KR790000982B1 - Process for the manufacture of s-triazinsulfenimide - Google Patents

Abstract

The sulfenamide (I; R1,R2,R3,R4 = H or C1-4 alkyl, Y = divalent hydrocarbyl, methyleneimino, ureylene group, X = R1R2N, imidothio) are scorch inhibitors for rubber vulcanization. Thus, addition of 6-(diethylamino)-2, 4-s-triazinedisulfenyl chloride (from 43.2g dimercaptan) in 250el phMe dropwise to 5, 5-dimethylhydantoin 53. 8, NaOH 16. 8, and H2O 250el and stirring at 0 - 5≰C for 30 min gave 72. 5g 2 (diethylamino)-4, 6-bis [(5, 5-dimethyl hydantoinyl)thio -s-triazine.

Description

Method for preparing S-triazine sulfenimide

The present invention relates to a process for preparing triazine sulfenimide of the following structural formula (I), which is a novel compound useful for increasing the crosslinking of natural rubber and increasing the ease of its operation.

R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are hydrogen or alkyl of 1-4 carbon atoms,

(여기에서의 R₇및 R₈은 같거나 다른 것으로서, 수소, 1-8개 탄소원자의 알킬, 알릴 또는 페닐이다)을 나타낸다.Equal or different, hydrogen, alkyl of 1-8 carbon atoms, alkylthioalkyl all having 2-8 carbon atoms, CH ₃ -S-, alkyloxyalkyl having all 2-8 carbon atoms, CH ₃ -S- Or phenyl), or

(Where R ₇ and R ₈ are the same or different and represent hydrogen, alkyl of 1-8 carbon atoms, allyl or phenyl).

According to the production method of the present invention, the S-triazine sulfenimide of formula (I) is prepared by reacting sulfen halide of formula (II) with an imide of formula (III).

Hal in the above formulas (II) and (III) represents chlorine or cancellation, and R ₁ , R ₂ , X and Y are as defined in the above formula (I).

The reaction in the above-mentioned production process of the present invention is carried out in a homogeneous phase at a temperature of about 100 ° C. or lower, preferably at a temperature of about 50 ° C. or lower, more preferably in a temperature range of −10 ° C. to 50 ° C. Or at a temperature of about 25 ° C. or less, preferably at a temperature of about 10 ° C. or less, and more preferably in a heterogeneous phase in a temperature range of −10 ° C. to + 10 ° C. However, the reaction can also be carried out in a system of two phases, where one phase is water (when an inorganic alkali compound is used as the acceptor of hydrogen halide) and the other phase is an organic solvent or solvent mixture. do.

Sulfenhalides, in particular sulfelchloride, used in the present invention are known. Sulfenamides of triazines are also known compounds (see British Patent No. 1,201,862).

According to the general process of this invention, the novel triazine sulfenimide is manufactured as follows.

That is, the corresponding mercapto triazine is first reacted with chlorine or a chlorine donor (e.g. sulfuryl chloride) to react the sulfene chloride of triazine with the imide of formula III mentioned above. This condensation reaction is best carried out in the presence of HCl-receptor.

Examples of the imide of dicarboxylic acid of structural formula (III) include imides of the following dicarboxylic acids: succinic acid (succinimide), methyl amber acid, glutaric acid, methyl glutaric acid, Compounds considered to be 4-cyclohexene-1,2-dicarboxylic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid, naphthalic acid and imide, i.e. hydantoin and hydantoin derivatives (e.g. in the 5-position by methyl, ethyl or phenyl); Hydantoin substituted one to two times), isocyanurate and N, N'-dialkyl-diphenyl-isocyanurate.

The sulfene chlorides of triazine can be reacted with imides in homogeneous and heterogeneous phases. When the reaction is carried out in a homogeneous phase, an organic HCl-receptor, preferably a tertiary base such as trimethylamine, triethylamine, tributylamine, N-methylmorpholine and the like can be used in the condensation reaction of the present invention. When performing this reaction in a system consisting of two phases, it is best to use water as one phase and organic solvent as the second phase, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, Potassium carbonate or the like can be added to the organic HCl-receptor and used.

The temperature of this condensation reaction is variable and determined empirically. In general, however, the reaction temperature is governed by the particular reaction process and the type of imide used. When the condensation reaction is carried out in a homogeneous phase, the reaction temperature can be used up to 100 ℃, when the two phases are carried out at a low temperature because the imide ring is ring-opened at a high temperature. As mentioned above, the sulfenchloride of the starting material S-triazine is prepared by reacting the corresponding mercapto triazine with chlorine or chlorine donor in an inert solvent. And methylene chloride, chloroform, carbon tetrachloride, ethane dichloride, ethane trichloride, benzene chloride, dichlorobenzene, trichlorobenzene and the like. The chlorination reaction is best carried out at low temperatures because the yield is reduced when the reaction is carried out at low temperatures.

In this reaction, ditriazinyl disulfide can also be used in place of mercaptotriazine. After completion of the chlorination reaction, excess chlorine must be removed from the sulfenchloride solution, for example by blowing nitrogen gas or other inert gas or partially distilling off the solvent. .

The condensation reaction of the sulfenchloride compound with the imide is advantageously carried out in the same or in the same solvent mixture as the chlorination reaction. However, the sulfenchloride solution is first freed completely from an inert solvent (e.g. using a continuous evaporation or triple triple evaporator), and then the liquid or solid sulfenchloride is replaced by benzene, toluene, dioxane, ether, or other inert organic solvents. Dissolved in to carry out the following reaction.

In most cases, the compounds of formula (I) prepared according to the invention are white or slightly colored crystalline materials, most of which are very stable compounds.

Next, the preparation method of the present invention for preparing the compound of the structural formula (I) will be described in detail as the following examples. However, the following examples do not limit the scope of the invention.

Example 1

2-diethylamino-4,6-bis- (5,5-dimethylhydantoyl thi) -triazine

43.2 g (0.2 mol) of 2-diethylamino-4,6-dimercaptotriazine was suspended in 250 ml of methylene chloride. 64.8 g of sulfuryl chloride was added dropwise while stirring the electric suspension at 0 DEG C, followed by further stirring for 1 hour. The triazine sulfenchloride residue obtained by concentration of the solution under reduced pressure to 12 Torr / 25 占 폚 was in the off-yellow oil state, which was added to 250 ml of toluene. 53.8 g of 5,5-dimethylhydantoin, 250 ml of water and 16.8 g of sodium hydroxide were mixed and cooled to 0 ° C. While stirring this cooled solution, toluene solution of triazine sulfenchloride obtained in the above process was added dropwise at 0-5 占 폚. This reaction was completed after about 30 minutes.

The mixture obtained by suction filtration was washed with water and dried to obtain 72.5 g (equivalent to 78% of theory) of a white crystal having a decomposition melting point of 170 占 폚. Hydantoinyl groups are also referred to briefly as hydantoyl groups.

Example 2

2-diethylamino triazinyl-4,6-bis-thio- (3,5-dimethyl cyanurate)

65.6 g (0.23 mol) of 2-diethylamino-4,6-bis-sulphenyl chloride was dissolved in 150 ml of dioxane. Further, 72 g (0.46 mol) of 3,5-dimethyl isocyanurate was dissolved in 250 ml of diacetamide, and then 48 g of triethylamine was added. To the solution of isocyanurate thus obtained was added dropwise the above sulfenyl chloride solution at 0-5 占 폚. When the reaction is complete, the reaction mixture shows a neutral reaction. This was then poured into 2 liters of water, followed by suction filtration to wash the filter residue. After drying, it was recrystallized as dioxane to give an amount equivalent to 44% of theory, 53.4 g. The obtained product was a white crystal phase with a melting point of 270-272 °.

Example 3

2-diethylamino-4,6-bis-succinimido-thio triazine

43.2 g (0.2 mol) of 2-diethylamino-4,6-dimercapto triazine was suspended in 250 ml of carbon tetrachloride to react with 64.8 sulfuryl chloride at 0-10 ° C. to yield the corresponding selpenchloride. Half of the solvent was then evaporated off.

44 g of succinimide was dissolved in 250 ml of dimethylformamide and then 60 g of triethylamine was added. At a temperature of 0-10 ° C., the carbon tetrachloride solution of sulfen chloride produced in the previous step was added dropwise to the solution, followed by stirring at room temperature for 2 hours. After evaporation and concentration under reduced pressure, 76.5 g of crude product was obtained by drying the filtrate residue obtained by suction filtration after adding the raw document to water. This was recrystallized as a mixture made of dioxane and dimethylformamide in a ratio of 3: 1 to give 57.5 g of a pure substance having a melting point of 239-241 ° C., equivalent to 70.1% of theory.

