, and when oxygen uptake is little, terminal is arrived in reaction, stops stirring, white precipitate is through washing, being dehydrated, be drying to obtain
Product.
3. preparation method according to claim 1 it is characterised in that：Its concrete production process is：Have temperature,
Add 42ml ammonia in the 1L autoclave of pressure-detecting device and permanent magnetic stirrer, under strong agitation, put into reactant two sulfur
Change bisbenzothiazole 33.25g (0.1mol), cuprammonium catalyst 0.18g and surfactant TW-20 0.006g, temperature control to 16
DEG C, being passed through oxygen and making pressure is 0.6MPa, adds the tert-butylamine of 15.36g in 2h, and now temperature in the kettle raises, and controls temperature
38 DEG C, react 1.5h, when oxygen uptake is little, terminal is arrived in reaction, stops stirring, white precipitate is through washing, being dehydrated, be drying to obtain product
Product.
4. preparation method according to claim 1 it is characterised in that：Its concrete production process is：Have temperature,
Add 50ml ammonia in the 1L autoclave of pressure-detecting device and permanent magnetic stirrer, under strong agitation, put into reactant two sulfur
Change bisbenzothiazole 33.25g (0.1mol), cuprammonium catalyst 0.20g and surfactant TW-20 0.008g, temperature control to 10
DEG C, being passed through oxygen and making pressure is 0.5MPa, adds the tert-butylamine of 17.55g in 3.0h, and now temperature in the kettle raises, and controls temperature
35 DEG C of degree, reacts 2h, and when oxygen uptake is little, terminal is arrived in reaction, stops stirring, white precipitate is through washing, being dehydrated, be drying to obtain product
Product.
5. preparation method according to claim 1 it is characterised in that：Its concrete production process is：Have temperature,
Add 56ml ammonia in the 1L autoclave of pressure-detecting device and permanent magnetic stirrer, under strong agitation, put into reactant two sulfur
Change bisbenzothiazole 33.25g (0.1mol), cuprammonium catalyst 0.22g and surfactant TW-20 0.006g, temperature control to 10
DEG C, being passed through oxygen and making pressure is 0.6MPa, adds the tert-butylamine of 18.29g in 3.0h, and now temperature in the kettle raises, and controls temperature
35 DEG C of degree, reacts 2h, and when oxygen uptake is little, terminal is arrived in reaction, stops stirring, white precipitate is through washing, being dehydrated, be drying to obtain product
Product.
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| CN103539756A (en) * | 2013-10-16 | 2014-01-29 | 科迈化工股份有限公司 | Method for dehydrating in process of producing rubber vulcanizing accelerant MBTS (2-mercaptobenzothiazole disulfide) by using hydrogen peroxide method |
| CN106866577B (en) * | 2017-01-24 | 2018-11-23 | 蔚林新材料科技股份有限公司 | The method of catalytic molecular oxygen oxidation preparation sulfenamide thiofide in water phase |
| CN110354900A (en) * | 2019-08-27 | 2019-10-22 | 聊城宝和化学科技有限公司 | Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method |
| CN110776478A (en) * | 2019-11-11 | 2020-02-11 | 山东阳谷华泰化工股份有限公司 | Low-temperature continuous synthesis method of rubber vulcanization accelerator NS |
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