CN108586383A - A kind of continuous production method of accelerator D CBS - Google Patents
A kind of continuous production method of accelerator D CBS Download PDFInfo
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- CN108586383A CN108586383A CN201810502215.1A CN201810502215A CN108586383A CN 108586383 A CN108586383 A CN 108586383A CN 201810502215 A CN201810502215 A CN 201810502215A CN 108586383 A CN108586383 A CN 108586383A
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- mbt
- aqueous slkali
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- dicyclohexyl amine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
Abstract
The present invention provides a kind of continuous production method of accelerator D CBS, the method includes：The aqueous slkali of MBT, the acid solution of dicyclohexyl amine, solvent and oxidant are subjected to oxidation reaction in a continuous flow reactor, later, reacting rear material is post-processed, obtains accelerator D CBS.The MBT high conversion rates of the method, product purity are high；It is fast with reaction speed, product yield high, waste water COD are low (after the waste water after reaction carries out air-distillation recycling residual solvent, COD can be reduced to 8000ppm or less in remaining water), many advantages, such as disposable is a kind of new technology of more industrialization value.
Description
Technical field
The invention belongs to rubber chemicals fields, are related to a kind of continuous production method of accelerator D CBS.
Background technology
During with various rubber products such as rubber production tire, sebific duct and rubber overshoes, it is necessary to five big analog assistants are used,
They are that thiofide (abbreviation accelerating agent), rubber antioxidant, the vulcanization of rubber and vulcanizing activator, processing type rubber help
Agent and special functional auxiliary agent.
Vulcanization accelerator abbreviation accelerating agent.It can promote the substance of sulfurization.Vulcanization time can be shortened, reduce vulcanization temperature
Degree reduces vulcanizing agent dosage and improves the physical mechanical property etc. of rubber.
Diphenylguanidine CBS (Chinese name N, N- dicyclohexyl -2-[4-morpholinodithio sulfenamide) is delayed action accelerator, in rubber
Dispersion performance is good in glue, and char length is long in sizing material, and processing safety is high, has vulcanization promotion and adhesive effect, is suitable for
The big sizing material of high activity reinforcement dosage, especially suitable for radial.Therefore, with tire yield and tire meridian rate
It improves, dosage is significantly increased in recent years by accelerator CBS, TBBS and DCBS.It is counted according to Chinese rubber Industry Association, China in 2014
37.5 ten thousand tons of accelerating agent total output, wherein CBS, TBBS and DCBS are that the late effect property sulfenamide type accelerators of representative accounts for accelerating agent
The 42.51% of yield.
At present the industrialization method of thiofide DCBS be using sodium hypochlorite as oxidant by accelerant MBT or
Its sodium salt of person generates diphenylguanidine CBS with dicyclohexyl amine oxidation.Sodium-hypochlorite process is a kind of more traditional method, production process
Middle wastewater flow rate is big, and post-processing difficulty is higher, and discharge then pollutes the environment, and industrially mostly uses larger reaction kettle and carry out interval
Formula produces, and the factor between batch by personnel's operation is affected, and product quality is susceptible to unstable situation.
Micro passage reaction because have large specific surface area, mixing velocity is fast, and mass-and heat-transfer is efficient, reaction condition it is uniform and
The concern of chemical industry synthesis field personnel is received, high mass transfer and heat transfer efficiency, which much to react, may be implemented accurately to control
System, and then close to theoretical moment reaction, for improving product yield, process safety and product quality in building-up process all
There is great help.
CN102838564A discloses a kind of preparation method of thiofide DCBS, the use of sodium hypochlorite is oxidation
Agent is directly synthetically produced DCBS using MBT crude products, isopropanol and dicyclohexyl amine as raw material, is as follows：1) by reaction under high pressure
The thick MBT of gained is added directly under stiring in the container equipped with water, water with it is pure after MBT weight ratio be 0.5-1:1,
The sodium hydrate aqueous solution of mass content 20-40% is added dropwise into container, pH value in container is maintained to keep MBT complete in 9.5-10.5
M-Na salting liquids are made in portion's dissolving, and terminal point determining method is that pH does not change in 30min, by supernatant liquor after standing
It is transferred to measuring tank；2) it is added dropwise simultaneously obtained by liquor natrii hypochloritis, the first step into the container equipped with isopropanol and dicyclohexyl amine
M-Na salting liquids, sulfuric acid solution, the molar ratio of control pH10-11, pure MBT and sodium hypochlorite is 1 during being added dropwise:1.2-
1.4, reaction temperature maintains 35-70 DEG C, reaction time 2-4h, after the M-Na salting liquids taken are added dropwise, stops drop
Add remaining two kinds of solution, continues after stirring 15min, stop stirring；3) it will be reacted to the reaction mixture sat of terminal, isolated
Brine and isopropanol, isopropanol direct reuse, material bed to be filtered, filter cake is washed to neutrality, washes material water and is distilled to recover isopropyl
Alcohol, dry materials obtain DCBS finished products.But this method is still traditional reaction kettle batch production.
CN 106800540A disclose a kind of method preparing rubber vulcanizing accelerator CBS using micro passage reaction,
Make in catalyst as reaction raw materials, and using hydrogen peroxide, sodium hypochlorite or oxygen using after excessive hexamethylene amine solvent raw material MBT
Under, the synthesis accelerant CBS in micro passage reaction.Although preparing the vulcanization of rubber this method provides a kind of serialization to promote
The method of agent CBS, but this method to using micro passage reaction prepare DCBS there is no enlightenment effects, the reason is as follows that：The party
Solvent of the method using excessive cyclohexylamine as product CBS so that without solid generation in entire reaction process, reaction can smoothly into
Row.And the raw material dicyclohexyl amine of DCBS then can not lysate DCBS, a large amount of solid will be generated in building-up process, blocks pipe
Road makes reaction that can not carry out.And the reaction time in this method in micro passage reaction is long, and single reactor
Flux peak is only 15L/h so that the technology does not have capability of industrialization completely, and reaction yield is relatively low (only in 87%-
Between 95%), reaction product purity is also unable to get guarantee.
The technology that DCBS is prepared using micro passage reaction is needed to be further studied.
Invention content
In view of the deficiencies of the prior art, the present invention intends to provide a kind of the continuous of accelerator D CBS
Change production method, the method is greatly shortened the reaction time while stabilizing product quality, compared with traditional handicraft, improves
Reaction yield, the shortcomings that effectively overcoming traditional autoclave Batch Process.
For this purpose, the present invention uses following technical scheme：
A kind of continuous production method of accelerator D CBS, the method includes：
The aqueous slkali of MBT, the acid solution of dicyclohexyl amine, solvent and oxidant are carried out aoxidizing in a continuous flow reactor anti-
It answers, later, reacting rear material is post-processed, obtain accelerator D CBS.
In the present invention, the MBT, that is, 2-mercaptobenzothiazole, abbreviation MBT.
In the present invention, the acid solution of the aqueous slkali and dicyclohexyl amine that use MBT selects suitable solvent and oxidation for raw material
Agent carries out oxidative synthesis reaction, substantially reduces in reactor in a continuous flow reactor in the case where not using catalyst
Reaction time, it is only 2s~20s to make the optimal residence time.
In the present invention, for traditional MBT for preparing vulcanization accelerator Na salt technique (be generally common in DCBS production,
Such as the method involved in CN 102838564A), it changes inorganic acid (sulfuric acid, hydrochloric acid etc.) and needs and liquor natrii hypochloritis and MBT
Aqueous slkali synchronize be added dropwise mode, be changed to acid mixed first with dicyclohexyl amine, it is only necessary to respectively prepare MBT aqueous slkali and
The acid solution of dicyclohexyl amine mainly has following purpose：
On the one hand, the aqueous slkali for first preparing the acid solution and MBT of dicyclohexyl amine respectively keeps acid mixed with dicyclohexyl amine first
It closes, can play the role of neutralizing dicyclohexyl amine, reduce the risk of esters solvent hydrolysis；And with autoclave or vial-type dropwise reaction
Difference, in the continuous flow reactors such as tubular reactor, micro passage reaction or tower reactor, if directly by acid, MBT
Aqueous slkali mixed with dicyclohexyl amine, react in addition to will appear hydrochloric acid with dicyclohexyl amine other than generating cyclohexylamine hydrochloride, while
The aqueous slkali that will appear MBT reacts the reaction for generating chloride and MBT with acid, and MBT is contacted with oxidant, can be occurred secondary anti-
It answers, generates MBTS or other resinae by-products improve the risk of line clogging while reducing yield.Therefore, it is necessary to
The acid solution of the aqueous slkali and dicyclohexyl amine of MBT is first prepared respectively, then carries out subsequent reaction；
On the other hand, the acid solution of the aqueous slkali and dicyclohexyl amine of preparing MBT respectively also simplifies feeding mode, will originally
Dicyclohexyl amine, acid, five kinds of solvent, the aqueous slkali of MBT and oxidant raw materials feed respectively, made four kinds of chargings into, reduced
Control points when continuous production, improve the stability of technique.
The preparation method of the aqueous slkali of the MBT includes the following steps：MBT is mixed with aqueous slkali under agitation,
The aqueous slkali of MBT is made.
Preferably, the aqueous slkali includes NaOH solution, KOH solution or NH3·H2Any one in O solution or at least two
The combination of kind, the combination is typical but non-limiting examples have：The combination of NaOH solution and KOH solution, KOH solution and NH3·
H2The combination etc. of O solution, preferably NaOH solution.
Preferably, a concentration of 1wt%~50wt% of the aqueous slkali, for example, 3wt%, 5wt%, 10wt%,
15wt%, 25wt% or 40wt% etc., preferably 20wt%~35wt%.
Preferably, the molar ratio of the MBT and solute in aqueous slkali is 1:(0.3~4.0), such as 1:0.5、1:1.1、
1:1.5、1:2.0、1:2.5、1:2.8、1:2.9、1:3.2、1:3.5 or 1:3.8 etc., preferably 1:(0.5~1.5).
Preferably, the time of the mixing be 0~4h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4h etc.,
Preferably 0~2h.
Preferably, the temperature of the mixing be 0~100 DEG C, such as 5 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., preferably 40 DEG C~60 DEG C.
The preparation method of the acid solution of the dicyclohexyl amine includes the following steps：Under agitation with acid by dicyclohexyl amine
Mixing, obtains the acid solution of dicyclohexyl amine.
Preferably, combination of the acid including any one in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid or at least two, it is described
Combination is typical but non-limiting examples have：The combination of the combination of hydrochloric acid and sulfuric acid, nitric acid and phosphoric acid, sulfuric acid, nitric acid and phosphoric acid
Combination etc..
