JPS5910583A - 2-mercaptobenzothiazole derivative, its preparation and rubber additive containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X is CH2, CO, C(OH)H, C(OR1)H (R1 is 1-18C alkyl), or group of formula II (R2 is 1-17C alkyl)]. EXAMPLE:2-(4-Hydroxy-2,2,6,6-tetramethyl-1-piperidinylthio)benzothiazole. USE:A non-discoloring, non-staining excellent vulcanization accelerator, The vulcanized rubber product prepared therewith has excellent ozone resistance. PROCESS:The compound of formula I can be prepared by reacting the 2,2,6,6- tetramethylpiperidine compound of formula III with 2-mercaptobenzothiazole at a reaction molar ratio of 1:0.8-1.3 at 0-60 deg.C, preferably at 10-30 deg.C. Preferably, the reaction is carried out by dissolving the compound of formula IIIin water in the form of an acid addition salt, and adding an aqueous solution of an alkali metal salt of 2-mercaptobenzothiazole and an aqueous solution of an oxidizing agent simultaneously dropwise to the solution of the compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (1).
The Komelkabutobenzoti7sol derivative represented by the above, its production method, and a non-coloring, non-staining rubber additive with excellent vulcanization accelerating effect and ozone deterioration prevention effect containing natural rubber and its production method as an active ingredient. Various vulcanization accelerators are selected and used for sulfur vulcanization of synthetic rubbers such as styrene-butadiene rubber, nitrile rubber, butadiene rubber, and isoprene rubber, but most of them are N-cyclohexy-benzothi-7-di-λ-sulfene. Sulfenamide derivatives such as 7mido, N-tertiary butylbenzothiazilucose sulfenamide have been used. However, these sulfenamide derivatives have the disadvantage of coloring and staining vulcanized rubber products, making them generally difficult to use for white to brightly colored products.

As a result of various studies, the present inventors found that the compound represented by the above general formula (1) is useful as a new non-coloring and non-staining vulcanization accelerator, and furthermore, vulcanized rubber products made using this compound have excellent resistance. It was discovered that it has ozone properties, and the present invention was completed.

The nomercaptobenzoti7zole derivative represented by the general formula (1) is a novel compound that was first synthesized by the present inventors K and has not been described in any literature.

λ-mercabutobenzothi7 represented by this general formula (1)
The sol derivative is 2,2. A, it can be produced by reacting 6-tetramethylpiperidines and 2-mercaptobenzothiazole.

Here, the substituent R in the above general formulas (1) and (■)
As the alkyl group of 1, methyl, ethyl, propyl,
Examples include butyl, octyl, lauryl, stearyl, etc., and examples of the alkyl group of R2 include methyl, ethyl, butyl, nonyl, undecyl, heptadecyl, etc. 6
．． In 6-tetramethylpiperidines, -X- is -
G-oxo-,2,,2,4,6-tetramethylpiperidine can be obtained by reacting 7sedone and ammonia by a known method. Further, by subjecting the above-mentioned 9-oxo-,2t-2,At6-tetramethylpiperidine to Wolffukischener reduction, 2,,2, where -X- is -12-. By reducing A, A-tetramethylpiperidine with lithium aluminum hydride, hydroxyl-2°, in which -X- is -OH-,
! , /, 4-tetramethylpiperidine can be obtained, respectively.

Furthermore, the above-mentioned Nori-Hydroxy, 2. ．． 2. A.

When 6'-tetramethylpiperidine is reacted with an alkyl halide represented by RlX (R has the same meaning as above or represents a halogen atom), p-X- changes to -0H- due to Rt. gualkoxy,2
,,2,A,4-tetramethylpiperidine,'
R200R3 (R2 has the same meaning as above, and R3 represents a hydroxyl group, a halogen atom, or a lower flukoxyl group).

) and the esterification equivalent of the carboxylic acids represented by the formula, preferably about 1 to 1 g molar equivalent.

, 2. ．． The reaction molar ratio between 2,4.6-tetramethylpiperidines and Komelkabutobenzothiazole is usually /
:θ0. ! r~/. It is 3.

The reaction is usually carried out at a temperature of θ to θ℃, preferably /θ to
3θ°C.

The reaction method is preferably 2. J, A, A-Tetramethylpiperidines are dissolved in water in the form of an acid addition salt, and an aqueous solution of an alkali metal salt of λ-mercaptobenzothiazole and an aqueous solution of an oxidizing agent are simultaneously added dropwise thereto. .

After the reaction is completed, the product can be separated and collected from the reaction mixture using a conventional method, for example, the reaction mixture is filtered, the first filtrate is dried, and then recrystallized with an appropriate solvent to obtain a high-purity target product. can be obtained.

Typical compounds thus obtained as the 2-mercaptobenzothiazole derivatives of the present invention are exemplified below.

Such mercaptobenzothiazole derivatives not only exhibit excellent effects as vulcanization accelerators, but also vulcanized rubber products using them exhibit excellent ozone resistance, making them excellent as rubber additives. It has a good effect.

2-Mercaptobenzothiazole derivatives as additives for rubber include not only natural rubber but also styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polybutadiene, polyisoprene, polychloroprene, ethylene-propylene copolymer rubber, etc. It is added to various synthetic rubbers, and the amount added is usually 9.3 to 7 parts by weight per 14,700 parts by weight. The method for adding it to rubber is the same as when using ordinary vulcanization accelerators and ozone deterioration inhibitors.

In addition, other vulcanization accelerators,
Antiozonants and other additives may be used in combination.

The present invention will be explained below with reference to Examples.

Example/Goo Hydroxy, 2,6. A-Tetramethylpiperidine j,/y (θ, θ! mol)/θ Bibin thihydrochloric acid aqueous solution/3. /f? (0,036 mol).

to this! - To the sodium salt of mercaptobenzothiazole was added an aqueous solution of f (0.03 mol) dissolved in 30 d of water and a 70% by weight aqueous sodium hypochlorite solution, 24./P (θ, OSS mol). The temperature inside the flask at this time was 20°C. After cooling, the resulting solid was separated and washed with water, and then heated to 50°C.
for 7.2 hours to obtain 5.61 (yield, r7) of white crystalline 2-<y-hydroxy-2,,2,6,1,-tetramethyl-/-piperidinylthio)benzothiazole.
%) get f. mp/j, 2~/J3°C The parent ion peak in the mass spectrum was J, 2.2.

Elemental analysis value 0(@1((91) NC'l)
1%) Example cog-oxo-,2,,2,A,A-tetramethylpiperidine! , / f (θ, θ 33 moles) was used, but the same raw materials and the same amounts as in Example/ were used and reacted in the same manner,
A similar post-treatment is performed to obtain white crystalline 2-(4t-oxoco,2,6.4-tetramethyl-7-piperidinylthio)penzothiazolta, θti<yield 93%).

mp /gu3～/gugu℃ Parent ion peak of mass spectrum: 3.2θ elemental analysis value C(%n H(%)N(phantom) The same raw materials and the same amounts as in Example 1 were used, except that piperidine j, JP (θ, θυ mol) was used, and the amount of /θ wt% hydrochloric acid aqueous solution was 7.2.07 (0,033 mol). The reaction was carried out in the same manner as above, and the post-treatment was carried out in the same manner to obtain white crystalline 2-(coumethoxy-11, co-methoxy).

6. In 6-titramethyl-/-piperidinylthio)benzothiazole, 1 (yield ts) is obtained.mp 1
30-131℃ Parent ion peak of mass spectrum: 33A elemental analysis value
0(@H(→N(@S(@Example Dacou octadecyloxy, 2..2.A, 4-tetramethylpiperidine/3./fcθ, 032 mol) and 70% by weight aqueous hydrochloric acid solution. Set the usage amount to /2.Of<0.
The same raw materials as in Example 1 were used in the same amounts, except that 033 mol) was used, and the reaction was carried out in the same manner as in Example 1.
-Titramethyl-/-piperidinylthio)benzothiazole/J, θfI (yield, r7'%) is obtained. mp
/7/~/7.2℃ Mass spectrum parent ion beak: 17</Elemental analysis value C(hook H(4)' N(chi) B(→Note)
4-ethoxy, 4-propoxy or 4-butoxy
, 2, co, 6,6-titramethylpiveridine as a raw material and reacted in the same manner as in Example/1 to obtain the corresponding 11-mercabutobenzothiazole derivatives.

Example J The same raw materials and the same amounts as in Example 1 were used, except that 7.0P (0,035 mol) of goomethylcarboxy-λ,λ,4,4-tetramethylpiperidine was used, and the reaction was carried out in the same manner.
A similar post-treatment is performed to obtain white crystalline 2-(gumethylcarboxyco,2,4.A-tetramethyl-/-piperidinylthio)benzothiazole θ1 (yield 73%). mp/guar~/4t℃ mass spectrum parent ion peak: 36 elemental analysis value 0(%9a(7)N(
(6) S (To) Example 6 Coundecylcarboxy 2.1. A.

6-tetramethylpiperidine/2. ,2iV(θ, θ
The same raw materials and the same amounts as in Example 1 were used, except that 36 mol) was used, and the reaction was carried out in the same manner as in Example 1. ,
Omp /za3 to obtain A-tetramethyl-/-piperidinylthio)benzothiazole/co,/1 (yield g0%)
～/g℃Parent ion peak of mass spectrum: soy
Elemental analysis value: 0 (@H(4)) N(@S(@Example 7) A rubber compound was prepared by mixing ingredients having the following compounding ratios using an oven roll according to a conventional method.

Stearic acid - Zinc white S Soft calcium carbonate 7j Process oil /θ Wax
3 I O
! , j Test sample Table J The obtained rubber compound was subjected to Mooney scorch trial sales in accordance with JIEJ K-A3θθ, and rheometer vulcanization tests were conducted to examine the vulcanization rate.

In addition, press vulcanization was performed for 6θ minutes at a vulcanization temperature/gθ℃, and J
The hue and physical properties of the vulcanized rubber and ozone deterioration tests were conducted in accordance with ISK-1s307.

In addition, the ozone deterioration test measures the ozone concentration in an ozone weather meter! Oppm, temperature θ℃, dynamic elongation rate -
The time required for rack to become visible to the naked eye was measured at 〇chi. The results are shown in Table 1.

Example i A rubber compound was prepared by mixing compounding ingredients having the following proportions using an oven roll according to a conventional method.

Stearic acid 3 Zinc 5HAF
Black SO Process oil S Wax 3 I O
Test sample Table 3: The obtained rubber compound was subjected to the Mooney scorch test and the rheometer test in the same manner as in the example. Also, the vulcanization temperature [/II! Press vulcanization was performed at r°C for 40 minutes, and the physical performance of the vulcanized rubber and ozone deterioration tests were conducted.90 The results are shown in Table 3.

Procedural amendment (voluntarily filed on February 73, 1920, Mr. Kazuo Wakasugi, Director General of the RR Office, 1966, Patent Application No. //9'l, No. 7, 2, Title of the Invention, 1 - Mercaptobenzothiazole Derivatives) , its manufacturing method, and its relationship with the case of a person who made a rubber additive 3, supplementary 1F containing the same as an active ingredient Patent applicant address Kita @ 5-chome, Higashi-ku, Osaka City Name of exposed land (209
') Hijikata, Representative of Sumitomo Chemical Industries, Ltd.
4. Column 6 of detailed description of the invention in the agent's specification, contents of amendment (1) Insert page 7 of the attached sheet between page 6 and page 3 of the specification.

The above-mentioned 1-furkylcarboxy J, l, A, 6-titramethylbiperidine can be obtained, respectively. A, The reaction between 6-tetramethylpiperidines and 1-mercaptobenzothiazole is usually carried out in the presence of an oxidizing agent. On this occasion,
The piperidines are used in the form of acid addition salts such as hydrochloric acid, sulfuric acid and p-toluenesulfonic acid, while -monomercabutopenzothiazole is used in the form of alkali metal salts such as sodium and potassium.

In this reaction, compounds used in general oxidation reactions are used as the oxidizing agent, and suitable examples include hydrogen peroxide, sodium hypochlorite, and iodine.

Claims (1)

[Claims] (1) In the general formula R, 1R2 represents a C1-17 furkyl group. ) Komelkabutobenzothiazole derivatives. (P2) In the general formula R group, R2 represents an alkyl group of 01 to 1□. ) indicated by 1, 2. A,/;-Tetramethylpiperidines and Komelkabutobenzothiazole are reacted, and the Komelkabutobenzothiazole salt is represented by the general formula (wherein -X- has the same meaning as above). Method of manufacturing conductors. (3) Represents a general formula group. ) A rubber additive containing a λ-mercaptobenzothiazole derivative as an active ingredient.