CN103193732B - Preparation method of rubber vulcanization accelerator DM - Google Patents
Preparation method of rubber vulcanization accelerator DM Download PDFInfo
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- CN103193732B CN103193732B CN201310147902.3A CN201310147902A CN103193732B CN 103193732 B CN103193732 B CN 103193732B CN 201310147902 A CN201310147902 A CN 201310147902A CN 103193732 B CN103193732 B CN 103193732B
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Abstract
The invention discloses a preparation method of a rubber vulcanization accelerator DM. The preparation method comprises the following steps of: (1) adding 500 parts by mass of M-Na salt solution with the mass percentage of 10-50 percent and 0.1-10 parts by mass of catalyst A to a reactor; (2) dropwise adding a mixed solution containing hydrogen peroxide with the mass concentration of 2-20 percent and sulfuric acid with the mass concentration of 1-20 percent to the reactor, and stirring under the condition of 20-100 DEG C; and (3) sampling and measuring the PH value of a sample, when the PH value is 4.0-8.0, stopping reacting, and carrying out suction filtration, water washing, filtering and drying to obtain the product, namely the rubber vulcanization accelerator DM. The preparation method disclosed by the invention is simple in process and easy for industrial production; as an environment-friendly oxidant is adopted, the environmental pollution is effectively avoided, the water treatment cost is reduced, and the product cost is indirectly reduced; and the rubber vulcanization accelerator DM prepared by using the preparation method is high in melting point and yield, large in particle size and convenient to filter, dry, package and transport.
Description
Technical field
The present invention relates to rubber vulcanization accelerator DM production technical field, particularly relate to the preparation method of a kind of rubber vulcanization accelerator dibenzothiazyl disulfide (DM).
Background technology
Rubber accelerator plays very important effect in Vulcanization Process of Rubber, accelerates the reaction of rubber and vulcanizing agent, improves production efficiency, and DM is indispensable a kind of auxiliary agent in rubber accelerator industry.About the production technique of DM, also some are had to report both at home and abroad, mainly with 2-mercaptobenzothiazole (M) for raw material, use oxidizing obtaining, main oxygenant has nitrous acid, oxygen, chlorine, potassium permanganate etc., though these methods respectively have advantage above, but produce a large amount of byproducts, exert a certain influence to environment, Water purification engineering brings very large pressure, processing condition are wayward, complicated operation.
(Speciality Petrochemicals is in progress document, 2006,7 (9): 35) report with hydrogen peroxide oxidation M, prepare DM with Virahol as carrier, Virahol can follow bad use, although this processing method have employed environment-friendly type oxygenant, environmental pollution decreases pressure, is the increase in mother liquor separation circuit, the energy that the needs that mother liquor distills are very large, improve production cost, complex process, not easy to operate.
Patent (200710016805.5, after 2007-7-9) reporting M ammoniacal liquor or liquefied ammonia dissolving, obtain ammonium salt solution to filter, add catalyzer and under certain temperature and pressure, pass into oxygen or the air reaction regular hour obtains DM product, this processing method complicated operation, ammonium salt solution needs to filter, and whole technique needs catalyzer, and in waste water, ammonia-nitrogen content is high.
Patent (200810183218.X, 2008-12-16) report at 55 ~ 65 DEG C, be oxygenant with the mixture of hydrogen peroxide and sulfuric acid, direct oxidation Vencide salt, when pH is stabilized in 6.5 ~ 7.5, reaction terminates, solid-liquid separation is carried out at control temperature about 30 DEG C, obtain product DM, this processing method is simple to operate, pollute little, but also there is weak point, oxygenant is easy to decompose, oxidizing temperature is low, material viscosity is high, be not easy to solid-liquid separation, about 30 DEG C must be cooled to after reaction terminates, just separable, extend reaction time, energy dissipation is caused in temperature-fall period.And the standby product bulk density of above-mentioned each patent system is little, product particle is little, is unfavorable for dryly being separated, packaging.
Summary of the invention
The object of the invention is the technological deficiency for existing in prior art, and a kind of preparation method that effectively can improve the rubber vulcanization accelerator dibenzothiazyl disulfide (DM) of product particle is provided.
The technical scheme adopted for realizing object of the present invention is:
A preparation method for rubber vulcanization accelerator DM, comprises following process:
1) be that the M-Na salts solution of 10-50% and the catalyst A of 0.1-10 mass fraction join in reactor by the mass percentage of 500 mass fractions, wherein, described catalyst A is by PtO
2and RhO
2composition, PtO
2with RhO
2mass ratio at 1:0.1-99,
2) mixing solutions of to be the hydrogen peroxide of 2-20% and mass concentration by mass concentration the be sulfuric acid of 1-20% is added drop-wise in reactor, stirs under the condition of 20-100 ° of C,
3) sample and measure its pH value, when pH value is 4.0-8.0, stopped reaction, suction filtration, washing, filtration, dry rubber accelerator DM product.