Preferably, a concentration of 1wt%~98wt% of the acid, for example, 1wt%, 11wt%, 21wt%, 51wt% or
71wt% etc., preferably 20wt%~30wt%；
Preferably, the molar ratio of the dicyclohexyl amine and solute in acid is 1:(0.1~2), such as 1:0.2、1:0.4、 1:
0.6、1:0.8、1:1、1:1.2、1:1.4、1:1.6 or 1:1.8 etc., preferably 1:(0.3~1).
Preferably, the temperature of the mixing be 0~100 DEG C, such as 5 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., preferably 20~65 DEG C.
It is diluted after dicyclohexyl amine is mixed under agitation with acid.
Preferably, the solvent used that dilutes is water.
Preferably, the mass ratio of dicyclohexyl amine and dilution solvent for use is 1:(0~2), such as 1:0.5、1:0.8、 1:1、
1:1.2、1:1.4、1:1.6 or 1:1.8 etc., preferably 1:(0.5~1).
The solvent is selected from methyl formate, methyl acetate, Ethyl formate, ethyl acetate, acetic acid triglyceride, three chloromethanes
Any one in alkane, carbon tetrachloride, benzene, toluene, ethylbenzene, isopropylbenzene or hexamethylene or at least two combination, the combination allusion quotation
Type but non-limiting examples have：The combination of the combination of methyl formate and methyl acetate, Ethyl formate and ethyl acetate, acetic acid three are sweet
The combination of the combination of the combination of grease and chloroform, carbon tetrachloride and benzene, toluene and ethylbenzene, methyl formate, methyl acetate, first
The combination of acetoacetic ester and ethyl acetate, the combination of ethyl acetate, acetic acid triglyceride and chloroform are benzene, toluene, ethylbenzene, different
The combination etc. of propyl benzene and hexamethylene, preferably ethyl acetate and/or toluene.
In the present invention, the effect reached using ethyl acetate and/or toluene as solvent is optimal.
In the present invention, the aqueous slkali technique using the solvent and traditional MBT for preparing vulcanization accelerator is (general common
Produced in DCBS, such as the method involved in CN 102838564A) in solvent for use (such as isopropanol) have essential difference.
If reaction involved in CN 102838564A is solid-liquid heterogeneous reaction, which is raw material M-Na salt
The intermediate product that (NaOH solution of MBT) is formed with dicyclohexyl amine (mainly the complex salt to be formed is complexed with dicyclohexyl amine in MBT)
Redox reaction is carried out with oxidant (sodium hypochlorite), generates target product DCBS.And final product DCBS and intermediate production
Object can suspend in the reaction system in solid form, and the main purpose for introducing this water-soluble solvent of isopropanol is to increase
Solubility of the reaction intermediate in water phase, so that the redox reaction of partial intermediate and oxidant is by solid-liquid
Heterogeneous reaction becomes homogeneous reaction in water, and then improves reaction speed and reaction yield, when reducing long due to oxidant
Between with the side reaction that causes by deep oxidation in solid phase intermediate product contact process.But the isopropanol solvent of introducing, it is only capable of
Reaction speed is improved in part, can not inherently solve the process that DCBS is prepared as heterogeneous reaction.Therefore, most industrialization
Performance is found, after the technical industry, the conversion ratio of raw material MBT is even lower substantially 90% or so.Also, due to
Final product DCBS can in solid form suspend in the reaction system, cannot achieve and continuously given birth in flow reactor
Production.
Thus in view of the above-mentioned problems, present invention introduces solvent, i.e. methyl formate, methyl acetate, Ethyl formate, acetic acid second
Any one in ester, acetic acid triglyceride, chloroform, carbon tetrachloride, benzene, toluene, ethylbenzene, isopropylbenzene or hexamethylene or at least
Two kinds of combination.The purpose that the solvent uses not only is only that instead of isopropanol as solvent, while can make two ring of raw material
Hexylamine and intermediate product (salt to be formed is complexed with dicyclohexyl amine by MBT) make to aoxidize from moving in water phase in solvent phase
Journey become the reaction of the oil/water liquid-liquid diphase between water phase and oil phase by single water phase.Compared to patent CN 102838564A
In solid-liquid phase reaction, present invention introduces solvent make reaction occur mainly on oil/water liquid-liquid two-phase interface, oxidation process
Become more mild controllable, the generation of side reaction can be greatly reduced.
Meanwhile the target product DCBS of generation then can be very good dissolving in a solvent, avoid excessively contacting with oxidant,
To reduce the secondary oxidation of the product generated, and then further increase product yield.Therefore, reaction involved in the present invention
Process goal product yield can reach 95% or more.
The oxidant is oxygen, hydrogen peroxide, liquor natrii hypochloritis, dimethyl sulfoxide (DMSO), chlorine, liquor potassic permanganate or chlorine
Any one in sour potassium solution or at least two combination, the combination is typical but non-limiting examples have：Oxygen and hydrogen peroxide
Combination, the combination of hydrogen peroxide and liquor natrii hypochloritis, the combination of oxygen and chlorine, liquor potassic permanganate and potassium chlorate solution's
Combination, the combination etc. of liquor natrii hypochloritis, dimethyl sulfoxide (DMSO), liquor potassic permanganate and potassium chlorate solution, preferably sodium hypochlorite
Solution.
Preferably, in the liquor natrii hypochloritis available chlorine content be 8wt%~17wt%, such as 8wt%, 10wt%,
12wt%, 14wt%, 16wt% or 17wt% etc..
