CN110776478A - Low-temperature continuous synthesis method of rubber vulcanization accelerator NS - Google Patents
Low-temperature continuous synthesis method of rubber vulcanization accelerator NS Download PDFInfo
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- CN110776478A CN110776478A CN201911093657.6A CN201911093657A CN110776478A CN 110776478 A CN110776478 A CN 110776478A CN 201911093657 A CN201911093657 A CN 201911093657A CN 110776478 A CN110776478 A CN 110776478A
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- vulcanization accelerator
- rubber vulcanization
- tert
- reaction
- accelerator
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- 238000013040 rubber vulcanization Methods 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 29
- 239000012452 mother liquor Substances 0.000 claims abstract description 19
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 claims abstract description 15
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005070 sampling Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 230000009967 tasteless effect Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-temperature continuous synthesis method of a rubber vulcanization accelerator NS, which comprises the following steps of 1: adding the rubber vulcanization accelerator M and the rubber vulcanization accelerator DM into a reaction kettle, adding water, stirring, and slowly dropwise adding tert-butylamine within 30 min; step 2: reducing the temperature of the reaction system in the step 1 to minus 10 ℃ to 40 ℃, introducing air or compressed air for 10min to 50min for reaction, and sampling to detect the reaction end point of the product; and step 3: and (3) filtering, washing and drying the product obtained in the step (2) to obtain a finished product of N-tert-butyl-2-benzothiazole sulfonamide, and recycling the mother liquor. The lowest reaction temperature can reach-10 ℃, and the reaction time can reach 40min-80 min. Air/compressed air is used as an oxidant, the production process is safe, and salt-containing wastewater cannot be generated; the by-products contained in the mother liquor are very few, and the mother liquor can be recycled without the treatment of other process steps such as evaporation and the like.
Description
Technical Field
The invention relates to the technical field of rubber vulcanization accelerators, and particularly belongs to a low-temperature continuous synthesis method of a rubber vulcanization accelerator NS.
Background
The rubber vulcanization accelerator NS (or TBBS) is one of important varieties of sulfenamide vulcanization accelerators, has the advantages of scorch resistance and high vulcanization speed, is used for producing rubber products such as natural rubber, styrene-butadiene rubber, isoprene rubber and the like, and has higher activity than the currently used accelerators CBS, NOBS and the like.
The main method for synthesizing the rubber vulcanization accelerator NS is to use an accelerator M as a raw material and oxidize the accelerator M by using an oxidant, wherein the commonly used oxidant comprises sodium hypochlorite, hydrogen peroxide, oxygen and the like. In the synthesis method in the prior art, a plurality of technical problems exist: for example, the quality of products obtained by synthesizing NS by a sodium hypochlorite method is excellent, but the generated salt-containing wastewater is difficult to treat; the NS byproduct synthesized by adopting the hydrogen peroxide method has large amount and is difficult to process, the NS yield of the main product is low, the product purity is poor, and the highest yield is only 90 percent according to the literature report; the accelerator NS synthesized by adopting an oxygen method has good product quality, no salt is contained in the wastewater, but the unreacted oxygen in the system is easy to explode after being mixed with tert-butylamine steam, the process risk is large, the process adopts high-pressure reaction, the equipment manufacturing difficulty is high, and the cost is high.
Disclosure of Invention
The invention provides a low-temperature continuous synthesis method of a rubber vulcanization accelerator NS, which aims to achieve the purposes of good product quality, high yield, low cost, recyclable mother liquor without evaporation and easy industrial production.
A low-temperature continuous synthesis method of a rubber vulcanization accelerator NS is characterized by comprising the following steps:
rubber vulcanization accelerator 2-mercaptobenzothiazole is commonly referred to in the industry as rubber vulcanization accelerator M; 2. 2' -dithiodibenzothiazyl is commonly referred to in the industry as rubber vulcanization accelerator DM;
step 1: adding the rubber vulcanization accelerator M and the rubber vulcanization accelerator DM into a reaction kettle, adding water into the reaction kettle, starting stirring to uniformly mix the materials, maintaining stirring, and slowly dropwise adding tert-butylamine within 30 min; the molar ratio of the addition amount of the accelerator M to the addition amount of the accelerator DM is (0.5-3): 1; the mass ratio of the addition amount of the accelerator M to the addition amount of the tert-butylamine is (0.05-0.5): 1, the mass ratio of the addition amount of the accelerator DM to the addition amount of the tert-butylamine is (0.1-0.5): 1;
step 2: reducing the temperature of the reaction system in the step 1 to minus 10 ℃ to 40 ℃, introducing air or compressed air for 10min to 50min for reaction, sampling after the reaction is finished, detecting the reaction end point of the product, continuously introducing air when the reaction end point is not reached, and sampling again after a period of time to detect the index of the product;
and step 3: filtering, washing and drying the product obtained in the step 2 to obtain a finished product of N-tert-butyl-2-benzothiazole sulfonamide, and recycling mother liquor;
and 4, step 4: and (3) repeating the steps 1-3, and replacing the water added in the step 1 with the mother liquor obtained in the step 3.
Preferably, the air or compressed air in step 2 contains 21% by volume of oxygen, and the amount of oxygen added is 120% of the theoretical amount of oxygen required for generating the promoter NS.
Preferably, the stirring speed in the step 1 is 200-400 r/min.
Preferably, the operation steps of filtering, washing and drying in the step 3 are that the materials reacted in the step 2 are poured into a filter flask with filter paper, and a vacuum pump is used for carrying out suction filtration to obtain mother liquor and a crude product N-tert-butyl-2-benzothiazole sulfonamide; continuously washing and filtering the crude product N-tert-butyl-2-benzothiazole sulfonamide by using clear water until the N-tert-butyl-2-benzothiazole sulfonamide is tasteless; and (3) putting the washed N-tert-butyl-2-benzothiazole sulfonamide into a drying oven, and drying at the set temperature of 70 +/-2 ℃ to obtain the final product of the invention.
The reaction mechanism of the invention is as follows:
equation one: the promoter M reacts with oxygen in the air to synthesize the promoter DM.
Equation two: and (3) reacting the accelerator DM with tert-butylamine in air to synthesize the accelerator NS.
Equation three: and (3) reacting the promoter M with tert-butylamine in air to synthesize the promoter NS.
The recycled mother liquor is filled with water, tert-butylamine, a small amount of rubber vulcanization accelerator M and a small amount of rubber vulcanization accelerator DM, and after the raw materials are continuously added into the mother liquor, the mother liquor plays a role of a solvent in the reaction process, so that the recycling is realized.
The invention has the beneficial effects that:
the invention has simple process operation, easy realization of industrialization, lower reaction temperature, and the lowest reaction temperature of-10 ℃, and achieves the purposes of energy saving and consumption reduction compared with the reaction temperature of 40-90 ℃ in the prior art; the reaction time is shorter, reaches 40-80 min, and is obviously shortened compared with the reaction time of 1-4 hours in the prior art; the obtained product has good quality and high purity which is more than 99 percent; the product yield is high and reaches more than 97 percent.
2. The air/compressed air is used as an oxidant, the production process is safe, salt-containing wastewater cannot be generated, and the problem of difficulty in wastewater treatment is solved.
3. The mother liquor contains few by-products, can be recycled without treatment of other process steps such as evaporation and the like, reduces the consumption of tert-butylamine, and achieves the purpose of continuous production.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1:
step 1: adding 50g of rubber vulcanization accelerator M and 198g of rubber vulcanization accelerator DM into a reaction kettle, adding 1000g of water into the kettle, starting stirring at the rotation speed of 300r/min, slowly dropwise adding 500g of weighed tert-butylamine into the reaction kettle after materials in the kettle are uniformly mixed, wherein the dropwise adding time is 30 min;
step 2: after the dropwise addition, controlling a condensate circulating water switch valve to control the temperature in the reaction kettle to be 5 ℃, starting to slowly introduce 123.1g of air, introducing the air at the speed of 3.18L/min, carrying out oxidation reaction for 30min, sampling to detect whether a product reaches a reaction end point, and testing the purity by using a high performance liquid chromatography, wherein the reaction end point is reached when the purity is more than 96%; the purity is 95.5 percent by high performance liquid chromatography detection, air is continuously introduced, and after 20g, the purity is 97.5 percent by high performance liquid chromatography detection;
and step 3: and (3) filtering, washing and drying the reactant obtained in the step (2) to obtain the NS product and the mother liquor of the rubber vulcanization accelerator. The average purity of the obtained NS product is 99.1 percent, and the average yield is 97.2 percent.
The results of the product testing of example 1 are shown in the following table:
example 2:
step 1: adding 99.4g of rubber vulcanization accelerator M100g and rubber vulcanization accelerator DM into a reaction kettle, adding 1000g of water into the kettle, starting stirring at the rotating speed of 350r/min, slowly dropwise adding 500g of weighed tert-butylamine into the reaction kettle after materials in the kettle are uniformly mixed, wherein the dropwise adding time is 30 min;
step 2: after the dropwise addition, controlling a condensate circulating water switch valve to control the temperature in the reaction kettle to be 10 ℃, starting to slowly introduce 98.84g of air, introducing the air at the speed of 2.19L/min, carrying out oxidation reaction, wherein the reaction time is 35min, and sampling to obtain a sample with the purity of 98.5% by high performance liquid chromatography;
and step 3: and (3) filtering, washing and drying the reactant obtained in the step (2) to obtain the accelerator NS product and the mother liquor. The average purity of the obtained NS product is 99.2 percent, and the average yield is 96.8 percent.
Example 2 the results of the product testing are shown in the following table:
example 3:
step 1: putting rubber vulcanization accelerator M100g and rubber vulcanization accelerator DM 66.27g into a reaction kettle, adding 1000g of mother liquor obtained in the embodiment 2 into the kettle, starting stirring at the rotating speed of 200r/min, slowly dropwise adding 500g of weighed tert-butylamine into the reaction kettle after materials in the kettle are uniformly mixed, wherein the dropwise adding time is 27 min;
step 2: after the dropwise addition, controlling a condensate circulating water switch valve to control the temperature in the reaction kettle to be 8 ℃, starting to slowly introduce 68.68g of air, introducing the air at the rate of 1.83L/min, carrying out oxidation reaction, wherein the reaction time is 40min, and sampling to obtain a sample with the purity of 98.3% by high performance liquid chromatography detection;
and step 3: and (3) filtering, washing and drying the reactant obtained in the step (2) to obtain the accelerator NS product and the mother liquor. The average purity of the obtained NS product is 99.1 percent, and the average yield is 97.3 percent.
The results of the product testing in example 3 are shown in the following table:
example 4
In the embodiment 1-3, the operation steps of filtering, washing and drying are that the materials reacted in the step 2 are poured into a filter flask with filter paper, and a vacuum pump is used for carrying out suction filtration to obtain mother liquor and a crude product N-tert-butyl-2-benzothiazole sulfonamide; continuously washing and filtering the crude product N-tert-butyl-2-benzothiazole sulfonamide by using clear water until the N-tert-butyl-2-benzothiazole sulfonamide is tasteless; and (3) putting the washed N-tert-butyl-2-benzothiazole sulfonamide into a drying oven, and drying at the set temperature of 70 +/-2 ℃ to obtain the final product of the invention.
Claims (4)
1. A low-temperature continuous synthesis method of a rubber vulcanization accelerator NS is characterized by comprising the following steps:
rubber vulcanization accelerator 2-mercaptobenzothiazole is commonly referred to in the industry as rubber vulcanization accelerator M; 2. 2' -dithiodibenzothiazyl is commonly referred to in the industry as rubber vulcanization accelerator DM;
step 1: adding the rubber vulcanization accelerator M and the rubber vulcanization accelerator DM into a reaction kettle, adding water into the reaction kettle, starting stirring to uniformly mix the materials, maintaining stirring, and slowly dropwise adding tert-butylamine within 30 min; the molar ratio of the addition amount of the accelerator M to the addition amount of the accelerator DM is (0.5-3): 1; the mass ratio of the addition amount of the accelerator M to the addition amount of the tert-butylamine is (0.05-0.5): 1, the mass ratio of the addition amount of the accelerator DM to the addition amount of the tert-butylamine is (0.1-0.5): 1;
step 2: reducing the temperature of the reaction system in the step 1 to minus 10 ℃ to 40 ℃, introducing air or compressed air for 10min to 50min for reaction, sampling after the reaction is finished, detecting the reaction end point of the product, continuously introducing air when the reaction end point is not reached, and sampling again after a period of time to detect the index of the product;
and step 3: filtering, washing and drying the product obtained in the step 2 to obtain a finished product of N-tert-butyl-2-benzothiazole sulfonamide, and recycling mother liquor;
and 4, step 4: and (3) repeating the steps 1-3, and replacing the water added in the step 1 with the mother liquor obtained in the step 3.
2. The method for the continuous synthesis of rubber vulcanization accelerator NS according to claim 1, characterized in that in step 2, the air or compressed air contains 21% by volume of oxygen, and the amount of oxygen added is 120% of the theoretical amount of oxygen needed for the production of accelerator NS.
3. The method for continuously synthesizing a rubber vulcanization accelerator NS at a low temperature according to claim 1, characterized in that the stirring speed in step 1 is 200 to 400 rpm.
4. The low-temperature continuous synthesis method of the rubber vulcanization accelerator NS according to claim 1, characterized in that the filtering, water washing and drying steps in step 3 are to pour the reacted material in step 2 into a suction flask with suction filter paper, and to perform suction filtration with a vacuum pump to obtain mother liquor and crude N-tert-butyl-2-benzothiazole sulfonamide; continuously washing and filtering the crude product N-tert-butyl-2-benzothiazole sulfonamide by using clear water until the N-tert-butyl-2-benzothiazole sulfonamide is tasteless; and (3) putting the washed N-tert-butyl-2-benzothiazole sulfonamide into a drying oven, and drying at the set temperature of 70 +/-2 ℃ to obtain the final product of the invention.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911093657.6A CN110776478A (en) | 2019-11-11 | 2019-11-11 | Low-temperature continuous synthesis method of rubber vulcanization accelerator NS |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911093657.6A CN110776478A (en) | 2019-11-11 | 2019-11-11 | Low-temperature continuous synthesis method of rubber vulcanization accelerator NS |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461897A (en) * | 1979-11-23 | 1984-07-24 | Monsanto Europe S.A. | Process for the production of sulfenamides |
| US4670556A (en) * | 1983-07-16 | 1987-06-02 | Akzo Nv | Process for the production of thiazolyl-2-sulphenamides |
| CN101735171A (en) * | 2009-11-16 | 2010-06-16 | 天津市科迈化工有限公司 | Method for synthesizing thiofide NS by oxygen oxidation method |
| CN102936231A (en) * | 2011-10-13 | 2013-02-20 | 陈尔凡 | Synthesis of rubber accelerator NS via plasma one-step oxidation method |
| 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) |
| CN107163002A (en) * | 2017-06-16 | 2017-09-15 | 蔚林新材料科技股份有限公司 | A kind of method that oxygen method prepares rubber vulcanization accelerator DM |
-
2019
- 2019-11-11 CN CN201911093657.6A patent/CN110776478A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461897A (en) * | 1979-11-23 | 1984-07-24 | Monsanto Europe S.A. | Process for the production of sulfenamides |
| US4670556A (en) * | 1983-07-16 | 1987-06-02 | Akzo Nv | Process for the production of thiazolyl-2-sulphenamides |
| CN101735171A (en) * | 2009-11-16 | 2010-06-16 | 天津市科迈化工有限公司 | Method for synthesizing thiofide NS by oxygen oxidation method |
| CN102936231A (en) * | 2011-10-13 | 2013-02-20 | 陈尔凡 | Synthesis of rubber accelerator NS via plasma one-step oxidation method |
| 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) |
| CN107163002A (en) * | 2017-06-16 | 2017-09-15 | 蔚林新材料科技股份有限公司 | A kind of method that oxygen method prepares rubber vulcanization accelerator DM |
Non-Patent Citations (1)
| Title |
|---|
| 卞小豹 等: ""催化氧化法合成促进剂TBBS的工艺研究"", 《广东化工》 * |
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Application publication date: 20200211 |