CN101676274A

CN101676274A - Method for preparing N-tertiary butyl benzothiazole sulfonamide

Info

Publication number: CN101676274A
Application number: CN200810156072A
Authority: CN
Inventors: 付春; 刘伊文; 陶建青; 张云刚
Original assignee: Research Institute of Nanjing Chemical Industry Group Co Ltd
Current assignee: Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
Priority date: 2008-09-19
Filing date: 2008-09-19
Publication date: 2010-03-24
Anticipated expiration: 2028-09-19
Also published as: CN101676274B

Abstract

The invention relates to a method for preparing N-tertiary butyl benzothiazole sulfonamide, belonging to the field of fine chemical engineering. In the method, 2-thiol group benzothiazole crude product and tert-butylamine are used as raw materials, with the existence of surfactant, sodium hypochlorite is taken as oxidant for oxidation reaction, after completing the reaction proper amount of antioxidant is added, and excessive unreacted sodium hypochlorite is removed, thus stability of the product in the drying process is improved. The invention dispenses with consumption of sulphuric acid andsodium hydroxide, therefore waste water amount is small, product yield can be over 95%, consumption of main raw materials is low, thus the invention is suitable for industrial production.

Description

A kind of preparation method of N-tertiary butyl benzo thiazolesulfenamide

Technical field

It is the method that oxygenant prepares N-tertiary butyl benzo thiazolesulfenamide that the present invention is specifically related to a kind of hypochlorous sodium.

Background technology

N tert butyl benzothiazole 2 sulfenamide (hereinafter to be referred as accelerator NS) is one of important kind of sulfenamide vulcanization accelerator, have anti-incipient scorch and vulcanization rate fast two big advantages concurrently, be used for natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, polyisoprene rubber, be particularly useful for the higher furnace treated black sizing material of alkalescence, variable color and pollution are slight, alternative contain secondary amine the possible NOBS of carinogenicity (N morpholinyl benzothiaolesulfenamide) arranged, the NOBS that Germany uses tire industry in law-making stipulation in 1994 is replaced with CBS (CZ) or NS.The turnout of at present external NS and consumption account for thiazoles sulfuration 40% of chemical total amount.In recent years, along with China's radial development, the demand of accelerator NS is also presented the trend of quick length.

The synthetic method of NS mainly contains hypochlorite oxidation method, catalytic oxidation, electrolytic oxidation, chlorine oxidation process etc. at present, wherein the hypochlorite oxidation method has raw material and is easy to get, equipment requirements is not high, product yield height, advantage such as technology is simple and extensively being adopted by institute both at home and abroad.This method is to carry out condensation with 2-benzothiazolyl mercaptan (hereinafter to be referred as M) and TERTIARY BUTYL AMINE in the presence of the oxygenant clorox to generate NS.DE3021419 proposes in the 2 one butyl cellosolve solvents of moisture 10%-30% (weight ratio), add M, be warmed up to 20-50 ℃ then, add TERTIARY BUTYL AMINE, under 25-60 ℃, carry out oxidation with clorox again, be cooled to 5-15 ℃ of crystallization, suction filtration oven dry then, can obtain the NS of purity 99.7%, yield reaches 92%.DE3440801 proposes 160mL water, and the sulfuric acid of the sodium salt of 378g 50%M and 292g TERTIARY BUTYL AMINE and 588g 20% mixes stirring, is warming up to 60 ℃, adds 472mL15% clorox stirring reaction 30min again, obtains 202gNS, 109 ℃ of product fusing points, purity 99%.Domestic CN1069489 etc. change the sodium salt of raw material M into M, and suitably add tensio-active agent and then can obtain the product of average yield more than 93%, and fusing point is 105 ℃.The above method is to produce the main method that is adopted at present both at home and abroad.Its principal feature is a technical maturity, and condition relaxes, and quality product is better, and yield is higher.Shortcoming is to bring separated from solvent, problems such as recovery, owing in reaction, used sulfuric acid after reaction is finished, to neutralize to reclaim excessive TERTIARY BUTYL AMINE with sodium hydroxide, increased product cost, use sulfuric acid, the anticorrosion of equipment had higher requirement, produce relatively large trade effluent simultaneously, unfavorable to environment.Because the consumption of clorox is excessive in reaction, is not easy flush away, in the residual clorox decomposes of subsequent drying operation, discharge tart hydrochloric acid, NS is decomposed, easily cause the methyl alcohol insolubles of finished product NS not reach index request, cause the outward appearance of product to present redness simultaneously.

Summary of the invention

The present invention is directed to the shortcoming of above-mentioned synthetic method, propose the synthesis technique of a kind of NS, can effectively solve the problem that existing synthetic method exists, product yield is stabilized in more than 95%, fusing point reaches 105 ℃.The methyl alcohol insolubles meets national standard.

The present invention is a raw material with 2-benzothiazolyl mercaptan and TERTIARY BUTYL AMINE, in the presence of suitable tensio-active agent, hypochlorous sodium is the synthetic NS of oxygenant, do not need to add sulfuric acid and sodium hydroxide in the process of reaction, the reductive agent consumption that is added is very little, 0.01-0.05% for the 2-benzothiazolyl mercaptan weight that adds can not cause big influence to environment, specifically:

Under the agitation condition water, tensio-active agent are added in the reactor successively, dissolve fully until tensio-active agent; The 2-benzothiazolyl mercaptan in room temperature, is added in the above-mentioned solution that obtains under stirring in batches, add the back and stirred 30-60 minute, obtain a suspension; Under the agitation condition, add TERTIARY BUTYL AMINE continuously at 20-40 ℃, the mol ratio of 2-benzothiazolyl mercaptan and TERTIARY BUTYL AMINE is 1: 1.5-1.8, the control interpolation time is 15-60 minute, be preferably 30-40 minute, add and continue after the TERTIARY BUTYL AMINE to stir 1-2 hour, then the oxygenant clorox is added continuously in the reactor in 35-45 ℃ of scope at 20-40 ℃, the interpolation time was controlled at 1-4 hour, was preferably 2-3 hour; Added being warmed up to 60-65 ℃ behind the clorox and continuing to keep 0.5-2 hour, be preferably 1 hour; Keep and finish, add the sodium sulfite aqueous solution of concentration expressed in percentage by weight 2-10%, stirred 30-60 minute, to remove excessive clorox; Reaction solution is cooled to below 20 ℃, after filtration, washing, dry desired product.

The used tensio-active agent of the present invention is ionic or nonionic surface active agent; Used ionogenic surfactant is for drawing back powder; Used nonionic surface active agent is polyoxyethylene stearylamine or agricultural newborn 600#; The consumption of tensio-active agent is the 0.01%-0.5% of 2-benzothiazolyl mercaptan weight, is preferably 0.1%, and the mol ratio of 2-benzothiazolyl mercaptan and TERTIARY BUTYL AMINE is 1: 1.5-1.8; The mol ratio of 2-benzothiazolyl mercaptan and clorox is 1: 1.2-1.4; Be preferably 1: 1.2-1.25, the concentration of clorox is 10-13%; The concentration of sodium sulfite solution is 2-10%, is preferably 5%, and consumption is the 0.01-0.05% of 2-benzothiazolyl mercaptan weight.

According to the synthetic NS of processing condition of the present invention, product appearance is a white powder, and product yield is stabilized in more than 95%, and fusing point reaches 105 ℃, and the methyl alcohol insolubles meets national standard.

Embodiment:

Example 1

Having agitator, thermometer, add 80 milliliters of entry in the 250ml four-hole boiling flask of reflux exchanger, the newborn 600#0.1 gram of nonionogenic tenside farming is opened stirring, at room temperature adds 17g (0.1mol) gram captax in batches, add and stir half hour, add 12 gram (0.15mol) TERTIARY BUTYL AMINE then, add temperature and be controlled at 30-35 ℃, added time 20-30 minute, kept 2 hours at 30-35 ℃ after adding TERTIARY BUTYL AMINE, keep and finish,, added 60 milliliters of 10% clorox in 1-4 hour at 35-40 ℃, added and be warmed up to 60-65 ℃ behind the clorox and continued to keep 1 hour, 2 milliliters of the sodium sulfite solutions of adding 5% cool to 15-20 ℃ under stirring, and filter, with 40 ml waters washing four times, for the first time washing water merge distillation with mother liquor and reclaim TERTIARY BUTYL AMINE, and last wash water overlaps the dilution water that is used as next batch with 50 ℃ hot water, filter, 50 ℃ of dryings, sampling analysis is weighed, get 23 gram finished products, 105.4 ℃ of fusing points, NS yield 96.6%, methyl alcohol insolubles 0.3%.

Embodiment 2

Operational condition is with embodiment 1, but the use ionogenic surfactant replaces agricultural newborn 600# for drawing back powder 0.1 gram, gets 23.2 gram finished products, 105 ℃ of fusing points, NS productive rate 97.5%.Methyl alcohol insolubles 0.52%.

Embodiment 3

Operational condition replaces agricultural newborn 600# with embodiment 1 but use polyoxyethylene stearylamine 0.1 to restrain, and gets 23.1 gram finished products, 105.1 ℃ of fusing points, NS productive rate 97%, methyl alcohol insolubles 0.3%.

Embodiment 4

Operational condition is with embodiment 1, but replaces S-WAT with sodium sulphite, 23.2 gram finished products, 105 ℃ of fusing points, NS productive rate 97.5%, methyl alcohol insolubles 0.6%.

Embodiment 5

Operational condition is with embodiment 1, but the mol ratio of captax and TERTIARY BUTYL AMINE was increased to 1: 1.8 by 1: 1.5, gets 23 gram finished products, 106 ℃ of fusing points, NS productive rate 96.6%, methyl alcohol insolubles 0.28%.

Embodiment 6

Operational condition is with embodiment 1, but the mol ratio of captax and clorox was increased to 1: 1.4 by 1: 1.25, gets 23.2 gram finished products, 105 ℃ of fusing points, NS productive rate 97.5%, methyl alcohol insolubles 0.68%.

Comparative Examples

Operational condition is with embodiment 1, but do not use S-WAT, 23.2 gram finished products, 103.4 ℃ of fusing points, NS productive rate 97.5%, methyl alcohol insolubles 1.2%.

Claims

1. the preparation method of a N-tertiary butyl benzo thiazolesulfenamide is a raw material with 2-benzothiazolyl mercaptan and TERTIARY BUTYL AMINE, and in the presence of tensio-active agent, hypochlorous sodium is an oxygenant, it is characterized in that carrying out as follows:

1) under the agitation condition water, tensio-active agent are added in the reactor successively, dissolve fully until tensio-active agent;

2) with the 2-benzothiazolyl mercaptan in room temperature, stir down and add in the above-mentioned solution that obtains, add the back and stirred 30-60 minute, obtain a suspension;

3) under the agitation condition, add TERTIARY BUTYL AMINE, the mol ratio of 2-benzothiazolyl mercaptan and TERTIARY BUTYL AMINE is 1: 1.5-1.8, and the control interpolation time is 30-40 minute, adds 20-40 ℃ of temperature, continues 20-40 ℃ of stirring 0.5-2 hour after adding TERTIARY BUTYL AMINE;

4) under the agitation condition, the oxygenant clorox is added continuously in the reactor in 35-45 ℃ of scope, the interpolation time was controlled at 1-4 hour;

5) added and be warmed up to 60-65 ℃ behind the clorox and continued to keep 1-2 hour;

6) keep and finish, add 2-10% sulfite at concentration lower solution, stirred 30-60 minute, to remove excessive clorox;

7) reaction solution is cooled to below 20 ℃, after filtration, washing, dry desired product.

2. preparation method according to claim 1 is characterized in that used tensio-active agent is ionic or nonionic surface active agent.

3. preparation method according to claim 1 and 2 is characterized in that used ionogenic surfactant is for drawing back powder.

4. preparation method according to claim 1 and 2 is characterized in that, used nonionic surface active agent is polyoxyethylene stearylamine or agricultural newborn 600#.

5. preparation method according to claim 1 is characterized in that, the consumption of tensio-active agent is the 0.01%-0.5% of 2-benzothiazolyl mercaptan weight.

6. according to the preparation method of claim 1, it is characterized in that the mol ratio of 2-benzothiazolyl mercaptan and clorox is 1: 1.2-1.4.

7. preparation method according to claim 6 is characterized in that, the mol ratio of 2-benzothiazolyl mercaptan and clorox is 1: 1.2-1.25.

8. according to claim 1 or 6 described preparation methods, it is characterized in that the weight concentration of aqueous sodium hypochlorite solution is 10-13%.

9. according to the described preparation method of claim 1, the concentration that it is characterized in that sodium sulfite aqueous solution is 5%, and consumption is the 0.01-0.05% of 2-benzothiazolyl mercaptan weight.