The charge-mass ratio of the aqueous slkali of the MBT and the acid solution of dicyclohexyl amine is 1:(0.3~5), such as 1:0.5、
1:1、1:1.5、1:2、1:2.5、1:3、1:3.5、1:4、1:4.5 or 1:5 etc., preferably 1:(0.8~2.5)；
Preferably, the charge-mass ratio of the aqueous slkali of MBT and solvent is 1:(0.5~8), such as 1:1、1:1.5、 1:2、
1:2.5、1:3、1:3.5、1:5、1:6.5 or 1:7 etc., preferably 1:(1.5~4).
Preferably, the charge-mass ratio of the aqueous slkali of MBT and oxidant is 1:(1~8), such as 1:1、1:2、 1:3、1:
4、1:5、1:6、1:7 or 1:8 etc., preferably 1:(1~4).
The reaction temperature of the oxidation reaction be 10 DEG C~100 DEG C, such as 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., preferably 20 DEG C~50 DEG C.
Preferably, the residence time of the oxidation reaction be 0.5s~2400s, such as 0.5s, 1s, 3s, 5s, 7s, 10s,
30s, 50s, 70s, 100s, 130s, 150s, 170s, 200s, 220s, 240s, 300s, 500s, 800s, 1000s, 1500s or
1800s etc., preferably 2s~20s；
Preferably, the continuous flow reactor is any one in tubular reactor, micro passage reaction or tower reactor
Kind or at least two combination, preferably micro passage reaction.
In addition, the reaction of oil/water liquid-liquid diphase needs better two-phase mixtures can be the case where not changing reaction yield
Lower raising reaction speed.And micro passage reaction according to the present invention, the material mixing intensity in channel are very big, mass transfer effect
Rate is high.So reaction process according to the present invention, reaction time is only 2-20s, substantially less than currently reported
All reaction technologies.
Oil/water liquid-liquid diphase is reacted to be coordinated with micro passage reaction, during strengthening mixing, without considering side reaction
The problem of, therefore the reaction time can be greatly reduced so that this technology has more industrialization valence in the case where keeping product yield
Value.And the prior art reported, although having used micro passage reaction, homogeneous reaction yield is uncontrollable, when shortening reaction
Between can cause deep oxidation and reduce target product yield, so can not be by the feature of the high mass-and heat-transfer efficiency of micro passage reaction
It brings into play.And longer reaction time then represents lower reaction efficiency so that its industrialization value is greatly reduced.
The post-processing includes：Reacting rear material is crystallized, is washed after separation of solid and liquid, it is dry；
Preferably, the temperature of the crystallization be -5~20 DEG C, such as -3 DEG C, -2 DEG C, -1 DEG C, 0 DEG C, 5 DEG C, 8 DEG C, 10 DEG C, 15
DEG C or 18 DEG C etc., preferably 0~10 DEG C；
Preferably, the washing includes carrying out organic solvent washing and washing successively.
Preferably, the number of the organic solvent washing is at least primary, such as 2 times, 3 times, 5 times, 8 times or 10 inferior, institutes
The number for stating washing is at least twice, and such as 3 times, 4 times, 5 times, 8 times, 10 times or 11 are inferior.
Preferably, the organic solvent is selected from methanol, ethyl alcohol, isopropanol, methyl formate, methyl acetate, Ethyl formate, second
The aqueous solution of any one in acetoacetic ester, acetic acid triglyceride, acetone, tert-butylamine, cyclohexylamine or aniline or at least two
The aqueous solution of combination, typical but non-limiting combination such as the aqueous solution of methanol and ethyl alcohol, isopropanol, methyl formate and acetic acid first
The aqueous solution of ester, Ethyl formate, ethyl acetate and acetic acid triglyceride aqueous solution, acetone, tert-butylamine, cyclohexylamine and aniline
Aqueous solution, the preferably aqueous solution of isopropanol.
The continuous production method of the accelerator D CBS includes the following steps as a preferred technical solution,：
(1) MBT is mixed in 0 DEG C~100 DEG C under agitation with the aqueous slkali of a concentration of 1wt%~50wt%, is made
Obtain the aqueous slkali of MBT；Wherein, the molar ratio of MBT and solute in aqueous slkali is 1:(0.5~3), incorporation time are 0~4h；
Dicyclohexyl amine is mixed in 0 DEG C~100 DEG C under agitation with the acid of a concentration of 1wt~98wt%, water is used in combination
Dilution, obtains the acid solution of dicyclohexyl amine；Wherein, the molar ratio of dicyclohexyl amine and solute in acid solution is 1:(0.1~2), two
The mass ratio of cyclohexylamine and water is 1:(0~2)；
(2) aqueous slkali of MBT, the acid solution of cyclohexylamine, solvent and oxidant are passed through in continuous flow reactor at 10 DEG C
Oxidation reaction is carried out at~100 DEG C, the residence time of reaction is 0.5s~2400s, obtains reacting rear material；Wherein, the alkali of MBT
The charge-mass ratio of the acid solution of solution and cyclohexylamine is 1:(0.3~5), the aqueous slkali of MBT and the charge-mass ratio of solvent are
1:(0.5~8), the aqueous slkali of MBT and the feedstock quality of oxidant are 1:(1~8)；
(3) reacting rear material is cooled to -5~20 DEG C to crystallize, agent DCBS crude products is promoted after separation of solid and liquid,
After washed through primary organic solvent, wash twice, re-dry, obtain DCBS finished products.
