CN110354900A - Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method - Google Patents
Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method Download PDFInfo
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- CN110354900A CN110354900A CN201910796681.XA CN201910796681A CN110354900A CN 110354900 A CN110354900 A CN 110354900A CN 201910796681 A CN201910796681 A CN 201910796681A CN 110354900 A CN110354900 A CN 110354900A
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- vulcanization accelerator
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- tertiary butyl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention belongs to catalyst preparation technical field, it is related to a kind of thiofide catalyst preparation and application method.Catalyst is by the way that cobalt ammonia complex made from excessive ammonia is added in cobalt chloride.Catalyst have cobalt center site, can under the conditions of hydrogen peroxide oxidation synthetic rubber vulcanization accelerator N tert butyl benzothiazole 2 sulfenamide.Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide conversion ratio and selectivity are high, and production process is simple, at low cost.
Description
Technical field
The invention belongs to catalyst preparation technical field, it is related to a kind of thiofide catalyst preparation and user
Method, more particularly to a kind of hydrogen peroxide method synthetic rubber vulcanization accelerator N tert butyl benzothiazole 2 sulfenamide (NS) are urged
Agent preparation and application.
Background technique
N tert butyl benzothiazole 2 sulfenamide (NS) is a kind of common thiofide, is had wide
Cure range can be used alone, or be used in combination with dithiocarbamates, thiurams, guanidine and other alkaline accelerators.
Mainly for the manufacture of tire, adhesive tape, rubber overshoes and other industrial rubber articles.N tert butyl benzothiazole 2 sulfenamide is constant
The advantages of color, no blooming, and the performance that vulcanizate stretching strength, tensile strength are obviously improved, answer it extensively
With.Oxidant used in the method for industrial synthesis N tert butyl benzothiazole 2 sulfenamide is mainly hypochlorous acid at present
Two kinds of strong oxidizers of sodium, both oxidants have strong oxidizing property and corrosivity, the high requirements on the equipment, and the inadequate ring of oxidant
It protects, generates a large amount of waste water in production process and be difficult to handle, lead to environmental pollution, generate a large amount of inorganic salts containing chlorine, pollute environment；This
Outside, in traditional handicraft preparation process N tert butyl benzothiazole 2 sulfenamide conversion ratio and selectivity also up for further
It improves.
A kind of oxidant of the hydrogen peroxide (hydrogen peroxide) as feature of environmental protection, is in the past few years increasingly becoming the hot spot of research and development, still
Since hydrogen peroxide is relatively stable, never most suitable catalyst at present, so that the conversion ratio and selectivity of promotor
Reach higher level, therefore, the research of catalyst is current difficult point place.
Summary of the invention
The present invention is directed in traditional rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) preparation process
There are the problem of propose a kind of novel hydrogen peroxide method synthetic rubber vulcanization accelerator N- tert-butyl -2-[4-morpholinodithio time sulphonyl
Amine (NS) catalyst preparation and application method.
In order to achieve the above object, the present invention is realized using following technical solutions:
A kind of rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method for preparing catalyst, the catalysis
Agent is by the way that cobalt ammonia complex made from excessive ammonia is added in cobalt chloride.
Utilize the method for above-mentioned catalyst preparation rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide, institute
It is dibenzothiazyl disulfide, hydrogen peroxide, tert-butylamine, methylene chloride, ammonium hydroxide, cobalt ammonia complex and surface-active with raw material
Agent；Its formula rate is as follows:
Dibenzothiazyl disulfide: hydrogen peroxide=1.0:(0.5-0.8), molar ratio；
Dibenzothiazyl disulfide: tert-butylamine=1.0:(1.0-1.05), molar ratio
Dibenzothiazyl disulfide: methylene chloride=1.0:(2-5), molar ratio；
Dibenzothiazyl disulfide: ammonium hydroxide=1.0:(0.2-0.5), molar ratio；
Dibenzothiazyl disulfide: cobalt ammonia complex=1.0:(0.01-0.015), mass ratio；
Dibenzothiazyl disulfide: surfactant=1.0:(0.0001-0.00013), mass ratio.
Preferably, the surfactant is TW-80.
Preferably, described prepare rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method, step
It is as follows:
(1) ammonium hydroxide, surfactant and methylene chloride, stirring are added in the reactor；
(2) dibenzothiazyl disulfide and catalyst cobalt ammino-complex is added；
(3) it keeps temperature to 26 DEG C, hydrogen peroxide is added, tert-butylamine is added after reacting 2-3h；
(4) temperature of reactor is increased to 35-45 DEG C, reacts 0.5-0.8h, reaction terminates；Obtain white precipitate；
(5) white precipitate washing, filtering, drying.
Preferably, described prepare rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method, step
It is as follows:
(1) ammonium hydroxide of solutes content 8.5g is added in the reactor, 0.03g surfactant TW-80 and 185g bis- is added
Chloromethanes, stirring；
(2) dibenzothiazyl disulfide 33.2g and catalyst cobalt ammino-complex 0.3g is added；
(3) it keeps temperature to 27 DEG C, hydrogen peroxide is added, tert-butylamine 74.1g is added after reacting 2.5h；
(4) temperature of reactor is increased to 40 DEG C, reacts 0.5h, reaction terminates；Obtain white precipitate；
(5) white precipitate washing, filtering, drying.
Preferably, described prepare rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method, step
It is as follows:
(1) ammonium hydroxide, surfactant 0.031g and methylene chloride 400g, stirring are added in the reactor；
(2) dibenzothiazyl disulfide 33.2g and catalyst cobalt ammino-complex 0.40g is added；
(3) it keeps temperature to 25 DEG C, hydrogen peroxide is added, tert-butylamine 74.8g is added after reacting 3h；
(4) temperature of reactor is increased to 45 DEG C, reacts 0.8h, reaction terminates；Obtain white precipitate；
(5) white precipitate washing, filtering, drying.
Compared with prior art, the advantages and positive effects of the present invention are:
1. catalyst have cobalt center site, can under the conditions of hydrogen peroxide oxidation synthetic rubber vulcanization accelerator uncle N-
Butyl -2-[4-morpholinodithio sulfenamide.
2. rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide conversion ratio and selectivity are high, and produce
Journey is simple, at low cost.
3. not generating pollution villaumite in reaction process, by-product only has water generation, environmental-friendly.
Specific embodiment
To better understand the objects, features and advantages of the present invention, right combined with specific embodiments below
The present invention is described further.It should be noted that in the absence of conflict, the spy in embodiments herein and embodiment
Sign can be combined with each other.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, still, the present invention may be used also
To be implemented using other modes described herein are different from, therefore, the present invention is not limited to the specific of specification is described below
The limitation of embodiment.
Embodiment 1, the present embodiment provides rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide preparation methods
And method for preparing catalyst.
1. cobalt ammonia complex catalyst preparation
Ammonium hydroxide will be added dropwise in cobalt chloride solution, after generating precipitating, continue to be added dropwise ammonium hydroxide to disappearance is precipitated, cobalt ammonia can be obtained
Complex compound filters when being evaporated to compared with polycrystalline precipitation, is dried to obtain solid catalyst.
2.N- tert-butyl -2-[4-morpholinodithio sulfenamide preparation
The ammonium hydroxide of solutes content 8.5g is added in the reactor, 0.03g surfactant TW-80 and 185g dichloromethane is added
Alkane, stirring；
Dibenzothiazyl disulfide 33.2g and catalyst cobalt ammino-complex 0.3g is added；
It keeps temperature to 27 DEG C, hydrogen peroxide 1.7g is added, tert-butylamine 74.1g is added after reacting 2.5h；
Temperature of reactor is increased to 40 DEG C, reacts 0.5h, reaction terminates；Obtain white precipitate；
White precipitate is washed, filters, is dried to obtain N tert butyl benzothiazole 2 sulfenamide.
Through detecting, N tert butyl benzothiazole 2 sulfenamide conversion ratio is 99.3%, and selectivity is 99.1%.
Embodiment 2, the present embodiment provides rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide preparation methods
And method for preparing catalyst.
1. cobalt ammonia complex catalyst preparation
Ammonium hydroxide will be added dropwise in cobalt chloride solution, after generating precipitating, continue to be added dropwise ammonium hydroxide to disappearance is precipitated, cobalt ammonia can be obtained
Complex compound filters when being evaporated to compared with polycrystalline precipitation, is dried to obtain solid catalyst.
2.N- tert-butyl -2-[4-morpholinodithio sulfenamide preparation
Ammonium hydroxide 7.5g, surfactant 0.031g and methylene chloride 400g, stirring are added in the reactor；
Dibenzothiazyl disulfide 33.2g and catalyst cobalt ammino-complex 0.40g is added；
It keeps temperature to 25 DEG C, hydrogen peroxide 2.5g is added, tert-butylamine 74.8g is added after reacting 3h；
Temperature of reactor is increased to 45 DEG C, reacts 0.8h, reaction terminates；Obtain white precipitate；
White precipitate washing, filtering, drying.
Through detecting, N tert butyl benzothiazole 2 sulfenamide conversion ratio is 99.2%, and selectivity is 99.1%.
Embodiment 3, the present embodiment provides rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide preparation methods
And method for preparing catalyst.
1. cobalt ammonia complex catalyst preparation
Ammonium hydroxide will be added dropwise in cobalt chloride solution, after generating precipitating, continue to be added dropwise ammonium hydroxide to disappearance is precipitated, cobalt ammonia can be obtained
Complex compound filters when being evaporated to compared with polycrystalline precipitation, is dried to obtain solid catalyst.
2.N- tert-butyl -2-[4-morpholinodithio sulfenamide preparation
Ammonium hydroxide 3.4g, surfactant 0.033g and methylene chloride 300g, stirring are added in the reactor；
Dibenzothiazyl disulfide 33.2g and catalyst cobalt ammino-complex 0.45g is added；
It keeps temperature to 27 DEG C, hydrogen peroxide 2.7g is added, tert-butylamine 74.5g is added after reacting 3.5h；
Temperature of reactor is increased to 45 DEG C, reacts 0.6h, reaction terminates；Obtain white precipitate；
White precipitate washing, filtering, drying.
Through detecting, N tert butyl benzothiazole 2 sulfenamide conversion ratio is 99.1%, and selectivity is 99.3%.
Embodiment 4, the present embodiment provides rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide preparation methods
And method for preparing catalyst.
1. cobalt ammonia complex catalyst preparation
Ammonium hydroxide will be added dropwise in cobalt chloride solution, after generating precipitating, continue to be added dropwise ammonium hydroxide to disappearance is precipitated, cobalt ammonia can be obtained
Complex compound filters when being evaporated to compared with polycrystalline precipitation, is dried to obtain solid catalyst.
2.N- tert-butyl -2-[4-morpholinodithio sulfenamide preparation
Ammonium hydroxide 5.6g, surfactant 0.032g and methylene chloride 350g, stirring are added in the reactor；
Dibenzothiazyl disulfide 35g and catalyst cobalt ammino-complex 0.38g is added；
It keeps temperature to 24 DEG C, hydrogen peroxide 2.3g is added, tert-butylamine 70g is added after reacting 3h；
Temperature of reactor is increased to 43 DEG C, reacts 0.9h, reaction terminates；Obtain white precipitate；
White precipitate washing, filtering, drying.
Through detecting, N tert butyl benzothiazole 2 sulfenamide conversion ratio is 99.3%, and selectivity is 99.2%.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
It imitates embodiment and is applied to other fields, but without departing from the technical solutions of the present invention, according to the technical essence of the invention
Any simple modification, equivalent variations and remodeling to the above embodiments, still fall within the protection scope of technical solution of the present invention.
Claims (6)
1. a kind of rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method for preparing catalyst, it is characterised in that,
The catalyst is by the way that cobalt ammonia complex made from excessive ammonia is added in cobalt chloride.
2. utilizing rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide catalyst preparation rubber described in claim 1
The method of glue vulcanization accelerator N tert butyl benzothiazole 2 sulfenamide, which is characterized in that raw materials used is diphenyl disulfide
And thiazole, hydrogen peroxide, tert-butylamine, methylene chloride, ammonium hydroxide, cobalt ammonia complex and surfactant；Its formula rate is as follows:
Dibenzothiazyl disulfide: hydrogen peroxide=1.0:(0.5-0.8), molar ratio；
Dibenzothiazyl disulfide: tert-butylamine=1.0:(1.0-1.05), molar ratio；
Dibenzothiazyl disulfide: methylene chloride=1.0:(2-5), molar ratio；
Dibenzothiazyl disulfide: ammonium hydroxide=1.0:(0.2-0.5), molar ratio；
Dibenzothiazyl disulfide: cobalt ammonia complex=1.0:(0.01-0.015), mass ratio；
Dibenzothiazyl disulfide: surfactant=1.0:(0.0001-0.00013), mass ratio.
3. rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method is prepared according to claim 2,
It is characterized in that, the surfactant is TW-80.
4. rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method is prepared according to claim 2,
It is characterized in that, steps are as follows:
(1) ammonium hydroxide, surfactant and methylene chloride, stirring are added in the reactor；
(2) dibenzothiazyl disulfide and catalyst cobalt ammino-complex is added；
(3) it keeps temperature to 26 DEG C, hydrogen peroxide is added, tert-butylamine is added after reacting 2-3h；
(4) temperature of reactor is increased to 35-45 DEG C, reacts 0.5-0.8h, reaction terminates；Obtain white precipitate；
(5) white precipitate washing, filtering, drying.
5. rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method is prepared according to claim 2,
It is characterized in that, steps are as follows:
(1) ammonium hydroxide of solutes content 8.5g is added in the reactor, 0.03g surfactant TW-80 and 185g dichloromethane is added
Alkane, stirring；
(2) dibenzothiazyl disulfide 33.2g and catalyst cobalt ammino-complex 0.3g is added；
(3) it keeps temperature to 27 DEG C, hydrogen peroxide is added, tert-butylamine 74.1g is added after reacting 2.5h；
(4) temperature of reactor is increased to 40 DEG C, reacts 0.5h, reaction terminates；Obtain white precipitate；
(5) white precipitate washing, filtering, drying.
6. rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide method is prepared according to claim 2,
It is characterized in that, steps are as follows:
(1) ammonium hydroxide, surfactant 0.031g and methylene chloride 400g, stirring are added in the reactor；
(2) dibenzothiazyl disulfide 33.2g and catalyst cobalt ammino-complex 0.40g is added；
(3) it keeps temperature to 25 DEG C, hydrogen peroxide is added, tert-butylamine 74.8g is added after reacting 3h；
(4) temperature of reactor is increased to 45 DEG C, reacts 0.8h, reaction terminates；Obtain white precipitate；
(5) white precipitate washing, filtering, drying.
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| CN201910796681.XA CN110354900A (en) | 2019-08-27 | 2019-08-27 | Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method |
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| CN201910796681.XA CN110354900A (en) | 2019-08-27 | 2019-08-27 | Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112237924A (en) * | 2020-12-16 | 2021-01-19 | 科迈化工股份有限公司 | Catalyst for synthesizing promoter TBBS and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670556A (en) * | 1983-07-16 | 1987-06-02 | Akzo Nv | Process for the production of thiazolyl-2-sulphenamides |
| CN101717380A (en) * | 2009-12-09 | 2010-06-02 | 河南省开仑化工有限责任公司 | Clean production method of rubber vulcanizing accelerator TBBS |
| CN103073521A (en) * | 2012-09-20 | 2013-05-01 | 濮阳蔚林化工股份有限公司 | Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) |
| CN103508976A (en) * | 2013-09-30 | 2014-01-15 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator NS |
| CN108084114A (en) * | 2017-12-19 | 2018-05-29 | 蔚林新材料科技股份有限公司 | The preparation method of rubber vulcanizing accelerator CBS |
| CN108727302A (en) * | 2017-10-23 | 2018-11-02 | 科迈化工股份有限公司 | A kind of environment-friendly type N tert butyl benzothiazole 2 sulfenamide（NS）Synthesis technology |
-
2019
- 2019-08-27 CN CN201910796681.XA patent/CN110354900A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670556A (en) * | 1983-07-16 | 1987-06-02 | Akzo Nv | Process for the production of thiazolyl-2-sulphenamides |
| CN101717380A (en) * | 2009-12-09 | 2010-06-02 | 河南省开仑化工有限责任公司 | Clean production method of rubber vulcanizing accelerator TBBS |
| CN103073521A (en) * | 2012-09-20 | 2013-05-01 | 濮阳蔚林化工股份有限公司 | Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) |
| CN103508976A (en) * | 2013-09-30 | 2014-01-15 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator NS |
| CN108727302A (en) * | 2017-10-23 | 2018-11-02 | 科迈化工股份有限公司 | A kind of environment-friendly type N tert butyl benzothiazole 2 sulfenamide（NS）Synthesis technology |
| CN108084114A (en) * | 2017-12-19 | 2018-05-29 | 蔚林新材料科技股份有限公司 | The preparation method of rubber vulcanizing accelerator CBS |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112237924A (en) * | 2020-12-16 | 2021-01-19 | 科迈化工股份有限公司 | Catalyst for synthesizing promoter TBBS and application thereof |
| CN112237924B (en) * | 2020-12-16 | 2021-04-06 | 科迈化工股份有限公司 | Catalyst for synthesizing promoter TBBS and application thereof |
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