CN1069489A - A kind of reparation technology of thiofide - Google Patents
A kind of reparation technology of thiofide Download PDFInfo
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- CN1069489A CN1069489A CN 92109852 CN92109852A CN1069489A CN 1069489 A CN1069489 A CN 1069489A CN 92109852 CN92109852 CN 92109852 CN 92109852 A CN92109852 A CN 92109852A CN 1069489 A CN1069489 A CN 1069489A
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- CN
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- Prior art keywords
- reactor
- sulfenamide
- tert butyl
- tertiary butyl
- easy
- Prior art date
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- 238000005516 engineering process Methods 0.000 title abstract description 6
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 title description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 16
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 8
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 4
- -1 polyoxyethylene cetyl ether Polymers 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007775 late Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 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
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The novel process of the synthetic N tert butyl benzothiazole 2 sulfenamide of a kind of single stage method, characteristics are at promoting agent mixing in reactor with benzothiazolyl mercaptan and an amount of water and nonionic table, TERTIARY BUTYL AMINE being mixed the back slowly adds in the reactor with acidic aqueous solution under stirring at room again, heating up afterwards 40-90 ℃ slowly adds oxygenant again, treats fully promptly to make product after the reaction.It is easy that the present invention has technology, is easy to control, reduce cost, and the one-step synthesis steady quality, having improved conversion of raw material has yield.
Description
The invention belongs to the thiofide technical field, specifically the preparation method of N tert butyl benzothiazole 2 sulfenamide.
Rubber vulcanization accelerator N-tertiary butyl-2-[4-morpholinodithio sulphenamide, its trade name are N, S, and BBS or TBS, molecular formula: C11H14N2S2 is one of current vulcanization accelerator with the fastest developing speed.Along with elastomeric development and in a large amount of utilizations aspect the tire, particularly the complete processing of rubber develops towards the direction of high temperature and high speed in recent years, the phenomenon that scorching takes place in the course of processing sizing material is more outstanding, and N tert butyl benzothiazole 2 sulfenamide promptly is to eliminate the effective additive of this disadvantage.This additive is the sulfenamide type accelerators of late effect property, it can not have the promotor effect at the low thermophase of sulfuration beginning, and by the time just decompose rapidly during high temperature, generate sulfurio benzo thiazole and amine compound, thiazole performance under the basic amine activation promotes usefulness greatly, sulfuration is finished very soon, therefore produced the effect of slow effect high speed.It is to have the highest processing safety in all kinds of promotor at present, can make cross-linked rubber produce higher degree of crosslinking, so make cross-linked rubber have high intensity, possess in the Rubber processing process: time of scorch is long, process safety does not have the phenomenon of reverting, and improves the advantages such as rerum natura of cross-linked rubber.
At present, the method that is used for the synthetic N-tertiary butyl-2-[4-morpholinodithio time sulfanilamide (SN) industrial mainly be to be the aqueous phase oxidation method of condensing of solvent with water, adopt clorox to make oxygenant, earlier benzothiazolyl mercaptan is made sodium salt solution with sodium hydroxide solution, make N tert butyl benzothiazole 2 sulfenamide with the TERTIARY BUTYL AMINE oxidative condensation again.This processing method is synthetic in two steps, complex process, and restive, feed stock conversion (in benzothiazolyl mercaptan 80%) is low, so this height of final product ground.
The novel process that the purpose of this invention is to provide the synthetic N tert butyl benzothiazole 2 sulfenamide of a kind of single stage method direct oxidation method of condensing.
The object of the present invention is achieved like this, this reparation technology is: with the benzothiazolyl mercaptan of raw material 170-200g and an amount of water and 0.2-1.5g nonionogenic tenside uniform mixing in reactor, 70-100g TERTIARY BUTYL AMINE and 5-10%(is heavy) the mixed solution of sulfuric acid 100ml under agitation slowly add in the above-mentioned reactor in 10-40 ℃, be warming up to 40-90 ℃ of 14-20% clorox 500-650g then as oxygenant, postcooling to the room temperature that finishes was filtered in question response 1-2 hour, be washed to neutrality, get filtration cakes torrefaction and promptly make the product N tert butyl benzothiazole 2 sulfenamide.Above-mentioned nonionogenic tenside is meant fatty alcohol-polyoxyethylene ether.
Reaction equation of the present invention is:
Characteristics of the present invention are:
1, adopting water interpolation nonionogenic tenside to make benzothiazolyl mercaptan and TERTIARY BUTYL AMINE is advanced with the novel process of chlorine bleach liquor's oxidative condensation directly.
2, technology is easy, is easy to control, reduces cost.
3, in the devulcanization of rubber course of processing, be specially adapted to add in the sizing material of phenolic type antioxidant.
4, one-step synthesis steady quality has improved conversion of raw material and specific absorption.
5, processing unit there is not particular requirement.
6, wastewater flow rate is few, is easy to handle.
Below by specific embodiment the present invention is further described.
Example 1
172 gram benzothiazolyl mercaptans are added an amount of water and 0.4 gram polyoxyethylene cetyl ether to be mixed in reactor and minute makes its mixing, then with 75 gram TERTIARY BUTYL AMINE and 6-7%(weights) sulfuric acid 110ml mix after, its solution in 10-40 ℃ under agitation slowly (about 30 minutes) add in the above-mentioned reactor, be warming up to 45-60 ℃ of more slowly (under agitation) dropping 15-16% clorox 580 grams then, treat that reaction 1-2 advances the back stopped reaction for a short time under this temperature, being cooled to room temperature filters, be washed to neutrality, obtain product 210-225 gram in 50-60 ℃ of oven dry, average yield is more than 93%, quality product is qualified, and its quality product is relatively referring to table 1.