As most preferred technical solution, the continuous production method of the accelerator D CBS includes following step
Suddenly：
(1) MBT is mixed in 40 DEG C~60 DEG C under agitation with the aqueous slkali of a concentration of 20wt%~35wt%, is made
Obtain the aqueous slkali of MBT；Wherein, the molar ratio of MBT and solute in aqueous slkali is 1:(0.5~1.5), incorporation time are 0~2h；
Dicyclohexyl amine is mixed in 20 DEG C~65 DEG C under agitation with the acid of a concentration of 20wt~30wt%, water is used in combination
Dilution, obtains the acid solution of dicyclohexyl amine；Wherein, the molar ratio of dicyclohexyl amine and solute in acid solution is 1:(0.3~1), two
The mass ratio of cyclohexylamine and water is 1:(0.5~1)；
(2) by the aqueous slkali of MBT, the acid solution of cyclohexylamine, solvent and oxidant each lead into continuous flow reactor
Oxidation reaction is carried out at 20 DEG C~50 DEG C, the residence time of reaction is 2s~20s, obtains reacting rear material；Wherein, the alkali of MBT
The charge-mass ratio of the acid solution of solution and cyclohexylamine is 1:(0.8~2.5), the aqueous slkali of MBT and the charge-mass ratio of solvent
It is 1:(1.5~4), the aqueous slkali of MBT and the feedstock quality of oxidant are 1:(1~4)；
(3) reacting rear material is cooled to 0~10 DEG C to crystallize, agent DCBS crude products is promoted after separation of solid and liquid, it
It washes, washes twice, re-dry by an organic solvent, obtain DCBS finished products.
Numberical range of the present invention includes not only enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range includes described in the present invention no longer exclusive list
Specific point value.
Compared with prior art, beneficial effects of the present invention are：
(1) the method for the invention with the aqueous slkali of 2-mercaptobenzothiazole (MBT), the acid solution of cyclohexylamine, solvent and
Oxidant is raw material, prepares accelerator D CBS, DCBS yield (with the content meter of MBT) highest in a continuous flow reactor
Up to 96% or more, product purity is up to 99.wt% or more；
(3) the method for the invention has reaction speed fast, product yield high, and waste water COD is low, and (waste water after reaction carries out
Air-distillation recycle dicyclohexyl amine after, COD can be reduced to 8000ppm or less in remaining water), it is disposable many advantages, such as, be one
Kind has more the new technology of industrialization value.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Embodiment 1
A kind of continuous production method of accelerator D CBS, includes the following steps：
(1) M-Na salting liquids are configured：The accelerant MBT of 400g is mixed with the NaOH solution of a concentration of 32wt% of 360g,
2h is stirred at 50 DEG C, M-Na salting liquids are made；
Configure the hydrochloric acid solution of cyclohexylamine：567g dicyclohexyl amines are mixed with the technical hydrochloric acid of a concentration of 31wt% of 376g,
567g water is added, is stirred at 35 DEG C, obtains the hydrochloric acid solution of cyclohexylamine；
(2) hypochlorous acid for being 17% by M-Na salting liquids, the hydrochloric acid solution of dicyclohexyl amine, solvent toluene and available chlorine content
Sodium solution is according to M-Na salting liquids 69mL/min, the hydrochloric acid solution 136mL/min of dicyclohexyl amine, toluene 130mL/min and secondary chlorine
The speed of acid sodium solution 49mL/min, which is passed through in micro passage reaction, carries out oxidation reaction, reaction time 2s, reaction temperature
Degree is 30 DEG C, and micro passage reaction is that 4 reactors are connected, and every reactor volume is 3.2mL, post-reactor total measurement (volume) of connecting
For 12.8mL；
(4) material flowed out in reactor is collected, is cooled to 5 DEG C under stiring and is crystallized；It is obtained by filtration
Crude product washed once with 200mL isopropanol water solutions, after 200mL water washings 2 times, you can obtain DCBS wet feeds, drying
Afterwards, you can obtain DCBS finished products.
After measured, the present embodiment DCBS yields are 96.2% (with the content meter of MBT), and DCBS purity is 99.2wt%, outside
It is pale yellow powder to see, and for waste water after normal pressure is distilled to recover isopropanol, remaining COD is 5900ppm.
Embodiment 2
A kind of continuous production method of accelerator D CBS, includes the following steps：
(1) M-Na salting liquids are configured：The accelerant MBT of 400g is mixed with the NaOH solution of a concentration of 32wt% of 360g,
2h is stirred at 50 DEG C, M-Na salting liquids are made；
(2) hydrochloric acid solution of dicyclohexyl amine is configured：By the technical hydrochloric acid of 567g dicyclohexyl amines and a concentration of 31wt% of 376g
Mixing is added 567g water, is stirred at 35 DEG C, obtain the hydrochloric acid solution of dicyclohexyl amine；
(3) time for being 17% by M-Na salting liquids, the hydrochloric acid solution of dicyclohexyl amine, solvent ethyl acetate and available chlorine content
Sodium chlorate solution is according to M-Na salting liquids 59mL/min, the hydrochloric acid solution 116mL/min of cyclohexylamine, ethyl acetate 167mL/min
It is passed through in tower reactor with the speed of liquor natrii hypochloritis 42mL/min and carries out oxidation reaction, reaction time 10s, instead
It is 45 DEG C to answer temperature, and tower reactor volume is 64mL；
(4) material flowed out in reactor is collected, is cooled to 8 DEG C under stiring and is crystallized；It is obtained by filtration
Crude product washed once with 200mL isopropanol water solutions, after 200mL water washings 2 times, you can obtain DCBS wet feeds, drying
Afterwards, you can obtain DCBS finished products.
After measured, the present embodiment DCBS yields are 95.1% (with the content meter of MBT), and DCBS purity is 99.3wt%, outside
It is pale yellow powder to see, and for waste water after normal pressure is distilled to recover isopropanol, remaining COD is 6750ppm.
Embodiment 3
A kind of continuous production method of accelerator D CBS, includes the following steps：
(1) M-Na salting liquids are configured：The accelerant MBT of 400g and the NaOH solution of a concentration of 1wt% of 11520g are mixed
It closes, 2h is stirred at 50 DEG C, M-Na salting liquids are made；
(2) hydrochloric acid solution of dicyclohexyl amine is configured：By the technical hydrochloric acid of 567g dicyclohexyl amines and a concentration of 31wt% of 376g
Mixing is added 567g water, is stirred at 35 DEG C, obtain the hydrochloric acid solution of dicyclohexyl amine；
(3) by mixture (the acetic acid second of M-Na salting liquids, the hydrochloric acid solution of dicyclohexyl amine, solvent ethyl acetate and toluene
The mass ratio of ester and toluene is 1:4) liquor natrii hypochloritis for being 17% with available chlorine content is according to M-Na salting liquids 266mL/
Min, the hydrochloric acid solution 34mL/min of cyclohexylamine, the speed of ethyl acetate 48mL/min and liquor natrii hypochloritis 12mL/min are logical
Enter and carry out oxidation reaction in tubular reactor, reaction time 20s, reaction temperature is 45 DEG C, and tubular reactor volume is
120mL；
(4) material flowed out in reactor is collected, is cooled to 6 DEG C under stiring and is crystallized；It is obtained by filtration
Crude product washed once with 200mL isopropanol water solutions, after 200mL water washings 2 times, you can obtain DCBS wet feeds, drying
Afterwards, you can obtain DCBS finished products.
After measured, the present embodiment DCBS yields are 90.3% (with the content meter of MBT), and DCBS purity is 98.9wt%, outside
It is pale yellow powder to see, and for waste water after normal pressure is distilled to recover isopropanol, remaining COD is 780ppm.
Embodiment 4
A kind of continuous production method of accelerator D CBS, includes the following steps：
(1) M-Na salting liquids are configured：The accelerant MBT of 2t is mixed with the NaOH solution of a concentration of 30wt% of 2.4t,
2h is stirred at 60 DEG C, M-Na salting liquids are made；
(2) hydrochloric acid solution of dicyclohexyl amine is configured：By the technical hydrochloric acid of 3.3t dicyclohexyl amines and a concentration of 30wt% of 2.2t,
2.2t water mixes, and is stirred at 40 DEG C, obtains the hydrochloric acid solution of cyclohexylamine；
(3) hypochlorous acid for being 17% by M-Na salting liquids, the hydrochloric acid solution of dicyclohexyl amine, solvent toluene and available chlorine content
Sodium solution is according to M-Na salting liquids 0.77m3/ h, dicyclohexyl amine hydrochloride salting liquid 1.38m3/ h, toluene 1.71m3/ h, hypochlorous acid
Sodium solution 0.98m3The speed of/h, which is passed through in micro passage reaction, carries out oxidation reaction, reaction time 2s, reaction temperature
It it is 40 DEG C, micro passage reaction is that 10 monomer reaction devices are connected, and every reactor volume is 270mL, and series connection post-reactor is total
Volume is 2700mL；
(4) material flowed out in reactor is collected, 5 DEG C is cooled under stirring and is crystallized；It filters
To crude product washed once with 1t isopropanol water solutions, after 1t water washings 2 times, you can DCBS wet feeds are obtained, through drying
Afterwards, you can obtain DCBS finished products.
After measured, DCBS yields are 95.9% (with the content meter of MBT), and DCBS purity is 99.2wt%, and appearance is micro- Huang
Color powder, for waste water after normal pressure is distilled to recover cyclohexylamine, remaining COD is 5830ppm.
Embodiment 5
A kind of continuous production method of accelerator D CBS, includes the following steps：
(1) M-K salting liquids are configured：By the KOH solution of 400g accelerant MBTs and a concentration of 50wt% of 322g at 40 DEG C
3h is stirred, M-K salting liquids are made；
(2) sulfuric acid solution of dicyclohexyl amine is configured：By 780g dicyclohexyl amines, the sulfuric acid and 1160g of a concentration of 98wt% of 96g
Water stirs at 50 DEG C, obtains the sulfuric acid solution of dicyclohexyl amine；
(3) by M-K salting liquids, the sulfuric acid solution of dicyclohexyl amine, solvent acetic acid methyl esters and a concentration of 17% dioxygen it is water-soluble
Liquid is according to M-K salting liquids 6mL/min, cyclohexylamine sulfate liquor 36mL/min, methyl acetate 55mL/min, hydrogen peroxide solution
The speed of 15mL/min, which is passed through in micro passage reaction, carries out oxidation reaction, reaction time 5s, and reaction temperature is 50 DEG C,
Micro passage reaction is that 5 monomer reaction devices are connected, and every reactor volume is 1.86mL, and series connection post-reactor total measurement (volume) is
9.3mL；
(4) material flowed out in reactor is collected, 10 DEG C is cooled under stirring and is crystallized；It filters
To crude product washed once with 200mL isopropanol water solutions, after 200mL water washings 2 times, you can obtain DCBS wet feeds, pass through
After drying, you can obtain DCBS finished products.
After measured, DCBS yields are 85.6% (with the content meter of MBT), and DCBS purity is 98.9wt%, and appearance is yellowish-brown
Color microcrystalline powder, for waste water after normal pressure is distilled to recover cyclohexylamine, remaining COD is 7500ppm.
Comparative example 1：
This comparative example provides a kind of production method of accelerator D CBS, and the method is with reference to side in embodiment 3
Method, difference lies in：The hydrochloric acid solution for not preparing dicyclohexyl amine in step (1), by the aqueous slkali of MBT, hexamethylene in step (2)
The liquor natrii hypochloritis that amine, hydrochloric acid, solvent ethyl acetate and available chlorine content are 17% presses the consumption proportion in embodiment 1 respectively
It is added in micro passage reaction；
In this comparative example, due to not preparing the hydrochloric acid solution of dicyclohexyl amine, repeatedly occurs equipment in reaction process and block feelings
Condition, after measured, DCBS yields are 66.7% (with the content meter of MBT), and DCBS purity is 94.1wt%, and waste water is through air-distillation
After recycling cyclohexylamine, remaining COD is 20500ppm.
Comparative example 2
This comparative example provides a kind of production method of accelerator D CBS, and the method is with reference to side in embodiment 3
Method, difference lies in：Step (2) described solvent is isopropanol.
In this comparative example, due to being used as solvent using isopropanol, repeatedly there is equipment stopping state in reaction process, through survey
Fixed, DCBS yields are 71.6% (with the content meter of MBT), and DCBS purity is 95.5wt%, and waste water is distilled to recover hexamethylene through normal pressure
After amine, remaining COD is 17600ppm.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of continuous production method of accelerator D CBS, which is characterized in that the method includes：
The aqueous slkali of MBT, the acid solution of dicyclohexyl amine, solvent and oxidant are subjected to oxidation reaction in a continuous flow reactor,
Later, reacting rear material is post-processed, obtains accelerator D CBS.
2. continuous production method according to claim 1, which is characterized in that the preparation method of the aqueous slkali of the MBT
Include the following steps：MBT is mixed with aqueous slkali under agitation, the aqueous slkali of MBT is made；
Preferably, the aqueous slkali includes NaOH solution, KOH solution or NH3·H2Any one in O solution or at least two
Mixing, preferably NaOH solution；
Preferably, a concentration of 1wt%~50wt% of the aqueous slkali, preferably 20wt%~35wt%；
Preferably, the molar ratio of the MBT and solute in aqueous slkali is 1:(0.3~4.0), preferably 1:(0.5~1.5)；
Preferably, the time of the mixing is 0~4h, preferably 0~2h；
Preferably, the temperature of the mixing is 0~100 DEG C, preferably 40 DEG C~60 DEG C.
3. continuous production method according to claim 1 or 2, which is characterized in that the acid solution of the dicyclohexyl amine
Preparation method includes the following steps：Dicyclohexyl amine is mixed under agitation with acid, obtains the acid solution of dicyclohexyl amine；
Preferably, the acid includes any one in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid or at least two combination；
Preferably, a concentration of 1wt%~98wt%, preferably 20wt%~30wt% of the acid；
Preferably, the molar ratio of the dicyclohexyl amine and solute in acid is 1:(0.1~2), preferably 1:(0.3~1)；
Preferably, the temperature of the mixing is 0~100 DEG C, preferably 20~65 DEG C.
4. continuous production method according to claim 3, which is characterized in that under agitation with acid by dicyclohexyl amine
It is diluted after mixing；
Preferably, the solvent used that dilutes is water；
Preferably, the mass ratio of dicyclohexyl amine and dilution solvent for use is 1:(0~2), preferably 1:(0.5~1).
5. according to claim 1-4 any one of them continuous production methods, which is characterized in that the solvent is selected from formic acid first
It is ester, methyl acetate, Ethyl formate, ethyl acetate, acetic acid triglyceride, chloroform, carbon tetrachloride, benzene, toluene, ethylbenzene, different
Any one in propyl benzene or hexamethylene or at least two combination, preferably ethyl acetate and/or toluene.
6. according to claim 1-5 any one of them continuous production methods, which is characterized in that the oxidant be oxygen,
Any one in hydrogen peroxide, liquor natrii hypochloritis, dimethyl sulfoxide (DMSO), chlorine, liquor potassic permanganate or potassium chlorate solution or at least
Two kinds of combination, preferably liquor natrii hypochloritis；
Preferably, available chlorine content is 8wt%~17wt% in the liquor natrii hypochloritis.
7. according to claim 1-6 any one of them continuous production methods, which is characterized in that the aqueous slkali of the MBT and
The charge-mass ratio of the acid solution of dicyclohexyl amine is 1:(0.3~5), preferably 1:(0.8~2.5)；
Preferably, the charge-mass ratio of the aqueous slkali of MBT and solvent is 1:(0.5~8), preferably 1:(1.5~4)；
Preferably, the charge-mass ratio of the aqueous slkali of MBT and oxidant is 1:(1~8), preferably 1:(1~4).