Utilizing water carrier to substitute organic solvent to react, by adding a small amount of catalyzer, improving the oxidisability of oxygenant.From reaction mechanism, the size of product bulk density and the size of oxidizability of oxidants have direct relation, and reason is that the oxidisability of oxygenant is stronger, then more can improve speed of reaction, speed of reaction is faster, and during raw material generation product, the bulk density of product is larger.Adopt environment-friendly type oxygenant, the yield of altax reaches more than 95%, and product bulk density reaches more than 0.3g/ml., the particle making product keep larger, is convenient to follow-up processing, use etc.
Preferably, described M-Na salts solution preparation method is: the MBT being 170 ° of C by 50 grams of fusing points joins and is equipped with 80 grams, mass percent is in the beaker of the NaOH solution of 20%, be heated to 70-75 ° of C, MBT is dissolved and is prepared into M-Na salts solution, the endpoint pH of this M-Na salts solution remains on 12.
Described hydrogen peroxide and the mixing solutions of sulfuric acid are added drop-wise in reactor with the flow velocity of 10-30ml/min.
In described step 2, mixing speed is 10-500 rev/min, starts sampling and measuring after stirring 10-100min.
Compared with prior art, the invention has the beneficial effects as follows:
Preparation method's process of the present invention is simple, be easy to industrialization, adopt environment-friendly type oxygenant, effectively prevent environmental pollution, reduce cost of water treatment, indirectly reduce product cost, and the DM fusing point that this preparation method obtains is high, yield is high, product particle is large, is convenient to filtration, drying, packaging and transport.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
M-Na salts solution of the present invention can be general common M-Na salts solution, also following methods can be adopted to be prepared: the MBT being 170 ° of C by 50 grams of fusing points joins and is equipped with 80 grams, mass percent is in the beaker of the NaOH solution of 20%, be heated to 70-75 ° of C, MBT is dissolved and is prepared into M-Na salts solution, the endpoint pH of this M-Na salts solution remains on 12.
First embodiment
1) be that the M-Na salts solution of 25% and the catalyst A of 10kg join in reactor by the mass percentage of 500kg, wherein, described catalyst A is by PtO
2and RhO
2composition, PtO
2with RhO
2mass ratio at 1:1,
2) by mass concentration be 15% hydrogen peroxide and mass concentration be that the mixing solutions of the sulfuric acid of 20% is added drop-wise in reactor with the flow velocity of 30ml/min, stir under being the condition of 500 revs/min at 50 ° of C, rotating speed,
3) react after 30 minutes, sample and measure its pH value, when pH value is 4, stopped reaction, suction filtration, washing, filtration, dry must rubber accelerator DM product.
The yield of altax prepared by the present embodiment reaches 95.5%, and product bulk density reaches 0.35g/ml, fusing point 169 DEG C, and oarse-grained goods are that follow-up packaging separation provides great convenience.
Second embodiment
1) be that the M-Na salts solution of 40% and the catalyst A of 7kg join in reactor by the mass percentage of 500kg, wherein, described catalyst A is by PtO
2and RhO
2composition, PtO
2with RhO
2mass ratio at 1:0.1,
2) by mass concentration be 5% hydrogen peroxide and mass concentration be that the mixing solutions of the sulfuric acid of 1% is added drop-wise in reactor with the flow velocity of 15ml/min, stir under being the condition of 100 revs/min at 100 ° of C, rotating speed,
3) react after 100 minutes, sample and measure its pH value, when pH value is 6, stopped reaction, suction filtration, washing, filtration, dry must rubber accelerator DM product.
The yield of altax prepared by the present embodiment reaches 96.2%, and product bulk density reaches 0.34g/ml, fusing point 170.6 DEG C, and oarse-grained goods are that follow-up packaging separation provides great convenience.
3rd embodiment
1) be that the M-Na salts solution of 10% and the catalyst A of 0.1kg join in reactor by the mass percentage of 500kg, wherein, described catalyst A is by PtO
2and RhO
2composition, PtO
2with RhO
2mass ratio at 1:30,
2) by mass concentration be 2% hydrogen peroxide and mass concentration be that the mixing solutions of the sulfuric acid of 15% is added drop-wise in reactor with the flow velocity of 10ml/min, stir under being the condition of 500 revs/min at 20 ° of C, rotating speed,
3) react after 10 minutes, sample and measure its pH value, when pH value is 7, stopped reaction, suction filtration, washing, filtration, dry must rubber accelerator DM product.
The yield of altax prepared by the present embodiment reaches 95.5%, and product bulk density reaches 0.36g/ml, fusing point 169.2 DEG C, and oarse-grained goods are that follow-up packaging separation provides great convenience.
4th embodiment
1) be that the M-Na salts solution of 50% and the catalyst A of 5kg join in reactor by the mass percentage of 500kg, wherein, described catalyst A is by PtO
2and RhO
2composition, PtO
2with RhO
2mass ratio at 1:50,
2) by mass concentration be 20% hydrogen peroxide and mass concentration be that the mixing solutions of the sulfuric acid of 10% is added drop-wise in reactor with the flow velocity of 25ml/min, stir under being the condition of 300 revs/min at 100 ° of C, rotating speed,
3) react after 80 minutes, sample and measure its pH value, when pH value is 8, stopped reaction, suction filtration, washing, filtration, dry must rubber accelerator DM product.
The yield of altax prepared by the present embodiment reaches 95.8%, and product bulk density reaches 0.34g/ml, fusing point 169.9 DEG C, and oarse-grained goods are that follow-up packaging separation provides great convenience.
5th embodiment
1) be that the M-Na salts solution of 30% and the catalyst A of 2kg join in reactor by the mass percentage of 500kg, wherein, described catalyst A is by PtO
2and RhO
2composition, PtO
2with RhO
2mass ratio at 1:99,
2) by mass concentration be 10% hydrogen peroxide and mass concentration be that the mixing solutions of the sulfuric acid of 80% is added drop-wise in reactor with the flow velocity of 20ml/min, stir under being the condition of 400 revs/min at 70 ° of C, rotating speed,
3) react after 20 minutes, sample and measure its pH value, when pH value is 8, stopped reaction, suction filtration, washing, filtration, dry must rubber accelerator DM product.
The yield of altax prepared by the present embodiment reaches 95.9%, and product bulk density reaches 0.38g/ml, fusing point 168.9 DEG C, and oarse-grained goods are that follow-up packaging separation provides great convenience.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (3)
1. a preparation method for rubber vulcanization accelerator DM, is characterized in that, comprises following process:
1) be that the M-Na salts solution of 10-50% and the catalyst A of 0.1-10 mass fraction join in reactor by the mass percentage of 500 mass fractions, wherein, described catalyst A is by PtO
2and RhO
2composition, PtO
2with RhO
2mass ratio at 1:0.1-99,
2) mixing solutions of to be the hydrogen peroxide of 2-20% and mass concentration by mass concentration the be sulfuric acid of 1-20% is added drop-wise in reactor with the flow velocity of 10-30ml/min, stirs under the condition of 20-100 DEG C,
3) sample and measure its pH value, when pH value is 4.0-8.0, stopped reaction, suction filtration, washing, filtration, dry rubber accelerator DM product.
2. the preparation method of rubber vulcanization accelerator DM as claimed in claim 1, it is characterized in that, described M-Na salts solution preparation method is: the MBT being 170 DEG C by 50 grams of fusing points joins and is equipped with 80 grams, mass percent is in the beaker of the NaOH solution of 20%, be heated to 70-75 DEG C, MBT is dissolved and is prepared into M-Na salts solution, the endpoint pH of this M-Na salts solution remains on 12.
3. the preparation method of rubber vulcanization accelerator DM as claimed in claim 1, it is characterized in that, in described step 2, mixing speed is 10-500 rev/min, starts sampling and measuring after stirring 10-100min.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739570B (en) * | 2014-01-09 | 2015-11-11 | 山东尚舜化工有限公司 | The preparation method of rubber accelerator dibenzothiazyl disulfide |
| CN108341790B (en) * | 2018-01-08 | 2021-12-17 | 浙江鸿浩科技有限公司 | Method for photocatalytic organic synthesis of promoter |
| CN110523414B (en) * | 2018-05-25 | 2020-11-10 | 中国科学院大连化学物理研究所 | Preparation method of supported catalyst and application of supported catalyst in synthesis of rubber accelerator CBS |
| CN110523410B (en) * | 2018-05-25 | 2020-12-01 | 中国科学院大连化学物理研究所 | Preparation method of supported catalyst and application of supported catalyst in synthesis of rubber accelerator DM |
| CN115286593B (en) * | 2022-08-24 | 2024-01-12 | 鹤壁中昊新材料科技有限公司 | Preparation method of dibenzothiazyl disulfide serving as rubber vulcanization accelerator |
| CN115716811B (en) * | 2022-09-26 | 2024-05-28 | 河北翰成生物科技有限公司 | Method for preparing pharmaceutical grade DM by one step by using industrial grade accelerator M |
| CN117720480B (en) * | 2023-12-20 | 2024-06-18 | 平乡县丰业橡胶助剂有限公司 | High-purity rubber vulcanization accelerator DM and preparation method thereof |
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