It can also be manufactured by other methods, such as:

Carbon tetrachloride solution of triazine sulfen chloride is added to a solution of 44 g of succinimide dispersed in an aqueous solution of sodium hydroxide (to which 9 g of sodium hydroxide is added to 300 ml of water) at 0 ° C. By this method, the target product was obtained in a yield of 67.5%.

Example 4

2-dimethylamino-4,6-bis-succinimido-thiotriazine

To a solution of 16 g of chlorine in 250 ml of dichloroethane, 37.6 g (0.2 mol) of 2-dimethylamino-4,6-dimercapto-triazine was added at 0 ° C, stirred for 30 minutes, and then hydrogen chloride was added to the solution. Passed with.

50 g of succinimide was dissolved in a solution in which 20 g of sodium hydroxide was added to 250 ml of water, which was dropped into a round flask equipped with two drops and cooled to 0 ° C. The sulfene chloride solution was added dropwise to the mixture and allowed to stand for 2 hours. The reaction mixture was concentrated by evaporation under reduced pressure, added to water, and the filtrate obtained by suction filtration was washed with water and dried and recrystallized as isopropanol. This gave 57.1 g (74.7% of theory) of the target product of white crystals having a melting point of 258-259 ° C.

Example 5

2-ethylamino-4-diethylamino-6-phthalimido-thiotriazine

59.6 g of 2-ethylamino-4-diethylamino-6-chlorosulphenyl triazine hydrochloride was slowly added to a mixture consisting of 29.4 g of phthalimide, 40 g of triethylamine and 300 ml of dimethylformamide. The temperature of the reaction mixture was not to be 25 ° C or higher. A thick crystalline mass was formed, which was suction filtered after 2 hours. The filtrate was washed with water, dried and recrystallized from a mixture of dimethylformamide and isopropanol in a ratio of 1: 1 to give 51.4 g of the target product having a melting point of 187-188 ° C. as white crystals (69.2% of theory). Obtained.

Example 6

2-diethylamino-4,6-bis-phthalimido-thiotriazine

71.3 g of 2-diethylamino-4,6-bis-chlorosulphenyl triazine were dissolved in 750 ml of dimethylformamide. While cooling the solution of 65.7 g of triethylamine and 72.5 g of phthalimide dispersed in 250 ml of dimethylformamide, the previously prepared triazine solution was added dropwise to maintain the temperature below 45 ° C. After stirring at 45 ° C. for about 1 hour, the mixture was poured into 2 L of water and dried by filtration. Recrystallization as dimethylformamide gave 84.2 g (66.4% of theory) of the target product having a melting point of 256-257 ° C. as a white crystal.

By following a similar method as described in the previous examples, the following compounds were prepared:

2-dimethylamino-4,6-bis- (hydantoylthio) -triazine,

2-ethylamino-4,6- (methylmercaptoethyl hydantoylthio) -triazine,

2-n-butylamino-4,6-bis- (methylhydantoylthio) -triazine,

2-ethylamino-4-diethylamino-6-hydantoylthio triazine,

2,4-bis-diethylamino-6- (5-isopropyl hydantoylthio) -triazine,

2,4-bis-n-butylamino-6- (5-ethylhydantoylthio) -triazine,

2-methylamino-4-n-butylamino-6- (5-n-propylhydantoylthio) -triazine,

2-methylamino-triazinyl- (4,6) -bis-thio-3,5-dimethyl cyanurate,

2-ethylamino-4-diethylamino-triazinyl-6-thio-3,5-diethyl cyanurate,

2-amino-4-diethylamino-triazinyl-6-thio-3,5-dibutyl cyanurate,

2-n-butylamino-triazinyl- (4,6) -bis-thio-3,5-dimethyl cyanurate,

2-dimethylamino-4,6-bis-succinimido-thio-triazine,

2-amino-4,6-bis-succinimido-thio-triazine,

n -butylamino-4,6-bis-succinimido-thio-triazine

2-amino-4-diethylamino-6-succinimido-thio-triazine,

2,4-bis-ethylamino-6-succinimido-thio-triazine,

2-dimethylamino-4,6-bis-glutarimidochitriazine,

2,4-bis-ethylamino-6-phthalimidochitriazine,

2-amino-4-diethylamino-6-phthalimidothiotriazine,

2-ethylamino-4,6-bis-phthalimidochiotriazine,

2- n -butylamino-4,6-bis-phthalimidothiotriazine,

2- n -butylamino-4,6-bis-phthalimidothiotriazine,

2-diethylamino-4,6-bis-tetrahydrophthalimidothiotriazine,

2-methylamino-4-isopropylamino-6-tetrahydrophthalimidothiotriazine,

2-di- n -butylamino-4,6-bis-naphthalimidochitriazine,

2-methylamino-4-ethylamino-6-naphthalimidochitriazine,

2-diethylamino-4- n -butylamino-6-hexahydrophthalimidothiotriazine,

2,4-bis-dimethylamino-6-hexahydroportimidochiotriazine,

2,4-bis- n -propylamino-6-phthalimido-thio- s -triazine,

2-di- n -propylamino-4-diethylamino-6-succinimido-thio- s -triazine,

2,4-bis-i-propylamino-6-methylsuccinimido-thio- s -triazine,

2,4-bis-i-butylamino-6-glutaramide-thio-triazine,

2-ethylamino-4-diethylamino-6- [5- (2-methyl-thio-ethyl) -hydantoyl-thio] -s -triazine,

2,4-bis-i-butylamino-6- (4-cyclohexene-1,2-dicarbonimido-thio) -s -triazine,

2-di- n -butylamino-4,6-bis- [5- (2-methoxyethyl) -hydantoylthio] -s -triazine,

2,4-bis-i-propylamino-6-dimethylglutarimido-thio- s -triazine,

2- n -butylamino-4,6-bis- (5-methylhydantoyl-thio) -s -triazine

The novel compounds prepared according to the above are not only useful as herbicides in the pesticide portion, but also aid in the operation of the rubber mixture and are also useful as intermediates.

In the process of the rubber industry, the novel s -triazine derivatives prepared according to the invention can be used, for example, to increase the stability in the operation of non-emulsifying rubber mixtures. The rubber product is shaped or shaped after operation in the mixer before emulsifying the rubber mixture. Forming a mold always involves exothermic mechanical pressing, such as rolling, extruding, or calendering. If the emulsification is performed during the molding process, the stability of the operation process reaches a limit or exceeds the stability, because it is impossible to form a dimensionally stable plastic. This problem can be solved by using the compound obtained according to the present invention.

The novel s -triazine derivatives according to the invention impart very good physical properties when added to mixtures containing natural or synthetic rubber which are emulsified as sulfur and / or sulfur donors. Such rubber mixtures may include fillers and, for example, reinforced silica, natural or synthetic silicates, oxides and glass fibers or glass fiber products of aluminum, magnesium, calcium, zinc or titanium metals, and mixtures of these fillers. It contains the same thing. If white or light fillers are used in the rubber mixture, it is advisable to use together sulfur-containing silanes according to Belgian Patent No. 787,691.

Synthetic rubbers include, for example, polybutadiene, polyisoprene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, butyl rubber, ethylene terpolymers, propylene and nonconjugated dienes, trans-polypentene armors and rubber industries There are other rubbers used in.

The s -triazine derivatives of the present invention can add 0.1-10 parts to the rubber mixture with respect to 100 parts by weight of rubber, more specifically, 0.2-5 parts by weight with respect to 100 parts by weight of rubber It can contain 0.3-3 weight part.

Emulsification can be carried out with conventional organic rubber vulcanization accelerators, for example mercaptocompounds of benzothiazol or s -triazine, the corresponding disulfides or sulfenamides [e.g. N-cyclohexyl-2-benzothiazole sulfenamide, N -(Tert-butyl) -2-benzothiazol sulfaenead, 2- (morpholinothio) -benzothiazol] and, more particularly, s -triazine sulfenamide according to German Patent Specification 1,669,954. By adding something like this one can promote its emulsification.

The rubber mixture may also contain, for example, antioxidants, heat stabilizers, plasticizers, dyes, pigments, waxes, organic acids (stearic acid, benzoic acid, silicic acid) and other additives such as zinc oxide and activators.

Next, for example, the s -triazine compound according to the present invention is used in the operation process of the rubber mixture, to prove its effectiveness. However, the following test examples do not limit the use of the compounds according to the present invention, and it is noted that the "parts" used are weight ratios.

