GB2080294A - Method for the Production of N- Cyclohexylbenzothiazole-2- sulfenamide - Google Patents
Method for the Production of N- Cyclohexylbenzothiazole-2- sulfenamide Download PDFInfo
- Publication number
- GB2080294A GB2080294A GB8121021A GB8121021A GB2080294A GB 2080294 A GB2080294 A GB 2080294A GB 8121021 A GB8121021 A GB 8121021A GB 8121021 A GB8121021 A GB 8121021A GB 2080294 A GB2080294 A GB 2080294A
- Authority
- GB
- United Kingdom
- Prior art keywords
- cyclohexylamine
- mercaptobenzothiazole
- sulfenamide
- cyclohexylbenzothiazole
- oxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 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 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 63
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000003946 cyclohexylamines Chemical class 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000004636 vulcanized rubber Substances 0.000 claims 1
- 239000012043 crude product Substances 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 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)
- Thiazole And Isothizaole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for the production of N- cyclohexyl-benzothiazole-2- sulfenamide in which 2- mercaptobenzothiazole reacts with an excess of cyclohexylamine and the resulting cyclohexylamine salt of 2- mercaptobenzothiazole is then oxidized with an oxidant such as sodium hypochlorite at a temperature in the range of 20 to 70 DEG C. 2-mercaptobenzothiazole may be used in the form of the crude product formed by a high-pressure reaction of aniline, carbon disulphide and sulphur. N-cyclohexylbenzothiazole-2- sulfenamide may be employed as an accelerator in the vulcanization of rubber.
Description
SPECIFICATION
Method for the Production of N-cyclohexylbenzothiazole-2-sulfenamide This invention relates to a method for the production of N-cyclohexylbenzothiazole-2sulfenamide by a reaction of 2-mercaptobenzothiazole, cyclohexylamine and oxidant. Ncyclohexylbenzothiazole-2-sulfenamide is used as a fast safe accelerator in rubber vulcanization.
N-cyclohexylbenzothiazole-2-sulfenamide is usually produced by the oxidation of the cyclohexylamine salt of 2-mercaptobenzothiazole with a sodium hypochlorite solution or hydrogen peroxide:
The cyclohexylamine salt of 2-mercaptobenzothiazole may be prepared from sodium, calcium or ammonium salts. The 2-mercaptobenzothiazole appears during the refining of the crude melt of 2mercaptobenzothiazole.
The process of preparation from the sodium salt has been described, for instance, in
Czechoslovak Patent Specification No. 114 693, in USA Patent Specifications 2 191 657, 2 268 467, 2 762 814, in German Patent Specifications 855 564 and /DAS/ No. 1 940 364, in British Patent
Specifications 642 597, 665 668,1 106 577; the process involving calcium salt has been described in
Czechoslovak Patent Specification 11 3 006, in Federal Republic of Germany /DAS/ Patent
Specification 1 940 364, and the process from an ammonium salt has been described in Czechoslovak
Authorized Certificate 1 84 052.
The principle of all these processes is the same. To an aqueous solution of the appropriate salt of 2-mercaptobenzothiazole the appropriate quantity of cyclohexylamine is added and the solution or suspension of the cyclohexylamine salt of 2-mercaptobenzothiazole is oxidized with the appropriate oxidant. There are a number of documents that protect the preparation of sulfenamides directly from the amine salt of 2-mercaptobenzothiazole, such as: USA Patent Specifications 2 339 002, 2 772 279, 3 144 652, British Patent Specifications 452 044, 655 668, 106 577, 519 61 7 1 289 407, German Patent Specifications 615 580, 2 056 80, Federal Republic of Germany /DAS/ 2 056 762, French Patent Specifications 852 11 8, 950 693, 1 549 002 and Japanese application's 74110664,7413467.
The above mentioned processes possess considerable shortcomings in many cases. The inorganic aikalies used are transferred in the form of salts into waste liquors; if using the calcium salt of 2-mercaptobenzothiazole polluted calcium sludge is formed and the product must be purified by acid washing to eliminate all insoluble calcium compounds. If the process with ammonium salt is used, the requirements for production equipment increase. The sulfenamides prepared from the sodium and calcium salt of 2-mercaptobenzothiazole usually do not reach the required grades and, therefore, they must be purified /for instance, French Patent Specification 2 056 749, FRG (DAS) No. 1 940 365,
British Patent Specification 756 464, USA Patent Specification 276 281 4/, which results in higher losses and volumes of waste liquors.
It has now been found that a high-grade N-cyclohexylbenzothiazole-2-sulfenamide may be prepared by the reaction of 2-mercaptobenzothiazole, cyclohexylamines and oxidant according to this invention.
Thus, the present invention provides a method for the production of N-cyclohexylbenzothiazole2-sulfenamide by the reaction of 2-mercaptobenzothiazole, cyclohexylamine and oxidant in which 2mercaptobenzothiazole is reacted with an excess of cyclohexylamine and the resulting cyclohexylamine salt of 2-mercaptobenzothiazole is oxidized at a temperature in the range of 20 to 700 C. Preferably, 1.5 to 5 moles and advantageously 2.5 moles of cyclohexylamine are present per 1 mole of 2-mercaptobenzothiazole. Desirably, the oxidant is sodium hypochlorite or hydrogen peroxide and the temperature of oxidation of the order of 450C. The oxidation by-products may be separated by filtration. The 2-mercaptobenzothiazole may enter the reaction as the crude product originating at a high-pressure reaction of aniline, carbon disulphide and sulphur.This product is either free from volatile components (due to treatment with an inert gas) or is used without prior purification.
Production according to the invention gives high yields and purity of the Ncyclohexylbenzothiazole-2-sulfenamide, the process being simplfied to a maximum and the preparation of the cyclohexylamine salt of 2-mercaptobenzothiazole and its oxidation are performed in one stage.
Another advantage of the new process of production consists in a considerable reduction of waste and waste liquors which has great importance with respect to ecology.
The following examples illustrate, but do not restrict the production of Ncyclohexylbenzothiazole-2-sulfenamide according to this invention.
Example 1
Into a 500 ml four-neck flask fitted with a high-speed stirrer, a thermometer, a reflux condenser and a funnel 118.8 g /0.6 moles/ of 50% cyclohexylamine and 34.8 g of 96% commercial grade 2mercaptobenzothiazole (0.2 moles) were added. The charge was heated during stirring to a temperature of 850C and a solution of the cyclohexylamine salt of 2-mercaptobenzothiazol was produced; this product was cooled to 450C. Over a period of 60 minutes 110 ml of sodium hypochlorite (16.7 g Cl+/100 ml) were added by means of a separating funnel. The temperature was kept by slight cooling within a range from 42 to 450C. After addition of about three quarters of the volume of sodium hypochlorite a crystalline product precipitated.The reaction was completed and the product was cooled to 200 C. The crystalline product was then separated by filtration, washed with 100 ml of 10% cyclohexylamine, followed by washing with 700 ml of water. The wet cake was dried to a constant weight. The yield was 48.2 g, i.e. 91.2% calculated for N-cyclohexylbenzothiazole-2sulfenamide.
Melting point: 101.5--102"C Sulfenamides: 99.7% by weight
Insoluble residue: 0.14% by weight
Mother liquors and the first portions after washing with water (system of two phases) were pooled and distilled at a normal pressure of 0.1 MPa. Thus, 94.4 g of an aseotropic mixture of cyclohexylamine and water was produced and after addition of fresh cyclohexylamine it was recycled back into the process. The yield of the product calculated for the initial cyclohexylamine represents 94.2% of the theoretical value.
Example 2
The preparation was similar to that in Example 1, but 79.2 g (0,4 moles) of 50% cycfohexylamine was used. 48.6 g of the product was isolated (91.8% by theory) with a melting point of 100 to 1020 C, 98.2% by weight of sulfenamides, 0.25% by weight of insoluble residues.
Example 3
The preparation was similar to that in Example 1, but 200 g (1.0 mole) of 50% cyclohexylamine was used. The yield was 45.1 g of the product (85.3% by theory) with a melting point of 1 020C, 99.9% by weight of sulfenamides and 0.1% by weight of insoluble residues.
Example 4
The preparation was similar to that in Example 1, but the temperature during the addition of the sodium hypochlorite was 300 C. The yield was 47.2 g of the product representing 89.2% and the theoretically calculated value, with a melting point of 99-101 C,98.9% by weight of sulfenamides and 0.9% by weight of insoluble residues.
Example 5
The method of preparation was similar to that in Example 1, but the temperature during the addition of the sodium hypochlorite solution was 700 C. The yield was 42.6 g of product (80.55% by theory), which melts at 101.5-1 020C, 99.5% by weight of sulfenamides and 0.1 5% by weight of insoluble residues.
Example 6
The method of preparation was similar to that in Example 1, but 36.3 g of 92.0% crude product of a high-pressure reaction of aniline, carbon disulphide and sulphur was used. The yield was 48.0 g of the product which represents 90.8% of the theoretical value, with a melting point of 101--1 03.50C.
99.3% by weight of sulfenamides, and 0.14% by weight of insoluble residues.
Example 7
The preparation process was similar to that in Example 1, but 38.8 g of 86.3% crude product of the high-pressure reaction of aniline, carbon disulphide and sulphur was used. The yield was 46.4 g of the product (87.7% by theory), with a melting point of 100--1020C, 98.8% by weight of sulfenamides and 0.15% by weight of insoluble residues.
Example 8
The preparation process was similar to that in Example 1, but 102.5 ml (16.7 g Cl+/1 00 ml) of sodium hypochlorite was used. The yield was 45.3 g which represents 85.7% of the theoretical value, with 99.8% by weight of sulfenamides and 0.17% by weight of insoluble residues. Melting point: 100--1010C.
Example 9
The preparation process was similar to that in Example 1, but 1 84 g of 5% hydrogen peroxide was used in place of sodium hypochiorite as an oxidant. The yield was 46.1 g of the product (87.1% by theory), the melting point being 101--1020C, 99.4% by weight of sulfenamides and 0.13% by weight of insoluble residues.
Example 10
The preparation process was similar to that in Example 6, but 1 84 g of 5% hydrogen peroxide was used for oxidation. The yield was 46.0 g of the product (87.0% by theory), the melting point being 101-1 030C, 99.2% by weight of sulfenamides and 0.10% by weight of insoluble residues.
Example 11
The preparation process was similar to that in Example 7, but 1 84 g of 5% hydrogen peroxide was used for oxidation. The yield was 44.9 g of the product which is 84.9% of the theoretical value, the melting point being 1001O20C, 99.0% by weight of sulfenamides and 0.10% by weight of insoluble residues.
Claims (12)
1. A method for the production of N-cyclohexylbenzothiazole-2-sulfenamide of the following formula:
by the reaction of 2-mercaptobenzothiazole, cyclohexylamine and oxidant in which 2mercaptobenzothiazole reacts with an excess of cyclohexylamine and the resulting cyclohexylamine salt of 2-mercaptobenzothiazole is oxidized at a temperature in the range of 20 to 700 C.
2. A method according to Claim 1 in which 1.5 to 5 moles of cyclohexylamine are present per 1 mole of 2-mercaptobenzothiazole.
3. A method according to Claim 2 in which 2.5 moles of cyclohexylamine are present per 1 mole of 2-mercaptobenzothiazole.
4. A method according to any one of the preceding claims in which the oxidant is sodium hypochlorite.
5. A method according to any one of Claims 1 to 3 in which the oxidant is hydrogen peroxide.
6. A method according to any one of the preceding claims in which the cyclohexylamine salt of 2mercaptobenzothiazole is oxidized at a temperature of the order of 45"C.
7. A method according to any one of the preceding claims in which the oxidation by-products are separated by filtration.
8. A method for the production of N-cyclohexylbenzothiazole-2-sulfenamide of the following formula:
by the reaction of 2-mercaptobenzothiazole, cyclohexylamine and oxidant where the first stage consists in a reaction of 2-merdaptobenzothiazole with an excess of cyclohexylamine in a quantity of 1.5 to 5 moles of cyclohexylamine per 1 mole of 2-mercaptobenzothiazole, the formed solution of the cyclohexylamine salt of 2-mercaptobenzothiazole then being oxidized with sodium hypochlorite or hydrogen peroxide at 20 to 700C and the by-products of the oxidation process separated by filtration.
9. A method according to any one of the preceding claims in which 2-mercaptobenzothiazole is in the form of the crude reaction product of aniline, carbon disulphide and sulphur.
1 0. A method for the production of N-cyclohexylbenzothiazole-2-sulfenamide substantially as hereinbefore described with reference to any one of the Exampies 1 to 11.
11. N-cyclohexylbenzothiazole-2-sulfenamide when produced according to any one of the preceding claims.
12. A method of vulcanizing rubber when employing N-cyclohexylbenzothiazole-2-sulfenamide according to Claim 11 as an accelerator.
1 3. Vulcanized rubber when produced according to Claim 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS804887A CS215179B1 (en) | 1980-07-09 | 1980-07-09 | Method of making the n-cyclohexybenzthiazol-2-sulphenamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2080294A true GB2080294A (en) | 1982-02-03 |
| GB2080294B GB2080294B (en) | 1985-05-09 |
Family
ID=5392615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8121021A Expired GB2080294B (en) | 1980-07-09 | 1981-07-08 | Method for the production of n-cyclohexylbenzothiazole-2-sulfenamide |
Country Status (9)
| Country | Link |
|---|---|
| BE (1) | BE889546A (en) |
| CH (1) | CH648028A5 (en) |
| CS (1) | CS215179B1 (en) |
| DE (1) | DE3127193A1 (en) |
| ES (1) | ES8203868A1 (en) |
| FR (1) | FR2486527A1 (en) |
| GB (1) | GB2080294B (en) |
| IT (1) | IT8122813A0 (en) |
| YU (1) | YU41459B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670556A (en) * | 1983-07-16 | 1987-06-02 | Akzo Nv | Process for the production of thiazolyl-2-sulphenamides |
| EP0314663A1 (en) * | 1987-10-29 | 1989-05-03 | Monsanto Europe S.A./N.V. | Process for the preparation of benzothiazole-2-sulphenamides |
| EP1449837A1 (en) * | 2003-02-20 | 2004-08-25 | Bayer Aktiengesellschaft | Process for the preparation of benzthiazolylsulfenamides by reacting a primary amine with alkali salts of mercaptobenzthiazole in the presence of hydrogene peroxide and alkalimetal hypochlorite |
| CN102863402A (en) * | 2012-09-25 | 2013-01-09 | 科迈化工股份有限公司 | Preparation method of accelerator CBS |
| CN106432135A (en) * | 2016-09-30 | 2017-02-22 | 王显权 | Production method of N-cyclohexyl-2-benzothiazole sulfenamide |
| CN110523332A (en) * | 2019-09-16 | 2019-12-03 | 山东尚舜化工有限公司 | A kind of device and method of continuous production aniline fluid bed |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5436346A (en) * | 1991-12-21 | 1995-07-25 | Akzo Nobel N.V. | Process for the preparation of benzothiazolyl-2-sulphenamides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE615580C (en) * | 1933-04-14 | 1935-07-08 | I G Farbenindustrie Akt Ges | Process for the preparation of sulfenamides of secondary amines |
| FR852118A (en) * | 1938-03-25 | 1940-01-24 | Ici Ltd | Manufacturing process and application of new mercaptobenzthiazol derivatives |
| GB655668A (en) * | 1940-07-26 | 1951-08-01 | Monsanto Chemicals | Improvements in or relating to methods of making sulphenamides |
| BE754504A (en) * | 1969-08-08 | 1971-02-08 | Bayer Ag | PROCESS FOR THE PREPARATION OF BENZOTHIAZYLSULFENAMIDES |
-
1980
- 1980-07-09 CS CS804887A patent/CS215179B1/en unknown
-
1981
- 1981-07-07 CH CH4463/81A patent/CH648028A5/en not_active IP Right Cessation
- 1981-07-08 IT IT8122813A patent/IT8122813A0/en unknown
- 1981-07-08 GB GB8121021A patent/GB2080294B/en not_active Expired
- 1981-07-08 BE BE0/205344A patent/BE889546A/en not_active IP Right Cessation
- 1981-07-08 ES ES503774A patent/ES8203868A1/en not_active Expired
- 1981-07-09 FR FR8113528A patent/FR2486527A1/en active Granted
- 1981-07-09 DE DE19813127193 patent/DE3127193A1/en not_active Ceased
- 1981-07-09 YU YU1694/81A patent/YU41459B/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670556A (en) * | 1983-07-16 | 1987-06-02 | Akzo Nv | Process for the production of thiazolyl-2-sulphenamides |
| EP0314663A1 (en) * | 1987-10-29 | 1989-05-03 | Monsanto Europe S.A./N.V. | Process for the preparation of benzothiazole-2-sulphenamides |
| EP1449837A1 (en) * | 2003-02-20 | 2004-08-25 | Bayer Aktiengesellschaft | Process for the preparation of benzthiazolylsulfenamides by reacting a primary amine with alkali salts of mercaptobenzthiazole in the presence of hydrogene peroxide and alkalimetal hypochlorite |
| CN102863402A (en) * | 2012-09-25 | 2013-01-09 | 科迈化工股份有限公司 | Preparation method of accelerator CBS |
| CN106432135A (en) * | 2016-09-30 | 2017-02-22 | 王显权 | Production method of N-cyclohexyl-2-benzothiazole sulfenamide |
| CN110523332A (en) * | 2019-09-16 | 2019-12-03 | 山东尚舜化工有限公司 | A kind of device and method of continuous production aniline fluid bed |
| CN110523332B (en) * | 2019-09-16 | 2021-07-02 | 山东尚舜化工有限公司 | Equipment and method for continuously producing vulcanization accelerator CBS |
Also Published As
| Publication number | Publication date |
|---|---|
| CH648028A5 (en) | 1985-02-28 |
| BE889546A (en) | 1981-11-03 |
| ES503774A0 (en) | 1982-04-01 |
| FR2486527A1 (en) | 1982-01-15 |
| GB2080294B (en) | 1985-05-09 |
| YU41459B (en) | 1987-06-30 |
| FR2486527B3 (en) | 1983-05-13 |
| ES8203868A1 (en) | 1982-04-01 |
| CS215179B1 (en) | 1982-07-30 |
| DE3127193A1 (en) | 1982-05-19 |
| IT8122813A0 (en) | 1981-07-08 |
| YU169481A (en) | 1983-06-30 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |