CN103193732A - Preparation method of rubber vulcanization accelerator DM - Google Patents
Preparation method of rubber vulcanization accelerator DM Download PDFInfo
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- CN103193732A CN103193732A CN2013101479023A CN201310147902A CN103193732A CN 103193732 A CN103193732 A CN 103193732A CN 2013101479023 A CN2013101479023 A CN 2013101479023A CN 201310147902 A CN201310147902 A CN 201310147902A CN 103193732 A CN103193732 A CN 103193732A
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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 the 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 important effect in vulcanization of rubber process, accelerated the reaction of rubber and vulcanizing agent, has improved production efficiency, and DM is indispensable a kind of auxiliary agent in the rubber accelerator industry.Production technique about DM, some reports are also arranged both at home and abroad, mainly be to be raw material with 2-mercaptobenzothiazole (M), use the oxygenant oxidation to obtain, the oxygenant of main usefulness has nitrous acid, oxygen, chlorine, potassium permanganate etc., more than these methods though advantage is respectively arranged, but produce a large amount of byproducts, environment is exerted a certain influence, brought very big pressure for the water treatment engineering, processing condition are wayward, complicated operation.
Document (Speciality Petrochemicals progress, 2006,7 (9): 35) reported with hydrogen peroxide oxidation M, prepared DM with Virahol as carrier, Virahol can follow bad the use, though this processing method has adopted the environment-friendly type oxygenant, environmental pollution has reduced pressure, has increased the mother liquor separation circuit, the very big energy of needs of mother liquor distillation, improved production cost, complex process, not easy to operate.
Patent (200710016805.5,2007-7-9) reported that M is with the dissolving of ammoniacal liquor or liquefied ammonia after, obtaining ammonium salt solution filters, adding catalyzer aerating oxygen or air reaction regular hour under certain temperature and pressure obtains the DM product, this processing method complicated operation, ammonium salt solution needs to filter, and whole arts demand has catalyzer, ammonia-nitrogen content height in the waste water.
Patent (200810183218.X, 2008-12-16) reported under 55～65 ℃, mixture with hydrogen peroxide and sulfuric acid is oxygenant, direct oxidation 2-mercaptobenzothiazole sodium salt, pH are stabilized at 6.5～7.5 o'clock, and reaction finishes, carry out solid-liquid separation under about 30 ℃ of the temperature of control, obtain product DM, this processing method is simple to operate, pollute for a short time, but weak point is arranged also, oxygenant is easy to decompose, oxidizing temperature is low, and material viscosity height is not easy to solid-liquid separation, reaction must cool to about 30 ℃ after finishing, just separable, prolonged reaction time, cause energy dissipation in the temperature-fall period.And the product bulk density of above-mentioned each patent preparation is little, and product particle is little, is unfavorable for dry separation, packing.
Summary of the invention
The objective of the invention is at the technological deficiency that exists in the prior art, and a kind of preparation method that can effectively improve the rubber vulcanization accelerator dibenzothiazyl disulfide (DM) of product particle is provided.
For realizing that the technical scheme that purpose of the present invention adopts is:
A kind of preparation method of rubber vulcanization accelerator DM comprises following process:
1) the quality percentage composition with 500 mass fractions is that the M-Na salts solution of 10-50% and the catalyst A of 0.1-10 mass fraction join in the reactor, and wherein, described catalyst A is by PtO
2And RhO
2Form PtO
2With RhO
2Mass ratio at 1:0.1-99,
2) be that the hydrogen peroxide of 2-20% and mixing solutions that mass concentration is the sulfuric acid of 1-20% are added drop-wise in the reactor with mass concentration, under the condition of 20-100 ° of C, stir,
3) take a 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.
Utilize water carrier to substitute organic solvent and react, by adding little amount of catalyst, improve 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 more strong, then more can improve speed of reaction, and speed of reaction is more fast, and the bulk density of product was just more big when raw material generated product.Adopt the environment-friendly type oxygenant, the yield of altax reaches more than 95%, and the product bulk density reaches more than the 0.3g/ml., make product keep bigger particle, be convenient to follow-up processing, use etc.
Preferably, described M-Na salts solution preparation method is: be that the MBT of 170 ° of C joins and is equipped with in the beaker that 80 grams, mass percent are 20% NaOH solution with 50 gram fusing points, be heated to 70-75 ° of C, make the MBT dissolving be prepared into the M-Na salts solution, the endpoint pH of this M-Na salts solution remains on 12.
The mixing solutions of described hydrogen peroxide and sulfuric acid is added drop-wise in the reactor with the flow velocity of 10-30ml/min.
Mixing speed is 10-500 rev/min in the described step 2, begins sampling and measuring behind the 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 the environment-friendly type oxygenant, effectively avoided environmental pollution, reduce cost of water treatment, reduced product cost indirectly, and this preparation method the DM fusing point height, the yield height that obtain, product particle is big, is convenient to filtration, drying, packing and transportation.
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 explaining the present invention, and be not used in restriction the present invention.
M-Na salts solution of the present invention can be general common M-Na salts solution, also can adopt following method to be prepared: to be that the MBT of 170 ° of C joins and is equipped with in the beaker that 80 grams, mass percent are 20% NaOH solution with 50 gram fusing points, be heated to 70-75 ° of C, make the MBT dissolving be prepared into the M-Na salts solution, the endpoint pH of this M-Na salts solution remains on 12.
First embodiment
1) be that 25% M-Na salts solution and the catalyst A of 10kg join in the reactor with the quality percentage composition of 500kg, wherein, described catalyst A is by PtO
2And RhO
2Form PtO
2With RhO
2Mass ratio at 1:1,
2) being that 15% hydrogen peroxide and mass concentration are that the mixing solutions of 20% sulfuric acid is added drop-wise in the reactor with the flow velocity of 30ml/min with mass concentration, is to stir under 500 rev/mins the condition at 50 ° of C, rotating speed,
3) reaction was taken a sample and is measured its pH value after 30 minutes, when pH value is 4, and stopped reaction, suction filtration, washing, filtration, dry rubber accelerator DM product.
The yield of the altax of present embodiment preparation reaches 95.5%, and the product bulk density reaches 0.35g/ml, and 169 ℃ of fusing points, oarse-grained goods separate for follow-up packing provides very big facility.
Second embodiment
1) be that 40% M-Na salts solution and the catalyst A of 7kg join in the reactor with the quality percentage composition of 500kg, wherein, described catalyst A is by PtO
2And RhO
2Form PtO
2With RhO
2Mass ratio at 1:0.1,
2) being that 5% hydrogen peroxide and mass concentration are that the mixing solutions of 1% sulfuric acid is added drop-wise in the reactor with the flow velocity of 15ml/min with mass concentration, is to stir under 100 rev/mins the condition at 100 ° of C, rotating speed,
3) reaction was taken a sample and is measured its pH value after 100 minutes, when pH value is 6, and stopped reaction, suction filtration, washing, filtration, dry rubber accelerator DM product.
The yield of the altax of present embodiment preparation reaches 96.2%, and the product bulk density reaches 0.34g/ml, and 170.6 ℃ of fusing points, oarse-grained goods separate for follow-up packing provides very big facility.
The 3rd embodiment
1) be that 10% M-Na salts solution and the catalyst A of 0.1kg join in the reactor with the quality percentage composition of 500kg, wherein, described catalyst A is by PtO
2And RhO
2Form PtO
2With RhO
2Mass ratio at 1:30,
2) being that 2% hydrogen peroxide and mass concentration are that the mixing solutions of 15% sulfuric acid is added drop-wise in the reactor with the flow velocity of 10ml/min with mass concentration, is to stir under 500 rev/mins the condition at 20 ° of C, rotating speed,
3) reaction was taken a sample and is measured its pH value after 10 minutes, when pH value is 7, and stopped reaction, suction filtration, washing, filtration, dry rubber accelerator DM product.
The yield of the altax of present embodiment preparation reaches 95.5%, and the product bulk density reaches 0.36g/ml, and 169.2 ℃ of fusing points, oarse-grained goods separate for follow-up packing provides very big facility.
The 4th embodiment
1) be that 50% M-Na salts solution and the catalyst A of 5kg join in the reactor with the quality percentage composition of 500kg, wherein, described catalyst A is by PtO
2And RhO
2Form PtO
2With RhO
2Mass ratio at 1:50,
2) being that 20% hydrogen peroxide and mass concentration are that the mixing solutions of 10% sulfuric acid is added drop-wise in the reactor with the flow velocity of 25ml/min with mass concentration, is to stir under 300 rev/mins the condition at 100 ° of C, rotating speed,
3) reaction was taken a sample and is measured its pH value after 80 minutes, when pH value is 8, and stopped reaction, suction filtration, washing, filtration, dry rubber accelerator DM product.
The yield of the altax of present embodiment preparation reaches 95.8%, and the product bulk density reaches 0.34g/ml, and 169.9 ℃ of fusing points, oarse-grained goods separate for follow-up packing provides very big facility.
The 5th embodiment
1) be that 30% M-Na salts solution and the catalyst A of 2kg join in the reactor with the quality percentage composition of 500kg, wherein, described catalyst A is by PtO
2And RhO
2Form PtO
2With RhO
2Mass ratio at 1:99,
2) being that 10% hydrogen peroxide and mass concentration are that the mixing solutions of 80% sulfuric acid is added drop-wise in the reactor with the flow velocity of 20ml/min with mass concentration, is to stir under 400 rev/mins the condition at 70 ° of C, rotating speed,
3) reaction was taken a sample and is measured its pH value after 20 minutes, when pH value is 8, and stopped reaction, suction filtration, washing, filtration, dry rubber accelerator DM product.
The yield of the altax of present embodiment preparation reaches 95.9%, and the product bulk density reaches 0.38g/ml, and 168.9 ℃ of fusing points, oarse-grained goods separate for follow-up packing provides very big facility.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (4)
1. the preparation method of a rubber vulcanization accelerator DM is characterized in that, comprises following process:
1) the quality percentage composition with 500 mass fractions is that the M-Na salts solution of 10-50% and the catalyst A of 0.1-10 mass fraction join in the reactor, and wherein, described catalyst A is by PtO
2And RhO
2Form PtO
2With RhO
2Mass ratio at 1:0.1-99,
2) be that the hydrogen peroxide of 2-20% and mixing solutions that mass concentration is the sulfuric acid of 1-20% are added drop-wise in the reactor with mass concentration, under the condition of 20-100 ° of C, stir,
3) take a 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: be that the MBT of 170 ° of C joins and is equipped with in the beaker that 80 grams, mass percent are 20% NaOH solution with 50 gram fusing points, be heated to 70-75 ° of C, make the MBT dissolving be prepared into the 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 or 2 is characterized in that, the mixing solutions of described hydrogen peroxide and sulfuric acid is added drop-wise in the reactor with the flow velocity of 10-30ml/min.
4. the preparation method of rubber vulcanization accelerator DM as claimed in claim 3 is characterized in that, mixing speed is 10-500 rev/min in the described step 2, begins sampling and measuring behind the stirring 10-100min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739570A (en) * | 2014-01-09 | 2014-04-23 | 山东尚舜化工有限公司 | Preparation method of rubber accelerator-dibenzothiazyl disulfide |
| CN108341790A (en) * | 2018-01-08 | 2018-07-31 | 浙江鸿浩科技有限公司 | A kind of method of photocatalysis organic synthesis accelerating agent |
| CN110523414A (en) * | 2018-05-25 | 2019-12-03 | 中国科学院大连化学物理研究所 | A kind of preparation method of supported catalyst and its application in rubber accelerator CBS synthesis |
| CN110523410A (en) * | 2018-05-25 | 2019-12-03 | 中国科学院大连化学物理研究所 | A kind of preparation method of supported catalyst and its application in rubber accelerator DM synthesis |
| CN115286593A (en) * | 2022-08-24 | 2022-11-04 | 鹤壁中昊新材料科技有限公司 | Preparation method of rubber vulcanization accelerator dibenzothiazyl disulfide |
| CN115716811A (en) * | 2022-09-26 | 2023-02-28 | 河北翰成生物科技有限公司 | Method for preparing pharmaceutical DM from industrial promoter M in one step |
| CN117720480A (en) * | 2023-12-20 | 2024-03-19 | 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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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739570A (en) * | 2014-01-09 | 2014-04-23 | 山东尚舜化工有限公司 | Preparation method of rubber accelerator-dibenzothiazyl disulfide |
| 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 |
| CN108341790A (en) * | 2018-01-08 | 2018-07-31 | 浙江鸿浩科技有限公司 | A kind of method of photocatalysis organic synthesis accelerating agent |
| 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 |
| CN110523414A (en) * | 2018-05-25 | 2019-12-03 | 中国科学院大连化学物理研究所 | A kind of preparation method of supported catalyst and its application in rubber accelerator CBS synthesis |
| CN110523410A (en) * | 2018-05-25 | 2019-12-03 | 中国科学院大连化学物理研究所 | A kind of preparation method of supported catalyst and its application in rubber accelerator DM synthesis |
| 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 |
| CN115286593A (en) * | 2022-08-24 | 2022-11-04 | 鹤壁中昊新材料科技有限公司 | Preparation method of rubber vulcanization accelerator dibenzothiazyl disulfide |
| 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 |
| CN115716811A (en) * | 2022-09-26 | 2023-02-28 | 河北翰成生物科技有限公司 | Method for preparing pharmaceutical DM from industrial promoter M in one step |
| CN117720480A (en) * | 2023-12-20 | 2024-03-19 | 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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