[Test Example 1]

0.5 part of 2-diethylamino-4,6-bis-hydantoyl-thio-triazine compound was added to a rubber composition having the following composition. 137.5 parts of oiled styrene-butadiene rubber (SBR 1712), 65 parts of ISAF carbon black, 3 parts of zinc oxide, 1 part of stearic acid, 1.5 parts of aromatic plasticizer, 2 parts of antioxidant, 2 parts of sulfur. 1.2 parts N-tert-butyl benzothiazol-2-sulfenamide.

The crosslinking isotherm of the mixture thus obtained was measured at 155 ° C. The results are as follows.

t ₅ : 12.7 min, K ¹ : 357 / min, D∝-D _a : 0.551Nm (※ Nm is Newton meter)

For comparison, the crosslinking isotherms of the same composition without addition of the s -triazine compound were measured at 155 ° C. The measurement results are as follows.

t ₅ : 10.3 min, K ¹ : 328 / min, D∝-D _a : 5.972Nm

t ₅ is displayed, the measurement temperature 155 ℃, so 5% is switched represents the time required for the reaction emulsion. The longer this time, the greater the stability in the operation of the rubber mixture.

In addition, the indication of DD-D _a indicates that the torque of the non-emulsifying mixture is subtracted from the final torque measured while recording the crosslinking isotherm. Thus, this value represents an increase in torque caused by crosslinking of the mixture. After all, this is an expression that reflects the formation of the crosslinking site, and furthermore, it is also a measure of the quality of the emulsion.

It can be seen from the measurement indicated above that the t ₅ value was increased by 23% by adding 0.5 parts by weight of the compound according to the present invention. In other words, it can be seen that the stability of the operation step was significantly increased under the influence of the present compound.

At the same time, it can be seen that D∝-D _a is increased by 10%, which means that the crosslinking is increased by adding the compound according to the present invention.

The surface of K ¹ also points to the rate constant of the emulsification reaction occurring in the first order. Therefore, it is possible to derive an important fact from this value, that is, the s -triazine derivative of the present invention can be seen that slows the start of the emulsification but does not reduce the emulsification body.

Rubber mixture containing 0.5 parts by weight of 2-diethylamino-4,6-bis-hydantoyl-thio-triazine according to the present invention as a rate constant of crosslinking of the rubber mixture without addition of the compound according to the present invention Compared with the rate constant of, the emulsification is actually slightly accelerated.

[Test Example 2]

0.6 parts by weight of the various mixtures according to the present invention were added to the basic composition made as follows, and measured by the method described in use example 1.

Rubber composition

From the measurements shown in the above table, it can be seen that by using the compound according to the present invention, operational stability is increased in the manufacturing process of the rubber mixture. If it is not necessary to increase the formation of crosslinks, it is possible by reducing the amount of sulfur added in the elemental phase. This result means that the emulsion has only a few polyemulsions, and further shows a reduction in reduction.

[Test Example 3]

The materials according to the invention increase the stability of operation even in the processing of natural rubber. In this test, a compound 2-diethylamino-4,6-bis-succinimide-thio-triazine and 2-diethylamino-4,6-bis-hydane according to the present invention in a basic mixture having the composition Cross-linked isothermal was measured at 145 ° C. by adding 0.5 parts of toyl-thio-triazine.

From the table, it can be seen that even when the s -triazine compound according to the present invention is used in natural rubber, it increases stability in the process and increases the formation of crosslinks.

Claims (1)

As described above in the text, a method for preparing s -triazine sulfenimide of the following formula (1), characterized by reacting a sulfenhalide of the formula (II) with an amide of the formula (III).

R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are hydrogen or alkyl of 1-4 carbon atoms; Y is —CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —CH ₂ —, —CH (CH ₃ ) —CH | _2- ,

As the same or different; Hydrogen, alkyl of 1-8 carbon atoms, alkylthioallyl having all 2-8 carbon atoms, CH ₃ -S-, alkyloxyalkyl having all 2-8 carbon atoms, CH ₃ -O- or phenyl), or,

(Where R ₇ and R ₈ are the same or different; hydrogen is alkyl, allyl or phenyl of 1-8 carbon atoms), and Hal represents chlorine or cancellation.