Example 2
(1), in the reactor that reflux exchanger, dropping funnel, thermometer are housed, adds 400ml water and 1.2 gram fatty alcohol-polyoxyethylene ether (as nonionogenic tenside), stirring and evenly mixing under the normal temperature added 185 gram benzothiazolyl mercaptan stir abouts 30 minutes then.
(2), 96 gram TERTIARY BUTYL AMINE mixed the back add in the dropping funnel with 8% sulfuric acid 110ml, dropping was finished in about 35 minutes in 25-40 ℃ of stirring downhill reaction device, was warming up to about 60 ℃.
(3), keep 60 ℃ ± 5 under agitation dripping about 600 grams of 18%NaOCl solution 1.2ml(), advance to drip for a short time 2, constant temperature continues reaction 1.5 hours.
(4), question response postcooling to room temperature filters, and is washed to neutrality, gets filter cake and is drying to obtain the product N-tertiary butyl-2-benzene thiazolesulfenamide in 50-60 ℃, its product volume is with table 1.
Table 1
This technology is ground in all Japanese imperial palace of test event Meng Shan Qingdao
Institute's product is studied carefully by newly developed company of company
Outward appearance buff powder tawny powder white powder pale yellow powder
Molten point ℃＞105 103 105 105
Weight loss on heating % 0.5 0.3 0.17 0.3
Ash content % 0.4 0.3 0.22 0.3
Methyl alcohol insolubles % 3 3-2
20 screen residues trace trace does not have trace
Ask units such as shenyang rubber institute, Shanghai tire plant and Chongqing tire plant to carry out rubber in addition and join the refining contrast, its result proves that time of scorch is long than accelerant C z, and cross-linked rubber 300% tensile modulus is than Cz height, and all other indexs are identical with external product.
Claims (2)
1, a kind of processing method of producing N tert butyl benzothiazole 2 sulfenamide, it is characterized in that: with the benzothiazolyl mercaptan of raw material 170-200g and an amount of water and 0.2-1.5g nonionogenic tenside uniform mixing in reactor, under agitation slowly add in above-mentioned reactor in 10-40 ℃ the mixed solution of sulfuric acid 100ml of 70-100g TERTIARY BUTYL AMINE and 5-10% (weight), be warming up to 40-90 ℃ of 14-20% clorox 500-650g then as oxygenant, postcooling to the room temperature that finishes was filtered in question response 1-2 hour, be washed to neutrality, get filtration cakes torrefaction and promptly make the product N tert butyl benzothiazole 2 sulfenamide.
2, processing method according to claim 1 is characterized in that nonionogenic tenside is meant fatty alcohol-polyoxyethylene ether or polyoxyethylene cetyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109852 CN1069489A (en) | 1992-08-28 | 1992-08-28 | A kind of reparation technology of thiofide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109852 CN1069489A (en) | 1992-08-28 | 1992-08-28 | A kind of reparation technology of thiofide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1069489A true CN1069489A (en) | 1993-03-03 |
Family
ID=4944405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92109852 Pending CN1069489A (en) | 1992-08-28 | 1992-08-28 | A kind of reparation technology of thiofide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1069489A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390162C (en) * | 2003-03-11 | 2008-05-28 | 武汉化工学院 | The method for preparing pure 2-dibenzothiazole sulfide from the production of AE-active ester waste residue |
| CN100404518C (en) * | 2005-05-31 | 2008-07-23 | 中国石油天然气集团公司 | A method and device for preparing 2-benzothiazole sulfenamide |
| CN101676273B (en) * | 2008-09-19 | 2011-05-18 | 南化集团研究院 | Method for directly synthesizing accelerant N-tertiary butyl benzothiazole sulfenamide |
| CN101717379B (en) * | 2009-12-09 | 2011-06-01 | 河南省开仑化工有限责任公司 | A kind of production method of rubber vulcanization accelerator CBS |
| CN102936231A (en) * | 2011-10-13 | 2013-02-20 | 陈尔凡 | Synthesis of rubber accelerator NS via plasma one-step oxidation method |
-
1992
- 1992-08-28 CN CN 92109852 patent/CN1069489A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390162C (en) * | 2003-03-11 | 2008-05-28 | 武汉化工学院 | The method for preparing pure 2-dibenzothiazole sulfide from the production of AE-active ester waste residue |
| CN100404518C (en) * | 2005-05-31 | 2008-07-23 | 中国石油天然气集团公司 | A method and device for preparing 2-benzothiazole sulfenamide |
| CN101676273B (en) * | 2008-09-19 | 2011-05-18 | 南化集团研究院 | Method for directly synthesizing accelerant N-tertiary butyl benzothiazole sulfenamide |
| CN101717379B (en) * | 2009-12-09 | 2011-06-01 | 河南省开仑化工有限责任公司 | A kind of production method of rubber vulcanization accelerator CBS |
| CN102936231A (en) * | 2011-10-13 | 2013-02-20 | 陈尔凡 | Synthesis of rubber accelerator NS via plasma one-step oxidation method |
| CN102936231B (en) * | 2011-10-13 | 2015-07-01 | 陈尔凡 | Synthesis of rubber accelerator NS via plasma one-step oxidation method |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |