DD263298A5 - Use of substituted N-trichloromethylthiohydantoins in combination with bis (2,4-diamino-s-triazin-6-yl) -oligosulfides in vulcanizable rubber mixtures and rubber mixtures of this type - Google Patents

Abstract

The invention relates to the use of substituted N-trichloromethylthiohydantoins in combination with bis (2,4-diamino-s-triazin-6-yl) -oligosulfides in vulcanizable rubber mixtures and to improve the vulcanization characteristics and such rubber mixtures.

Description

Field of application of the invention

The invention relates to the use of substituted N-Trichlormethylthiohydantoinen in combination with bis (2,4-diamino-s-triazin-6-yl) -oligosulfiden in vulcanizable rubber blends as Vulkanisationsverzögerer with a crosslinking density-increasing effect and such rubber blends.

Characteristic of the known state of the art

For the crosslinking of elastomers with sulfur, the vulcanization itself is completely insufficient, a number of vulcanization accelerators are available, which - already added in a small amount - both increase the chemically reachable crosslinking density and improve the kinetics of crosslinking so much in that the vulcanisation process can also be carried out ratiorjell on a production scale.

Although crosslinking of rubber compounds is also feasible without free sulfur, for example by means of peroxides or thiurams, the invention relates to accelerated sulfur vulcanization and crosslinking with Ν, Ν'-substituted bis (2,4-diamino-s-triazine -6-yl) -ol1gosulfiden according to formula (II).

The latter without free sulfur with tetrasulfides (n = 4) and mixtures of oligosulfides whose mean chain length corresponds to S ₄ (also η = 4).

Benzothiazole-based mercaptans, dusulfides and sulfenamides are the main accelerators of sulfur vulcanization. The triazine-based compounds are similar in their mode of action, described in DE-PS 1 669954 and DE-PS 1 298706. The Ν, Ν'-substituted bis (2,4-diamino-s-triazine) belongs in the same category. 6-yl) -oligosulfides (n = 4) which, in contrast to the abovementioned accelerators, also crosslink without the addition of free sulfur, with the formation of an -S,

-S-S - ^ - S-Sx-S Vemetzungsstruktur. ,

The crosslinking process in the accelerated sulfur vulcanization can usually be divided into 3 phases, namely the incubation time of the crosslinking reaction, the crosslinking process itself, characterized by the rate constant and the crosslinking yield, and the overheating period. The aforementioned accelerators usually differ in their behavior in all three phases.

For reasons of processing safety of rubber compounds, especially when the processing temperature must be increased to increase productivity, so-called retarders or "pre-vulcanization inhibitors" are used to prolong the incubation time of the vulcanization reaction In practice, the delay in sulfur vulcanization with sulfenamides preferably N-cyclohexylthio-phthalimide (CD Trivette et al., Rubber Chem.

Technol. 50, 570 [1977], Monsanto, USP 3427319, 3546185, 3752824, 3855262) and for Benzthiazolyldisulfid preferably the N-phenyl-N- (trichloromethylsulfenyl) benzene sulfonamide (DE-OS 1957484) as effective agents.

Object of the invention

The aim of the invention is to improve the vulcanization characteristics of rubber compounds.

Explanation of the essence of the invention

The invention relates to the use of compounds of the general formula

R ⁵

6 - "" ^ ^ N-S- 'CCl-

in which mean:

R ^5, R ^6: H, C ₁ -C ₆ -alkyl, preferably Ci-C ₄ alkyl, benzyl, phenyl, identical or different, R ⁵ and R ⁸ a closed _C4-C6 -methylene, wherein the ring formed may be substituted once or twice by CH ₃ groups (spiro compounds),

in vulcanizable rubber mixtures in combination with oligosulfidic compounds of the general formulas

(ID,

in which mean: -.

R ¹ , R ² = H; R ² = benzyl.

R ² , R ³ , R ⁴ = C ₁ -C ₈ -alkyl, preferably C ₁ -C ₄ -alkyl, branched or unbranched. Alkyl, C ₃ -C ₈ -CyClOaIkYl, the latter unsubstituted

or substituted with 1-3 methyl groups, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or R ³ and R ⁴ (together): C ₄ -C ₆ -alkylene, - (CH ₂ -CHX) ₂ Y

with X = -CH ₃ , H; Y = 0.5 η = 2q of the 4,

or a mixture of compounds according to formula II, where the S _{n has} an average statistical chain length

with η = 4 corresponds.

The process for preparing the pure tetrasulfides having a linear S ₄ chain between the two substituted triazine radicals is characterized in that an aqueous, alkaline solution of the corresponding N, N'-substituted 2,4-diamino-6-mercaptotriazme in a two-phase -nsystem with a S ₂ Cl ₂ solution in an inert organic solvent in which the reaction product is not or very little soluble, at temperatures between -5 ° Cbis <+ 20 ° C, preferably of + 1O ⁰ C, reacted , It is advantageous to prepare an alkaline aqueous solution of mercaptotriazine which contains at least the stoichiometric amount of alkali hydroxide necessary for the reaction, preferably an excess of 1-20 mol%, based on the mercaptotriazine used.

This solution is treated with a solvent in which the final product of the reaction is not or slightly soluble; is preferably C5-Cio-Aikanen or Cs-C ₃ cycloalkanes, optionally substituted by 1 to 3 methyl groups, and mixtures thereof. This mixture is stirred vigorously and cooled, preferably to + 10 ° C.

Now allowed to drop into this mixture with good cooling, a solution of S ₂ Cl ₂ in the solvent used. S ₂ Cl ₂ is used at least in the ratio of 2 mol of mercaptotriazine: 1 mol of S ₂ Cl ₂ , but depending on the excess of alkali, this ratio may also be 2: 1.1-1.2.

Under the given conditions, S ₂ Cl _{2 is} exclusively condensing.

The resulting product is separated by means of generally known measures and advantageous at temperatures up to

+50 ⁰ C under vacuum dOTorr) dried. ,

Also used are mixtures consisting of compounds of the general formula

(ID,

in which R ¹ , R ² , R ³ and R ^{4 have the} abovementioned meaning and S _n corresponds to an average statistical chain length with η = 4.

These mixtures of oligosulfides, hereinafter also referred to as disproportionates, since they are formed by disproportionation of tetrasulfides according to formula II can be represented in several ways.

The reaction conditions are controlled so that no free sulfur is formed.

One method is characterized in that the mixture is heated to an isolated tetrasulfide of formula II above its melting point, preferably to 20-50 ⁰ C.

In a further process, the tetrasulfides according to formula II are dissolved in an inert organic solvent and the disproportionation reaction is carried out in the temperature range between 20 ° C. (allowed to stand at room temperature) and boiling point of the solvent used.

A particularly elegant method consists of reacting an aqueous alkaline solution of the corresponding rJ, N'-substituted 2,4-diamino-6-mercaptotriazines in a two-phase system with a solution of S2CI ₂ in an inert organic solvent dissolving the resulting tetrasulfide. The resulting linear tetrasulfide is then immediately disproportionated into the mixture according to the invention.

Particularly suitable solvents are chlorinated hydrocarbons, for example CH ₂ Cl ₂ and CHCl ₃ , but also ethers, esters and aromatic hydrocarbons and ketones are suitable for the disproportionation reaction in the absence of water. In tetrasulfide formation, they are useful when forming a biphasic mixture with water. The reaction conditions for the preparation of the disproportionates are otherwise identical to those for the preparation of pure tetrasulfides.

To what extent the disproportionation reaction has progressed remains irrelevant to the suitability of the resulting mixture.

There must not be any free sulfur during disproportionation.

It can be seen that when the compounds of formulas (1) and (II) are used together, not only can the scorching be greatly retarded, but the vulcanization characteristic is simultaneously improved so that all the physical density-responsive data, such as maximum torque (rheometer) or the tension values at 300% elongation, can be raised considerably.

For example, preference is given to using

VZ g 3-trichloromethylthio-5,5-dimethylhydantoin

VZ h S-trichloromethylthio-B-benzylhydantoin

VZ i S-trichloromethylthio-S-n-propylhydantoin

VZ k S-trichloromethylthio-B-isopropylhydantoin

VZI S-trichloromethylthio-B-pentamethylenehydantoin

These substances are known.

(Kittleson, Science 115, 84 [1952], USP 2,553,770, G.P. Lampson and H.O. Singher, J. Org. Chem., 21, 644-685). They are characterized by strong fungicidal and partly bactericidal action. They are prepared from the corresponding hydantoins and trichloromethylsulfenyl chloride in the presence of an acid acceptor.

The Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) disulfides according to formula (II) are described in DE-PS 1669954; for example, bis (2-ethylamino-4-diethylamino-s-triazin-6-yl) disulfide, bis (2-ethylamino-4-di-n-isopropylamino-s-triazin-6-yl) disulfide.

The other Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetra oligosulfide according to formula (II) are in the application P

called.

For example, preference is given to:

N bis (2-ethylamino-4-diethylamino-triazin-6-yl) tetrasulfide

A bis (2-ethylamino-4-di-isopropylamino-s-triazin-6-yl) tetrasulfide

B bis (2-n-butylamino-4-diethylamino-s-triazin-6-yl) tetrasulfide

C bis (2-isopropylamino-4-di-isopropylamino-s-triazin-6-yl) tetrasulfide

D Bis (2-ethylamino-4-diisobutylamino-s-triazih-6-yl) tetrasulfide

E bis (2-ethylamino-4-di-n-propylamino-s-triazin-6-yl) tetrasulfide

F bis (2-n-propylamino-4-diethylamino-s-triazin-6-yl) tetrasulfide

G bis (2-n-propylamino-4-di-n-propylamino-s-triazin-6-yl) tetrasulfide

H bis (2-n-butylamino-4-di-n-propylamino-s-triazin-6-yl) tetrasulfide

I Bis (2-ethylamino-4-di-n-butylamino-s-triazin-6-yl) tetrasulfide

K bis- (2-isopropylamino-4-di-isopropylamino-s-triazin-6-yl) -oligosulfide mixture

L bis (2-cyclohexylamino-4-diethylamino-s-triazin-6-yl) -oligosulfide mixture

M bis (2-ethylamino-4-diethylamino-s-triazin-6-yl) -oligosulfide mixture

O bis (2-amino-4-diethylamino-s-triazin-6-yl) -oligosulfide mixture

In rubber mixtures known in the art with natural rubber (NR), isoprene rubbers (IR), butadiene rubbers (BR), styrene-butadiene rubbers (SBR) isobutylene-isoprene rubbers (HR), ethylene-propylene terpolymers (EPDM), nitrile rubbers (NBR), halogen-containing Rubbers and also epoxidized natural rubbers (ENR) as well as blends of these rubbers with one another, the substituted N-trichloromethylthiohydantoins according to formula (I) are to be used as vulcanization retardants with a crosslinking density-increasing effect in combination with Ν, Ν'-substituted bis (2,4-) diamino-s-triazin-6-yl) -oligosulfides according to formula (II).

The invention also relates to rubber mixtures containing the compounds of the formulas (I) and (II), in particular mixtures containing 0.1-5 parts, preferably 0.1-2 parts, one or more substituted N-Trichlormethylthiohydantoine and 0 , 1-10 parts, preferably 0.1-5 parts of one or more Ν, Ν'-substituted bis (2,4-diaminos-triazin-6-yl) oligosulfides, each based on 100 parts of rubber. In a preferred embodiment, the molar ratio of hydantoin to triazine derivatives is 0.3-1.5: 1.0, especially 0.3-1.2: 1.0. Free sulfur does not contain such mixtures. The oligosulfides are then tetrasulfides or mixtures of compound 3n according to formula II, in which -S _n - means an average chain length corresponding to S ₄ .

The invention further provides sulfur vulcanizable rubber mixtures which additionally contain sulfur, so that a molar ratio of 0.3-1.5 (hydantoin derivative): 1 (triazine derivative): 0.5-1.5 (sulfur ), preferably 0.3-1.2: 1: 0.5-1.5.

To achieve a further variation of the vulcanization kinetics, it may prove expedient to use the triazine compounds according to formula II in the form of mixtures of two or more individuals, with adherence to the above mentioned. Application levels, in particular the preferred molar ratios, the substitution is to be made on an equimolar basis.

For kinetic reasons, it may prove to be expedient, the Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides according to formula II in admixture with conventional accelerators of Benzthiazolreihe and / or thiuram Benzthiazolesulfenamide Benzthiazoldisulfid, 2-mercaptobenzothiazole or their zinc salts and tetramethylthiuram disulfide (see J. van Alphen, Rubber Chemicals [1977] pp 1-46).

With these dosage guidelines, the vulcanization problems can be solved without causing a loss of vulcanization property.

Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides according to formula II are advantageous to use together with organosilanes, for example

[(RO) ₃ Si (CH ₂ US _x (III) or (RO) ₃ -Si (CH ₂ I _n -SH '(IV)

with χ = 2-6, preferably 4, R = C ₁ -C ₆ -alkyl, cycloalkyl η = 2 or 3

(RO) ₃ -Si

or

"S _x (V)

with χ = 2-6, preferably 3, Alk = methyl, ethyl, preferably bis (3-triethoxysilylpropyl) tetrasulfide (Si 69, Degussa AG) are used, namely in the sulfur-free Si 69 crosslinking (DE PS 2536674) , in sulfur vulcanization with Si 69 (DE-PS 2255577) and also in the preparation of reversion-stable vulcanizates by construction of equilibrium cure systems (Lit.) according to DE-PS 2848559. In all the above cases act N-Trichlormethylthiohydantoine according to formula I as Vulkanisationsverzögerer Crosslinking density-increasing effect.

The vulkanisationsverzögernde effect of the substituted N-Trichlormethylthiohydantoine according to formula I also occurs when the Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides according to formula II individually or in a mixture together be used with conventional accelerators and / or conventional sulfur donors such as Suifasan® R (morpholine disulfide).

The use of the substituted N-Trichlormethylthiohydantoine according to formula I as a retarder with crosslinking density-increasing effect in combination with Ν, Ν'-substituted BisBis- (2,4-diamino-s-triazin-6-yl) sulfides according to formula II is carried out in rubber mixtures that may contain as other common mixture components:

- amplification systems, i. Furnace blacks, channel blacks, flame blacks, thermal blacks, acetylene blacks, electric arc blacks, carbon blacks, etc., and synthetic fillers, such as silicas, silicates, alumina hydrates, calcium carbonates, and natural fillers, such as clays, silicates, chalks, talcs, etc., as well as silane-modified fillers and their blends in quantities of 5-300 files per 100 parts of rubber.

Zinc oxide and stearic acid as vulcanization promoters in quantities of 0.5-10 parts per 100 parts of rubber,

- commonly used aging, ozone, fatigue inhibitors such as IPPD ₁ TMQ, etc. and waxes as light stabilizers and their blends,

Any plasticizers, such as aromatic, naphthenic, paraffinic, synthetic plasticizers and their blends,

Organosilanes used in the rubber industry according to the prior art, for example, chloropropyltrialkoxisilanes, vinyltrialkoxysilanes, γ-mercaptopropyitrialkoxisilanes and aminoalkyltrialkoxisilanes, as well as their blends in an amount of 0.1-25, preferably 1-10 parts per 100 parts of silanol-group-carrying fillers such as silicas, silicates, clays, etc.

- if necessary. Dyes and processing aids in the usual dosage.

The scope of the rubber mixtures prepared using substituted N-trichloromethylthiohydantoins according to formula I in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligosulfides according to formula II extends to the preparation from tires, to technical articles such as blends for conveyor belts, V-belts, molded articles, hoses with and without inserts, roll rubbers, liners, spray profiles, freehand articles, films, shoe soles and tops, cables, solid rubber tires and their vulcanizates.

Production and vulcanization of the rubber mixtures is carried out by the known methods and under the usual conditions.

Example 1:

454 g of 2-ethylamino-4-diethylamino-6-mercaptotriazine are dissolved in sodium hydroxide solution, which has been prepared from 84 g of NaOH + 1.5 liters of H ₂ O.

The solution is placed in a 4 liter 3 tube flask, then add 1.5 liters of mineral spirits (Kp80-110 ⁰ C) and the mixture is cooled with vigorous stirring to 0 ⁰ C from.

Now one can within 20 min a solution of 137 g of S ₂ CI ₂ run into 100 ml of gasoline, care being taken that the temperature does not exceed +5 ^0C.

The tetrasulfide precipitates immediately. At the end of the reaction is stirred for 5 min, then filtered with suction and washed.

The snow-white fine powder is dried in vacuum / 12Torr at 40-45 ⁰ C.

Amount: 499.5 g, corresponding to 97.1% of theory, mp 149-150 ⁰ C.

Analysis:

Bis- (2-ethylamino-4-diethylamino-s-triazin-6-yl) tetrasulfide,

Mol wt. 516, C ₁₃ H ₃₂ N ₁₀ S ₄

C H N S calc. 41.9 6.2 27.1 24.8 gef. 41.8 6.5 26.8 24.8

TLC and HPLC analysis show that the product contains 97.1% linear tetrasulfide.

Example 2:

Dissolve 56.6 g of 2-ethylamino-4-di-n-butylamino-6-mercaptotriazine in a solution of 8.8 NaOH in 250 ml of water. To do this, you give 250ml of gasoline. The mixture is cooled to +5 ⁰ C after good stirring. Now a solution of 13.5 g of S ₂ Cl ₂ in 30 ml of gasoline is allowed to run. It immediately forms a white precipitate. At the end of the reaction is worked up according to Example 1. Quantity: 56g, corresponding to 89.2% of theory

Analysis: C ₂₆ H ₄₈ N ₁₀ S ₄ (molecular weight 628)

C H N S calc. 49.68 7.64 22.29 20.38 gef. 49,59 7.59 22.18 20.40

HPLC analysis: purity> 96%.

Example 3:

107.6 g of 2-i-propylamino-4-diisopropylamino-6-mercapto-triazine is dissolved in sodium hydroxide solution, which is prepared from 17.6 g of NaOH in 600 ml of H ₂ O. To this is added 600 ml of methylene chloride.

At 0-5 ⁰ C is allowed to run a solution of 27g S ₂ Cl ₂ In 50ml CH ₂ Cl ₂ . At the end of the reaction, the organic phase is separated off in a separating funnel, dried and evaporated in vacuo. An amorphous powder is obtained; Softening point: 90 ^° C.

Yield: 112.5g, corresponding to 94% of the theory.

Analysis: C ₂₄ H ₄₄ N ₁₀ S ₄ (molecular weight 600)

C H N S calc. 48 7.33 23.3 21.3 gef. 48.2 7.36 23,01 20.95

Example 4:

45.4 g of 2-ethylamino-4-diethylamino-6-mercaptotriazine are dissolved in sodium hydroxide solution prepared from 8.8 g of NaOH and 200 ml of water.

To this is added 200 ml of methylene chloride. The mixture is turbined and cooled to ⁰ ° C. 14 g of S ₂ Cl ₂ in 50 ml of CH ₂ Cl _{2 are} now dissolved, and this solution is allowed to run into the mercaptide solution.

The reaction product dissolves in CH ₂ Cl ₂ . At the end of the reaction, the phases are separated and the CH ₂ Cl ₂ solution is worked up. This gives an amorphous powder with a softening point of about 11.O ⁰ C.

Quantity: 46.7g, corresponding to 90.5% of the theory.

Analysis: C ₁ SH ₃₂ N ₁₀ S ₄ (molecular weight 516)

N S calc. 27.1 24.8 gef. 26.8 24.4

According to TLC analysis, the product contains a mixture of 4Oligosulfide, but no free sulfur

Example 4:

45.4 g of 2-ethylamino-4-diethylamino-6-mercapto-triazine are dissolved in sodium hydroxide solution prepared from 8.8 g of NaOH and 200 ml of water.

200 ml of methylene chloride are added. The mixture is turbined and cooled to ⁰ ° C. 14 g of S ₂ Cl ₂ in 50 ml of CH ₂ Cl _{2 are} now dissolved, and this solution is allowed to run into the mercaptide solution.

The reaction product dissolves in CH ₂ Cl ₂ . At the end of the reaction, the phases are separated and the CH ₂ Cl ₂ solution is worked up. This gives an amorphous powder with a softening point of about 110 ⁰ C.

Quantity 46,7g, corresponding to 90,5% of the theory.

Analysis: Ci ₈ H ₃₂ N ₁₀ S ₄ (mol. Wt. 516)

N S. calc. 27.1 24.8 gef. 26.8 24.4

TLC analysis shows a mixture of 4 oligosulfides but no free sulfur

Example 5:

50 g of bis (2-ethylamino-4-diethylamino-s-triazin-6-yl) tetrasulfide having a purity of 97.1% are placed in a round bottom flask and heated to 160 ° C. in an oil bath for 1 hour. Cold, the melt solidifies amorphous. After TLC analysis, the product contains about 50% of the starting material 3 more oligosulfides.

Example 6:

70.25 g of 2-cyclohexylamino-4-diethylamino-6-mercaptotriazine are dissolved in 11 g of NaOH and 250 ml of water. To this is added 250 ml of chloroform. While stirring vigorously, a solution of 16.8 g of S ₂ Cl ₂ in 30 ml of CHCl _{3 is added} . At the end of the reaction, the phase is separated and the chloroform layer is worked up. This gives 71.9 g of a white amorphous powder, corresponding to 92% of theory.

Analysis: C ₂₆ H ₄₄ N ₁₀ S ₄ (molecular weight 624)

C H N S

ber. 50 7.05 22.4 20.51

gef. 49.1 6.90 21.8 20

According to TLC analysis, the product is composed of about 30% linear S _A product and 70% oligosulfides, but contains no free sulfur.

auditing standards

The physical tests were carried out at room temperature according to the following standard regulations:

DIN 53504 measured in Voltage value 300% DIN 53529 MPa Incubation time ti ASTM D 2084 min scorch DIN 53505 min Shore A hardness DIN 53529 Degree D -D nm

The application examples use the following names and abbreviations, the meaning of which is given below.

RSS: Ribbed Smoked Sheet (Natural Rubber)

CORAX® N 220: carbon black, surface area (BET) 120 m ² / g (Degussa)

Naftolen®ZD: softeners made from hydrocarbons

Vulkanox® 4010NA: N-isopropyl-N'-phenyl-p-phenylenediamine

Vulkanox®HS: poly-2,2,4-trimethyl-1,2-dihydroquinoline

Mesamoll®: Alkyl sulfonic acid esters of phenol and cresol

Protektor® G 35: Ozone protection wax

Vulkacit®MOZ: Benzothiazolyl-2-morpholinosulfenamide

Vulkalent®E: N-phenyl-N- (trichloromethylsulfenyl) benzenesulfonamide

Ultrasil®VN3: precipitated silica (Degussa)

Gran. Granules

V143: Bis (2-ethylamino-4-di-ethylamino-s-triazin-6-yl) disulfide

V 225 Bis- (2-isopropylamino-4-di-isopropylamino-s-triazin-6-yl) -disulfide

Sulfasin®R morpholine disulfide

Example 7:

Demonstrating the effectiveness of various hydantoins \ n NR rußgefülltem in combination mitBis- (2-ethylamino-4-diethylaminos-triazin-6-yl) tetrasulfide (N) as an accelerator

1 2 3 4 CJL 6 7 RSS 1, ML (1 +4) = 70-80 100 100 100 100 100 100 100 CORAX N 220 50 50 50 50 50 50 50 ZnORS 5 5 5 5 5 5 5 stearic acid 2 2 2 2 2 2 2 NaftolenZD 3 3 3 3 3 3 3 Protector G 35 1 1 1 1 1 1 1 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 2.5 2.5 VulkacitMOZ 1.43 - - - - - - N - 1.5 1.5 1.5 1.5 1.5 1.5 VZG - - 0.75 - - - - VZH - - - 0.91 - - - vzi - - - - 0.78 - - FACH - - - - - 0.78 - OCI - - - - - - 0.85 sulfur 1.5 0.8 0.8 0.8 0.8 0.8 0.8 D _max -D _min (170 ^o C), Nm 8.65 7.03 8.26 7.84 7.67 7.91 7.61 t, (170 ^° C.), min 4.5 2.9 4.5 4.0 4.0 4.1 4.0 t | (130 "C), min 22.5 9.5 21.8 21.0 21.0 21.5 22.0 Vulcanizate data at 170X Voltage value 300% 10.2 10.6 11.2 11.3 11.2 11.4 11.3

Example 7 shows that the addition of N-trichloromethylthiohydantoins for tetrasulfidic triazine accelerators gives a scorch extension (mixtures 2-7) which raises the scorch time to the level of sulfenamide acceleration (mixture 1). In carbon black filled NR, an increase of 300% is also observed.

Example 8:

Comparison of N-trichloromethylthiohydantoins with Vulcalent E in N 220-filled NR with N, N'-substituted bis (2,4-diaminos-triazin-6-yl) tetrasulfide (N) as accelerator

i = 70-80 8th 9 10 11 12 13 RSS1, ML (1 +4) 100 100 100 100 100 100 CORAX N 220 50 50 50 50 • 50 50 ZnORS CJL 5 CJL 5 5 CJL stearic acid 2 2 2 2 2 2

-

8th 9 10 11 12 - 13 , 3 3 3 3 3 3 1 1 1 1 1 1 2.5 2.5 2.5 2.5 2.5 2.5 CJL 1.5 1.5 1.5 1.5 1.5 1.43 - - - - 1.5 1.5 1.5 1.5 1.5 .0,8 - - - - 0.8 - - _ ^ '0.8 - _ - - 0.8 1.5 0.8 0.8 0.8 0.8 0.8 4.5 2.9 3.8 4.6 4.4 4.0 22.5 9.5 · 14.0 23.5 21.7 , 21.0

NaftolenZD Protector G 35 Vulkanox4010NA VulkanoxHS VulkacitMOZ

VulkalentE

Sulfur t | (170X), min. T (130X), min. Vulcanization. At 170X

Voltage 10.2 10.6 10.7 11.4 11.4 11.2

Comparison of Vulkalent E (Blend 10) with N-trichloromethylthiohydantoins (Blends 11-13) shows that these hydantoins result in longer incubation time and higher stress at 300% elongation.

Temperä ⁹ turabhängigkeit the effect of substituted N-Trichlormethylthiohydantoinen with bis (2-ethylamino, 4-diethylamino-s-triazin-6-yl) disulfide acceleration in N 220-filled NR.

14 15 RSS1, ML (1 + 4) = 70-80 100 100 CORAX N 220 50 50 ZnORS   5 5 stearic acid 2 2 NaftolenZD -i 3 3 Vulkanox4010NA 2.5 2.5 VulkanoxHS 1.5 1.5 Protector G 35 1 1 V143 1.29 1.29 OCI - 0.85 sulfur 1.5 1.5 ti, min: 145X 8.2 18.5 160X 5.2 8.6 170X 4.0 5.4 180X 2.8 4.1 Vulcanization rate, min: (T90% t10%) 145X 15.9 18.7 160X 4.1 5.5 170X ' 2.0 3.1 180X 1.3 1.5 vulcanizate: Voltage value 300%, MPa 145X 10.6 12.1 170X 3.5 11.7 Shore A hardness: 145X 65 68 170X 63 68

The addition of an N-trifluoromethyl thiohydantoin, at processing temperatures of the mixtures 145X, significantly prolongs the incubation time without significantly reducing the cure time at higher temperatures and, in any event, effectively increasing the 300% voltage value.

The use of substituted N-trichloromethylthiohydantoins in bis (2-ethylamino-4-diethylamino-s-triazin-6-yl) -oligosulfide mixture-containing, carbon black N 220 / silica-filled NR

16 17 18 RSS1, ML (1 +4) = 70-80 100 100 100 CORAX N 220 25 25 25 UltrasilVN3Gran. 25 25 25 ZnORS CJL 5 5 stearic acid 2 2 2 NaftolenZD 3 3 3 Protector G 35 1 1 1

16 17 18 Vulkanox4010NA 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 VulkacitMOZ 1.43 - - M - 3 3 vzi - - 0.78 sulfur 1.5 0.8 0.8 ti (170 ^° C.), min. 4.6 3.9 4.5 ti (130 ^° C.), min. 33.3 16.6 32.5 Vulcanizate data (17O ⁰ C): Voltage value 300% 3.6 6.0 8.3

In N2O / silica-filled NR mixtures, the addition of VZi (mixture 18) shows a reference level incubation time extension (mixture 16) and a 300% increase in mixture versus mixture

Example 11:

Effect of substituted N-trichloromethylthiohydantoin in N 220-filled NR accelerated with a V 225 / MOZ blend

19 20 .21 RSS 1, ML (1 +4) = 70-80 100 100 100 CORAX N 220 50 50 50 ZnORS 5 5 5 stearic acid 2 2 "' 2 NaftolenZD 3 3 3 Protector G 35 1 1 · 1 Vulkanöx4010NA 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 VulkacitMOZ 1.43 0.72 0.72 V 225 - 0.75 0.75 VZk- , - - 0.4 sulfur 1.5 1.5 1.5 D _max -D _min , (170 ° C.) Nm 8.56 8.19 8.79 ti (17O ⁰ C), min. 4.5 4.2 4.8 Τ, (13O ⁰ C), min. 22.5 15.6 20.1

When Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) disulfide is used together with commercially available sulfenamide accelerators (mixture 20), the addition of VZ k (mixture 21) also results in the incubation time extended.

Example 12:

Effect of VZ g on N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfide / Si 69-accelerated, N 220 / silica-filled NR mixtures,

22 23 24 RSS 1, ML {1 +4) = 70-80 100 100 100 CORAX N 220 25 25 25 UltrasilVN3Gran. 25 25 25 Si 69 3.75 3.75 3.75 ZnORS 5 5 5 stearic acid 2 2 2 NaftolenZD 3 3 3 Protector G 35 1 1 1 Vulkanox4010NA 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 VulkacitMOZ 1.43 - - B - 1.66 1.66 VZG - - 0.75 sulfur 1.5 1.5 1.5 t, (170 ° C), min .. 4.9 4.2 5.1 ti (130 ^° C.), min. 37.5. 25.4 37.0

As can be seen from Example 12, a scorch delay is achieved even in the presence of Si 69 in carbon black / silica-filled NR.

Example 1 S. Effect of VZ g in a D-crosslinked, N 220-filled NR mixture with sulfur donor

25 26 27 RSS 1, ML (1 + 4) = 70-80 100 100 100 CORAX N 220 50 50 50

25 26

ZnORS stearic acid NaftolenZD Protector G Vulkanox4010NA VulkanoxHS VulkacitMOZ D

Sulfur Sulfasane R t | (170 ° C), min. t | (130 ° C), min.

Also, when used in NR mixtures with sulfur donors together with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides, as mixture 27 shows, the VZ g addition a clear Scorch extension, based on the level of the reference mixture with sulfenamide acceleration and sulfur (mixture 25).

Step Example! Figure 14: Influence of VZI in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligosulfides in N 330-fused BR

25 26 27 CJL 5 5 2 2 2 3 3 3 1 1 1 2.5 2.5 2.5 CJL 1.5 1.5 1.43 - - - 1.76 1.76 -. - 0.75 1.5 -. - - 0.7 0.7 4.5 3.2 4.6 22.5 11.5 21.5

28 29 30 31 Buna CB10 100 100 100 100 CORAX N 330 60 60 60 60 ZnORS 3 3 3 3 stearic acid 2 2 2 2 NaftolenZD 15 15 15 15 Protector G 35 1 1 1 1 Vulkanox4010NA 1.5 1.5 1.5 1.5 D 1.76 1.76 - - V 225 - - 1.5 1.5 OCI - 0.85 - 0.85 sulfur 1.5 1.5 1.5 1.5 ^ (165 ⁰ C), min 4.3 5.8 6.8 9.5 Vulcanizate data at 165 ° C Voltage value 300% 7.1 9.6 6.0 9.0

  Example 14 shows the incubation time extension of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) di- and tetrasulfide-accelerated, N330-filled polybutadiene and, at the same time, the significant 300% increase in the addition value of N-trichloromethylthio-5-pentamethylenehydantoin

Example 15:

Effect of VZI in combination with Ν, Ν'-substituted 8is- (2,4-diamino-s-triazin-6-yl) -oligosulfides as promoters in N 330-filled NBR mixtures

32 33 34 35 Perbunan N 3307 NS 100 100 100 100 CORAX N 330 60 60 60 60 ZnO active 5 5 5 5 stearic acid 1 1 1 1 mesamoll 10 10 10 10 Paraffin solid 1 1 1 1 VulkanoxHS 1.5 1.5 1.5 1.5 D 1.76 1.76 - - V 225 - - 1.5 1.5 OCI , 0.85 0.85 sulfur 1.2 1.2 1.2 1.2 D _ma x D _min , (170 ° C) Nm 9.23 12.81 8.18 12.40 ι, (17O ⁰ C), min 3.5 4.7 4.8 8.3 vulcanization t90-t10%, min 8.2 2.8 9.4 3.3 Vulcanizate data at 170 ° C Voltage value 300% 14.0 16.9 11.6 15.6

By adding VZI to NBR mixtures in the presence of Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetra- and disulfides, it is possible to improve scorch safety while increasing the rate of vulcanization. Likewise, there is a considerable increase in the voltage value of 300%, despite the already very high output level.

Example 16:

Effect of VZi on vulcanization in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulphides in NR / BR blends.

36 37 38 39 RSS 1, ML (1 +4) = 70-80 70 70 70 70 BunaCBIO 30 30 30 30 CORAX N 220 50 50 50 50 ZnO active 5 5 5 5 stearic acid 2 2 2 2 NaftolenZD 3 3 3 3 Protector G 35 1 1 1 1 VulkanoxHS 1.5 1.5 1.5 1.5 Vulkanox4010NA 2.5 2.5 2.5 2.5 D 1.76 1.76 - - V143 - - 1.29 1.29 vzi - 0.78 - 0.78 sulfur 0.8 0.8 0.8 0.8 ti (170 "C), min. 2.7 4.3 4.1 5.7 ti (130 ^° C.), min. 6.6 17.2 16.8 32.8

Example 16 shows that even in the blend of N R with synthetic rubber, a significant gain in scorch safety can be achieved by adding N-trichloromethylthio-5-n-propylhydantoin.

Claims (5)

claims: R ⁵ , R ⁰ : H, C ₁ -C ₆ -Alkyl, benzyl, phenyl, identical or different, or R ⁵ and R ^{6 is} a closed C ₄ -C ₆ -methyl chain, wherein the ring formed once or twice by CH ₃ groups may be substituted in combination with oligosulfidic compounds of the general formula 2'- -i · 2 with χ = 2-6, preferably 3, AIk = methyl, ethyl are used in vulcanizable rubber mixtures. 2. Use of the compounds according to claim 1, characterized in that they are used in combination with conventional accelerators based on benzthiazole, in particular mercaptans, disulfides, sulfenamides and / or thiurams in vulcanizable rubber mixtures. 3. Use of compounds according to claim 1, characterized in that they in combination with organosilanes of the general formulas (III) [(RO) 3-Si (CH ₂ ) _n ] 2-S _x or (RO) ₃ -Si (CH ₂ J _n -SH with η = 2; 3, χ = 2-6, R = C ₁ -C ₆ alkyl, cyclohexyl or (RO) Si  (GH) 4. Use of compounds of general formula (I) and (II) according to claims 1 to 3, characterized in that they are used with additional sulfur donors in vulcanizable Käutschukmischungen. 4 \ l \ | \ i \ * N ^ N (S in which mean:
, R ¹ , R ² = H; R ² = benzyl R ² , R ³ , R ⁴ = C ₁ -C ₈ -AlkYl, allyl, Cs-Cs-cycloalkyl, the latter unsubstituted or substituted with 1-3 methyl groups, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or
R ³ and R ⁴ (together): C ₄ -C ₆ -alkylene, - (CH ₂ -CHX) ₂ Y with X = H, CH ₃ , Y = 0, S
η. = 2 or 4, or a mixture of compounds of the formula (II) in which S _{n is} a medium statistical chain length with η = 4, characterized in that they are used in rubber mixtures as Vulkanisationsverzögerer with crosslinking density-increasing effect. 5. Vulcanisable rubber mixtures, characterized in that they contain 0.1-5 parts of substituted N-trichloromethylthiohydantoins according to formula (I) and also contain 0.1-10 parts of N, N'-substituted bis (2,4-diamino-s) triazin-6-yl) - oligosulfides according to formula (II) (n = 4) and optionally 0.1-10 parts of sulfur, in each case based on 100 parts of rubber, wherein the two first-mentioned components in a molar ratio of 0.3-1, 5: 1, preferably 0.3-1.2: 1, while the. The ratio of oligosulfide according to formula (II) to sulfur amounts to 1: 0.5-1.5.