CN112625003B - N-cyclohexyl-2-benzothiazole sulfenamide and synthesis process thereof - Google Patents
N-cyclohexyl-2-benzothiazole sulfenamide and synthesis process thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000008569 process Effects 0.000 title claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 25
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims abstract description 92
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- 239000011343 solid material Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 6
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 10
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 74
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000004537 pulping Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- 239000010413 mother solution Substances 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 tires Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 241001085205 Prenanthella exigua Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical synthesis, in particular to N-cyclohexyl-2-benzothiazole sulfenamide and a synthesis process thereof. The synthesis process comprises the following steps: mixing a dispersant, water, a first portion of cyclohexylamine and DM coarse material to form a slurry; and mixing the slurry with a second part of cyclohexylamine, mixing the mixture with hydrogen peroxide for oxidation reaction, and then reacting the reaction liquid formed by the oxidation reaction with alkali. The process can fully and uniformly mix DM and cyclohexylamine, is favorable for reaction, generates little waste water, and greatly reduces the post-treatment difficulty of CBS.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to N-cyclohexyl-2-benzothiazole sulfenamide and a synthesis process thereof.
Background
Rubber vulcanization accelerator CBS (chemical name: N-cyclohexyl-2-benzothiazole sulfenamide, molecular formula: C) 13 H 16 N 2 S 2 Also called accelerator CZ), is a commonly used and active post-effectiveness accelerator, and has the structural formula:
the accelerator CBS has the advantages of high vulcanization speed, short vulcanization time, no scorch hazard at the operation temperature and safe processing, for example; the vulcanization temperature is above 138 ℃, the promotion effect is extremely strong, the color change is slight, and no frosting is generated. CBS is often used as a secondary accelerator in combination with accelerator TMTD, accelerator DPG or other alkaline accelerators. Alkaline accelerators such as thiurams or dithiocarbamates enhance their activity. The method is mainly used for manufacturing industrial rubber products such as tires, rubber tubes, rubber belts, rubber shoes, cables and the like.
Therefore, CBS has a wide application range and a large market demand, and at present, the most industrial methods for synthesizing CBS are as follows: is prepared by oxidizing M serving as a raw material and sodium hypochlorite serving as an oxidant. The process route for synthesizing CBS by using DM as the raw material is only used by a few enterprises such as Japanese Dain New material science and technology Co., ltd. The method is completed by two steps of oxidization with DM and cyclohexylamine as raw materials and hydrogen peroxide and sodium hypochlorite as oxidizing agents, the yield is about 93-97%, and the fluctuation among batches is large. Sodium hypochlorite is used as an oxidant, and a large amount of waste water containing waste salt NaCl is generated by reaction, so that the waste water is extremely difficult to treat; in addition, cl ions have corrosion risk to equipment in the processes of mother liquor distillation and recycling, and the method has higher requirements on purity, appearance and the like of the raw materials DM and cyclohexylamine, and the produced products have low melting point and large batch-to-batch difference. The material consumption and the energy consumption and the production cost are indirectly improved; meanwhile, a large amount of salt-containing wastewater is still generated by using sodium hypochlorite, so that the cyclohexylamine is difficult to distill and recover, and the recovery rate is low; mother liquor post-treatment and difficulties.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide N-cyclohexyl-2-benzothiazole sulfonamide and a synthesis process thereof. The process can fully ensure that DM (dimethylaminoethyl methacrylate) and cyclohexylamine are uniformly mixed, thereby being beneficial to the reaction, and the process generates little waste water, thereby greatly reducing the post-treatment difficulty of CBS.
The invention is realized in the following way:
in a first aspect, the present invention provides a process for the synthesis of N-cyclohexyl-2-benzothiazole sulfenamide, comprising: mixing a dispersant, water, a first portion of cyclohexylamine and DM coarse material to form a slurry; and mixing the slurry with a second part of cyclohexylamine, mixing the mixture with hydrogen peroxide for oxidation reaction, and then reacting the reaction liquid formed by the oxidation reaction with alkali.
In an alternative embodiment, the molar ratio of said first portion of cyclohexylamine to DM in said DM crude is from 1 to 1.25:1; the mass ratio of water to DM in the DM coarse material is 2-4.5:1, and the temperature for forming slurry is 25-35 ℃.
In an alternative embodiment, the DM coarse material has a purity of 70-96%, a melting point of 155-171 ℃, and a gray scale of 0.3-1.5%;
preferably, the cyclohexylamine has an organic impurity content of less than 2%, preferably from 0.2 to 2%.
In an alternative embodiment, the dispersant is at least one of tween, alkyl sulfonate and stearate;
preferably, the dispersing agent is at least one of tween-20, tween-80, sodium stearate and sodium dodecyl benzene sulfonate;
preferably, the dispersant is added in an amount of 0.05 to 0.1% by mass of the DM coarse fodder.
In an alternative embodiment, the molar ratio of said second portion of cyclohexylamine to DM in said DM crude is from 1 to 1.25:1;
preferably, the second portion of cyclohexylamine is slowly added to the slurry.
In an alternative embodiment, the molar ratio of hydrogen peroxide to DM in the DM coarse material is 0.7-1.1:1;
preferably, the concentration of the hydrogen peroxide is 10-30%;
preferably, the hydrogen peroxide is added in a dropwise manner;
preferably, the temperature of the oxidation reaction is 45-55 ℃, and the hydrogen peroxide dropwise adding time is 1.5-6.0h.
In an alternative embodiment, the molar ratio of the base to DM in the DM coarse stock is from 0.2:1 to 1.4:1;
preferably, the alkali is added in a manner of alkali liquor;
preferably, the concentration of the lye is 5-32%;
preferably, the reaction with the base is carried out at a temperature of 20-45 ℃.
In an alternative embodiment, the determination of the end point of the reaction by adding a base is as follows: performing a methanol insolubles test on the solid;
preferably, 5g of the reaction product is taken and fully dissolved in methanol at 70+/-2 ℃, the residue is filtered out, dried and weighed, and the reaction is considered to be finished when the content of the residual solid is not more than 0.5% of the total mass, otherwise, the reaction is continued.
In an alternative embodiment, the step of the synthesis process further comprises: after the reaction with alkali is finished, dehydrating the materials in the reaction system to form solid materials and mother liquor;
then washing, drying and granulating the solid material;
meanwhile, distilling the mother liquor, regulating the pH value, and then carrying out liquid-liquid separation;
preferably, the pH is in the range of 5-10.
In a second aspect, the present invention provides an N-cyclohexyl-2-benzothiazole sulfenamide prepared by the synthetic process of any one of the previous embodiments.
The invention has the following beneficial effects: according to the embodiment of the invention, the cyclohexylamine is added in batches, and the dispersing agent is adopted, so that DM coarse material is fully dispersed in the cyclohexylamine, the reaction can be fully carried out even if the oxidant hydrogen peroxide is adopted, and the yield of CBS is further ensured. In the embodiment of the invention, only hydrogen peroxide is used as a catalyst, and hypochlorous acid or sodium hypochlorite and the like are not used as an oxidant, so that the formation of salt-containing wastewater is reduced. Meanwhile, the embodiment of the invention enables the alkali liquor to react with the DM raw material remained in the reaction liquid by adding the alkali liquor to form M-Na, which is beneficial to separating the DM raw material from the CBS, and can sufficiently elute impurities in the CBS, further reduce the formation of wastewater, and the formed M-Na can be directly used for producing auxiliary varieties such as high purity M, DM or MZ and the like, namely, the embodiment of the invention can further improve the comprehensive utilization rate of resources.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a synthesis process of N-cyclohexyl-2-benzothiazole sulfenamide, which comprises the following steps: the dispersant, water, a first portion of cyclohexylamine, and DM coarse material are mixed to form a slurry, and the slurry is then mixed with a second portion of cyclohexylamine.
Firstly, the cyclohexylamine is added in batches, and DM is insoluble in water, so that floating materials are easy to form when the DM is directly added into water, and uniform dispersion of materials is not facilitated. The added part of cyclohexylamine can play a role of a surfactant, so that DM can be fully dispersed in the reaction liquid; if all cyclohexylamine is added at one time, DM is easy to gather, and direct precipitation is not favorable for the reaction to be fully carried out. Therefore, a part of cyclohexylamine needs to be added first, so that materials are convenient to disperse, floating materials are not generated, meanwhile, direct agglomeration is avoided, precipitation is avoided, and smooth reaction is affected.
And secondly, the dispersing agent is adopted to further facilitate the dispersion of DM and ensure the uniformity of each substance in the slurry. And the selected dispersing agent does not affect the reaction. Specifically, the dispersant which can be used is at least one of tween, alkyl sulfonate and stearate, more preferably at least one of tween-20, tween-80, sodium stearate and sodium dodecyl benzene sulfonate. And the addition amount of the dispersing agent is 0.05-0.1% of the mass of the DM coarse material. The type of dispersant and the amount of the dispersant are limited, so that the dispersion of DM coarse material is promoted, the formation of uniform slurry is facilitated, and the removal of organic impurities in CBS is facilitated.
Meanwhile, the temperature at which slurry is formed is different from the temperature at which oxidation reaction is performed as described below, and if DM is reacted in a large amount at the time of forming slurry, it may cause poor formation of CBS, which is disadvantageous for subsequent separation, or decrease in yield of CBS.
Specifically, the temperature for forming the slurry is 25-35 ℃, and the molar ratio of the first part of cyclohexylamine to DM in the DM coarse material is 1-1.25:1; the mass ratio of water to DM in the DM coarse material is 2-4.5:1. For example, the temperature may be any value between 25-35℃such as 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ and 35 ℃; the molar ratio may be any number between 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, and 1.25:1, etc. 1-1.25:1; the mass ratio is any value between 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.5:1, 4:1, 4.5:1 and the like and is 2-4.5:1. By adopting the proportion and the conditions, DM and cyclohexylamine can be reduced to react when slurry is formed, and DM in the slurry is well dispersed, so that subsequent reaction is facilitated.
Further, by adopting the embodiment of the invention for synthesis, DM coarse material can be adopted for reaction, and the DM raw material is not required to have higher purity, so that CBS with high yield can be produced even with low purity, and the cost is reduced. Specifically, the purity of DM coarse material is 70-96%, the melting point is 155-171 ℃, and the gray scale is 0.3-1.5%. For example, purity is any number between 70-96% such as 70%, 72%, 74%, 75%, 80%, 85%, 88%, 90%, 92%, 95%, 96%, etc.; the melting point is any value between 155-171 ℃ such as 155 ℃, 158 ℃, 160 ℃, 162 ℃, 165 ℃, 167 ℃, 170 ℃, 171 ℃ and the like; the gray scale is any value between 0.3% and 1.5%, such as 0.3%, 0.5%, 0.7%, 0.8%, 1%, 1.2%, 1.5%, etc.
Further, for cyclohexylamine, an industrial grade raw material may be used, and an aqueous solution of cyclohexylamine recovered by distillation may also be used. The organic impurity content is required to be less than 2%, preferably 0.2 to 2%, for example, 0.2%, 0.5%, 1.0%, 1.3%, 1.5%, 1.7%, 2.0% or the like, and the content may be any value less than 2%.
Further, the molar ratio of the second part of cyclohexylamine to DM in the DM coarse material is 1-1.25:1; for example, any number between 1 and 1.25:1, such as 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, and 1.25:1; and said second portion of cyclohexylamine is slowly added to said slurry. The method is favorable for fully mixing DM and cyclohexylamine, and further favorable for subsequent reactions.
Then, hydrogen peroxide is added, and through the operation, the embodiment of the invention can only adopt hydrogen peroxide as an oxidant, and can fully perform oxidation reaction under the condition of not adopting hypochlorous acid or oxidant such as sodium hypochlorite, so as to ensure the production of CBS. Meanwhile, the formation of chloride salt can be reduced without using hypochlorous acid or oxidant such as sodium hypochlorite, so that the formation of waste water is reduced, and the difficulty of CBS post-treatment is reduced.
Specifically, the molar ratio of hydrogen peroxide to DM in the DM coarse material is 0.7-1.1:1; examples are: any number between 0.7-1.1:1, 0.8:1, 0.9:1, 1:1, 1.1:1, etc. inclusive; the concentration of the hydrogen peroxide is 10-30%; for example, the concentration is any value between 10-30% such as 10%, 15%, 20%, 25% and 30%; adding the hydrogen peroxide in a dropwise manner; the temperature of the oxidation reaction is 45-55 ℃, and the hydrogen peroxide dropwise adding time is 1.5-6.0h. For example, the temperature is any value between 45 and 55℃such as 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃ and 55 ℃, and the time is any value between 1.5 and 6.0 hours such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours and 6 hours. The molar ratio of hydrogen peroxide to DM, the concentration of hydrogen peroxide, the addition mode, the temperature of oxidation reaction and the like are controlled, so that the reaction is promoted, the formation of CBS is facilitated, and the generation of local reaction is avoided.
After the oxidation reaction is finished, the reaction liquid reacts with alkali, and the residual reaction raw materials in the reaction liquid can be converted into M-Na and dissolved in the solution, so that separation of CBS and raw materials is realized, and the recycling of M-Na is facilitated. Meanwhile, the alkali liquor can play a role in removing organic impurities in CBS solids, so that the purity of CBS is improved, the quality of products is improved, the color of the products is brighter and whiter, and the granularity of the products is more uniform.
Specifically, the molar ratio of the alkali to DM in the DM coarse material is 0.2:1-1.4:1, such as 0.2:1, 0.5:1, 0.8:1, 1:1, 1.1:1, 1.3:1, 1.4:1, etc. 0-1.4: any number between 1; the alkali is added in the form of alkali liquor; the concentration of the lye is 5-32%, for example, any value between 5-32% such as 5%, 10%, 15%, 20%, 25%, 28%, 30% and 32%; the reaction temperature with the alkali is 20-45 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and other arbitrary values between 20-45 ℃. The adoption of the conditions is favorable for the reaction of alkali and DM, is favorable for the formation of M-Na, and improves the impurity removal effect. The alkali may be hydroxide such as sodium hydroxide or potassium hydroxide, carbonate or bicarbonate such as sodium carbonate, sodium bicarbonate or potassium carbonate, or ammonia water.
And the reaction end point judgment mode of adding alkali for reaction is as follows: performing a methanol insolubles test on the solid; preferably, 5g of the reaction product is taken and fully dissolved in methanol at 70+/-2 ℃, the residue is filtered out, dried and weighed, and the reaction is considered to be finished when the content of the residual solid is not more than 0.5% of the total mass, otherwise, the reaction is continued. Specific methods can be found in industry standard GB/T21184-2007. Embodiments of the present invention are not described in detail herein.
Further, after the reaction with alkali is finished, the materials of the reaction system are dehydrated to form solid materials and mother liquor, and then the solid materials and the mother liquor are treated respectively. Specifically, washing, drying and granulating the solid material; the required CBS is obtained, and granulation is performed to facilitate subsequent treatment of the CBS.
And (3) distilling the mother liquor, regulating the pH to 5-10, and then carrying out liquid-liquid separation. Specifically, directly distilling mother liquor, then recovering cyclohexylamine, then regulating the pH of the residual mother liquor at the temperature of 50-90 ℃ (for example, at any value between 50 ℃ and 90 ℃ such as 50 ℃, 60 ℃,70 ℃, 80 ℃ and 90 ℃) to gradually gather organic impurities to form a layered solution with colored impurities as an upper layer and colorless clear solution as a lower layer, then carrying out liquid-liquid separation, wherein the lower layer solution is an M-Na solution with higher purity, and the solution can be directly used for producing auxiliary agent varieties such as high purity M, DM or MZ and the like; and the upper organic impurities are waste. The residual DM forms M-Na which can be directly used, so that the comprehensive utilization rate of resources is further improved, and the formation of waste gas is reduced.
The concentration provided by the embodiment of the invention, such as concentration of hydrogen peroxide, concentration of alkali liquor and the like, is expressed as mass concentration.
The embodiment of the invention provides N-cyclohexyl-2-benzothiazole sulfenamide, which is prepared by using the synthesis process of the N-cyclohexyl-2-benzothiazole sulfenamide.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment of the invention provides a synthesis process of N-cyclohexyl-2-benzothiazole sulfenamide, which comprises the following steps:
the purity is 75%, the gray level is 0.82%, DM with the melting point of 116.0 ℃ is DM coarse material, tween-20 is dispersant, and the dosage of the dispersant is 0.2% of the mass of DM. The mass ratio of water to DM was 4:1, and the molar ratio of cyclohexylamine to DM was 3.2:1.
Pulping: mixing water, DM coarse material and 1/2 cyclohexylamine (1.6 times equivalent of DM), adding into a reactor, stirring and pulping, wherein the pulping temperature is 35 ℃, and DM is added for 0.5h; and after pulping, adding the rest cyclohexylamine, and uniformly mixing.
And then heating to 45 ℃, slowly adding hydrogen peroxide into the reactor according to the proportion of 0.85:1 of hydrogen peroxide (concentration is 18%) to DM, carrying out oxidation reaction, adding hydrogen peroxide for 3 hours, and stirring for 25 minutes after adding hydrogen peroxide and alkane.
Sodium hydroxide solution (0.15 times of the molar weight of DM) with the concentration of 20 percent is prepared, and the reaction system is slowly added until the insoluble matters of methanol are sampled and tested, wherein the insoluble matters are less than or equal to 0.1 percent. And filtering and dehydrating to obtain mother liquor and solid materials. The solid material is washed, filtered and dried to obtain the CBS product, the yield is 98 percent, the melting point is 99.5-101.5 ℃, the particle size is uniform, and the color is bright white.
Distilling the mother liquor to recover cyclohexylamine, and then adjusting the pH value at 60 ℃ until color impurities in the mother liquor are layered, wherein the lower layer of the mother liquor is clear and transparent; after phase separation, the lower layer was tested for M-Na concentration (6%), neutralized with sulfuric acid to give off-white M in 100% yield and melting point 175 ℃.
The main sources of the wastewater are two, namely, the upper organic impurities and MZ synthetic mother liquor, wherein the upper organic impurities can be incinerated, the COD of the MZ synthetic mother liquor is about 200, and the purer salt is obtained by directly evaporating.
Example 2
The embodiment of the invention provides a synthesis process of N-cyclohexyl-2-benzothiazole sulfenamide, which comprises the following steps:
the purity is 88 percent, the gray level is 0.69 percent, the DM with the melting point of 169.3 ℃ is DM coarse material, the dispersing agent is a mixture formed by mixing tween-80 and sodium stearate according to the mass ratio of 1:1, and the dosage of the dispersing agent is 0.05 percent of the mass of DM; the mass ratio of water to DM was 3.6:1, and the molar ratio of cyclohexylamine to DM was 3:1.
Pulping: mixing water, DM and 1/3 cyclohexylamine (1 time equivalent of DM), adding into a reactor, stirring and pulping, wherein the pulping temperature is 38 ℃, and DM is added for 0.8h; and after pulping, adding the rest cyclohexylamine and uniformly mixing.
Then heating to 45 ℃; and slowly adding hydrogen peroxide into the reactor according to the proportion of hydrogen peroxide (the concentration is 15%) to DM molar ratio of 1.1:1 for oxidation reaction, wherein the hydrogen peroxide addition time is 4.5h, and stirring for 35min after the hydrogen peroxide addition is finished.
Preparing sodium hydroxide solution with the concentration of 13% (1 time equivalent of the molar weight of DM), slowly dripping into the reaction system until the insoluble matters of the methanol are sampled and tested, wherein the insoluble matters are less than or equal to 0.2 percent. And filtering and dehydrating to obtain mother liquor and solid materials. The solid material is washed, filtered and dried to obtain the CBS product, the yield is 95 percent, the melting point is 100.1-103.2 ℃, the particle size is uniform, and the color is bright white.
Distilling the mother solution to recover cyclohexylamine, and then adjusting the pH value at 90 ℃ until color impurities in the mother solution are layered, wherein the lower layer of the mother solution is clear and transparent; after phase separation, a certain amount of zinc sulfate solution is added into the lower test M-Na concentration (11%) and reacts under certain conditions to obtain the accelerator MZ, the yield is 100%, the zinc content is 20%, the particle size dispersion of the product is 1.1, and the melting point is 200 ℃.
The main sources of the wastewater are two, namely, the upper organic impurities and MZ synthetic mother liquor, wherein the upper organic impurities can be incinerated, the COD of the MZ synthetic mother liquor is about 500, and the purer salt is obtained by directly evaporating.
Comparative example 1: CBS was synthesized with reference to the synthesis process provided in example 1, with the difference that: no dispersant was used, and the results were: in the pulping process, the materials have particles, and DM is not fully dispersed; after the addition of the hydrogen peroxide, the solid color is slightly dark in the stirring process, the CBS yield is 91%, the initial melting point is 97.5 ℃, the appearance is gray powder, and the solid color is slightly dark. The pH of the mother solution is adjusted, and the acid consumption is increased by 15%.
Comparative example 2: CBS was synthesized with reference to the synthesis process provided in example 1, with the difference that: all cyclohexylamine was added directly in one portion, not in portions, with the result that: DM is added and directly embraces the group and deposits in the reactor bottom, along with the gradual addition, through improving stirring speed and the mode of rising the temperature, the system state changes to some extent, but the material dispersion is very inhomogeneous, and the final product yield is only 82%, and has obvious impurity particles, and the product is unqualified.
Comparative example 3: CBS was synthesized with reference to the synthesis process provided in example 1, with the difference that: sodium hydroxide was not used, and the result was: the CBS product has yellow appearance, low initial melting point of 90.2 ℃ and long melting range; the purity of the liquid chromatography test is only 78%, and the liquid chromatography test contains DM components and other organic impurities. Meanwhile, the COD in the mother solution is up to 20000 or more due to the residual M and other components, and the mother solution can not be directly discharged.
Comparative example 4: CBS was synthesized with reference to the synthesis process provided in example 1, with the difference that: the equivalent oxidant is replaced by a mixed oxidant of which half is hydrogen peroxide and the other half is sodium hypochlorite, and the result is that: the reaction yields the product CBS with 97 percent, but the CBS has a slightly yellow appearance, the chlorine ions of about 8 percent are detected in the mother solution, after the pH is regulated, the organic impurities in the mother solution are not thoroughly changed after the pH is regulated, the COD is still about 3000, and the treatment is continued after the COD is reduced.
According to the analysis of the comparative example and the example 1, the invention strengthens the reaction process by regulating the adding mode of cyclohexylamine and using a dispersing agent, and finally, the reaction yield can be obviously improved by alkali treatment, the product quality is improved, the post-treatment is convenient, and the effect is obvious.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. A process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide, which is characterized by comprising the following steps: mixing a dispersant, water, a first portion of cyclohexylamine and DM coarse material to form a slurry; mixing the slurry with a second part of cyclohexylamine, mixing the mixture with hydrogen peroxide to perform an oxidation reaction, and then reacting a reaction solution formed by the oxidation reaction with alkali;
wherein the molar ratio of the first part of cyclohexylamine to DM in the DM coarse material is 1-1.25:1; the mass ratio of water to DM in the DM coarse material is 2-4.5:1; the addition amount of the dispersing agent is 0.05-0.1% of the mass of the DM coarse material; the molar ratio of the second part of cyclohexylamine to DM in the DM coarse material is 1-1.25:1; the molar ratio of the hydrogen peroxide to DM in the DM coarse material is 0.7-1.1:1; the molar ratio of the alkali to the DM in the DM coarse material is 0.2:1-1.4:1.
2. The process for the synthesis of N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1, characterized in that the temperature of forming the slurry is 25-35 ℃.
3. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1 or 2, wherein the purity of the DM coarse material is 70-96%, the melting point is 155-171 ℃, and the gray scale is 0.3-1.5%.
4. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1 or 2, characterized in that,
the organic impurity content of the cyclohexylamine is less than 2%.
5. Process for the synthesis of N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1 or 2, characterized in that the organic impurity content of the cyclohexylamine is 0.2-2%.
6. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1, wherein said dispersant is at least one of tween, alkyl sulfonate and stearate.
7. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1, wherein said dispersant is at least one of tween-20, tween-80, sodium stearate and sodium dodecyl benzene sulfonate.
8. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1, wherein,
the second portion of cyclohexylamine is slowly added to the slurry.
9. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1, wherein the concentration of the hydrogen peroxide is 10-30%.
10. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1, wherein the hydrogen peroxide is added in a dropwise manner;
the temperature of the oxidation reaction is 45-55 ℃, and the hydrogen peroxide dropwise adding time is 1.5-6.0h.
11. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1, wherein,
the alkali is added in the form of alkali liquor; the reaction temperature with the alkali is 20-45 ℃.
12. The process for the synthesis of N-cyclohexyl-2-benzothiazole sulfenamide according to claim 11, characterized in that the concentration of said lye is 5-32%.
13. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 12, wherein the determination mode of the reaction end point of the reaction by adding alkali is as follows: the solids were tested for methanol insolubles.
14. The process for synthesizing N-cyclohexyl-2-benzothiazole sulfenamide according to claim 13, wherein 5g of the reaction product is fully dissolved in methanol at 70+/-2 ℃, the residue is filtered out, dried and weighed, and the reaction is considered to be finished when the residual solid content is not more than 0.5% of the total mass, otherwise, the reaction is continued.
15. The process for the synthesis of N-cyclohexyl-2-benzothiazole sulfenamide according to claim 1, characterized in that the steps of said synthesis process further comprise: after the reaction with alkali is finished, the materials of the reaction system are dehydrated to form solid materials and mother liquor,
then washing, drying and granulating the solid material;
and simultaneously, distilling the mother liquor, adjusting the pH value, and then carrying out liquid-liquid separation.
16. The process for the synthesis of N-cyclohexyl-2-benzothiazole sulfenamide according to claim 15, characterized in that the pH is in the range of 5-10.
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| US4801707A (en) * | 1984-08-18 | 1989-01-31 | Bayer Aktiengesellschaft | Process for the production of benzothiazole sulphene amides |
| CN1872845A (en) * | 2005-05-31 | 2006-12-06 | 中国石油天然气集团公司 | Method and equipment for preparing 2 - benzothiazole sulphenamide |
| CN101081840A (en) * | 2007-07-05 | 2007-12-05 | 濮阳市蔚林化工有限公司 | Production method of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide |
| CN106316981A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method of N-cyclohexyl-2-benzothiazolesulfenamide |
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| US4801707A (en) * | 1984-08-18 | 1989-01-31 | Bayer Aktiengesellschaft | Process for the production of benzothiazole sulphene amides |
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| CN101081840A (en) * | 2007-07-05 | 2007-12-05 | 濮阳市蔚林化工有限公司 | Production method of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide |
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