8. according to claim 1-7 any one of them continuous production methods, which is characterized in that the reaction of the oxidation reaction
Temperature is 10 DEG C~100 DEG C, preferably 20 DEG C~50 DEG C；
Preferably, the residence time of the oxidation reaction is 0.5s~2400s, preferably 2s~20s；
Preferably, the continuous flow reactor be tubular reactor, micro passage reaction or tower reactor in any one or
At least two combination.
9. according to claim 1-8 any one of them continuous production methods, which is characterized in that the post-processing includes：It will
Reacting rear material crystallizes, and is washed after separation of solid and liquid, dry；
Preferably, the temperature of the crystallization is -5~20 DEG C, preferably 0~10 DEG C；
Preferably, the washing includes carrying out organic solvent washing and washing successively；
Preferably, the number of the organic solvent washing is at least primary, and the number of the washing is at least twice；
Preferably, the organic solvent is selected from methanol, ethyl alcohol, isopropanol, methyl formate, methyl acetate, Ethyl formate, acetic acid second
The aqueous solution of any one in ester, acetic acid triglyceride, acetone, tert-butylamine, cyclohexylamine or aniline or at least two combination
Aqueous solution, the preferably aqueous solution of isopropanol.
10. according to claim 1-9 any one of them continuous production methods, which is characterized in that the method includes following
Step：
(1) MBT is mixed in 0 DEG C~100 DEG C under agitation with the aqueous slkali of a concentration of 1wt%~50wt%, MBT is made
Aqueous slkali；Wherein, the molar ratio of MBT and solute in aqueous slkali is 1:(0.5~3), incorporation time are 0~4h；
Dicyclohexyl amine is mixed in 0 DEG C~100 DEG C under agitation with the acid of a concentration of 1wt~98wt%, and is diluted with water,
Obtain the acid solution of dicyclohexyl amine；Wherein, the molar ratio of dicyclohexyl amine and solute in acid solution is 1:(0.1~2), dicyclohexyl amine
Mass ratio with water is 1:(0~2)；
(2) aqueous slkali of MBT, the acid solution of cyclohexylamine, solvent and oxidant are passed through in continuous flow reactor 10 DEG C~100
Oxidation reaction is carried out at DEG C, the residence time of reaction is 0.5s~2400s, obtains reacting rear material；Wherein, the aqueous slkali of MBT
Charge-mass ratio with the acid solution of cyclohexylamine is 1:(0.3~5), the aqueous slkali of MBT and the charge-mass ratio of solvent are 1:
(0.5~8), the aqueous slkali of MBT and the feedstock quality of oxidant are 1:(1~8)；
(3) reacting rear material is cooled to -5~20 DEG C to crystallize, agent DCBS crude products is promoted after separation of solid and liquid, after pass through
One time organic solvent is washed, and is washed twice, re-dry, and DCBS finished products are obtained.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105304A (en) * | 2019-06-21 | 2019-08-09 | 科迈化工股份有限公司 | A method of using liquid chlorine as oxidant continuous production vulcanization accelerator TBBS |
| CN110156718A (en) * | 2019-06-21 | 2019-08-23 | 科迈化工股份有限公司 | A method of using liquid chlorine as oxidant continuous production accelerator D CBS |
| CN111072595A (en) * | 2020-01-19 | 2020-04-28 | 山东尚舜化工有限公司 | Novel method for preparing rubber accelerator DCBS |
| CN112645900A (en) * | 2020-12-25 | 2021-04-13 | 科迈化工股份有限公司 | Synthesis method of accelerant DCBS |
| CN113582944A (en) * | 2021-10-08 | 2021-11-02 | 科迈化工股份有限公司 | Production process of accelerant DCBS |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524450A (en) * | 2013-09-30 | 2014-01-22 | 科迈化工股份有限公司 | Synthetic method for accelerator DZ by using methanol as solvent |
| CN106749096A (en) * | 2017-02-21 | 2017-05-31 | 山东尚舜化工有限公司 | The preparation method and device of a kind of rubber vulcanization accelerator DZ |
-
2018
- 2018-05-23 CN CN201810502215.1A patent/CN108586383A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524450A (en) * | 2013-09-30 | 2014-01-22 | 科迈化工股份有限公司 | Synthetic method for accelerator DZ by using methanol as solvent |
| CN106749096A (en) * | 2017-02-21 | 2017-05-31 | 山东尚舜化工有限公司 | The preparation method and device of a kind of rubber vulcanization accelerator DZ |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105304A (en) * | 2019-06-21 | 2019-08-09 | 科迈化工股份有限公司 | A method of using liquid chlorine as oxidant continuous production vulcanization accelerator TBBS |
| CN110156718A (en) * | 2019-06-21 | 2019-08-23 | 科迈化工股份有限公司 | A method of using liquid chlorine as oxidant continuous production accelerator D CBS |
| CN111072595A (en) * | 2020-01-19 | 2020-04-28 | 山东尚舜化工有限公司 | Novel method for preparing rubber accelerator DCBS |
| CN112645900A (en) * | 2020-12-25 | 2021-04-13 | 科迈化工股份有限公司 | Synthesis method of accelerant DCBS |
| CN113582944A (en) * | 2021-10-08 | 2021-11-02 | 科迈化工股份有限公司 | Production process of accelerant DCBS |
| CN113582944B (en) * | 2021-10-08 | 2022-03-15 | 科迈化工股份有限公司 | Production process of accelerant DCBS |
| WO2023056739A1 (en) * | 2021-10-08 | 2023-04-13 | 科迈化工股份有限公司 | Production process for accelerator dcbs |
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