CS276589B6 - N,n'-substituted bis(2,4-diamino-s-triazin-6-yl) tetrasulfides, process of their preparation and their use in curable masterbatches - Google Patents

Abstract

Compounds of the general formula <IMAGE> in which R<1>, R<2> denote H; R<2> denotes benzyl, R<2>, R<3>, R<4> denote C1-C8-alkyl, allyl, C3-C8-cycloalkyl, the latter being unsubstituted or substituted by 1-3 methyl groups, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or R<3> and R<4> (together) denote C4-C6-alkylene, -(CH2-CHX)2Y where X is H, CH3 and Y is O, S and their oligosulphide disproportionation products, whose average statistical chain length corresponds to S4 are prepared from the corresponding N,N'-substituted diaminomercaptotriazines. The substances according to the invention are used in vulcanisable rubber mixtures as crosslinking agents without sulphur or as vulcanisation accelerators together with sulphur.

Description

(57)

N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula I wherein R ¹ is hydrogen, R 1 is hydrogen or benzyl, each of R 1, R 2, and R 1 is C 1 -C 8 alkyl, allyl, C 3 -C 8 cycloalkyl optionally substituted with 1 to 3 methyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or R ³ and R 6 together or (CH ₂ -CHX) wherein X is methyl or hydrogen and Y is oxygen or sulfur are prepared by reacting the corresponding N, N'-substituted diaminomercaptotriazines in an aqueous alkaline solution with sulfur trichloride in an inert organic solvent forming a two-phase system with an aqueous medium. The disclosed compounds are used in vulcanizable rubber compositions as crosslinkers, sulfur-free or as vulcanization accelerators, together with sulfur.

H ^ 11

Λ Λ

N II NK ' ^X ' A _,; / 1 /

The present invention relates to N, N '-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides, a process for their preparation and their use as crosslinkers or vulcanization accelerators in rubber compositions.

N, N ¹ -substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides are known and are described in DE Patent No. 1,669,954. 4-diamino-6-mercaptotriazines by oxidation, such as iodine, sodium hypochlorite or hydrogen peroxide. The best known compound in this group is bis- (2-ethylamino-4-diethylaminotriazin-6-yl) disulfide. Disulfides of this group can be used in rubber mixtures as accelerators.

SUMMARY OF THE INVENTION It is an object of the present invention to provide compounds which improve the vulcanization behavior of rubber compositions and to impart improved properties to the vulcanizates produced therefrom, and to provide a process for the production of these compounds.

The present invention provides N, N '-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula I (I) wherein:

R ¹ represents a hydrogen atom,

R is hydrogen or benzyl; Each of R, R and R is C 1 -C 8 alkyl, preferably C 1 -C 4, which is branched or unbranched; allyl, C 3 -C 8 cycloalkyl optionally substituted with 1 to 3 methyl groups; 2-hydroxyethyl; 3-hydroxypropyl; Or 2-hydroxypropyl;

4

R 2 and R 2 together represent an alkylene group having 4 to 6 carbon atoms or a group of the formula

- (ch ₂ -chx) ₂ y where

X is methyl or hydrogen and Y is oxygen or sulfur.

The present invention further provides a process for the preparation of N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides, characterized in that an aqueous alkaline solution corresponding to N, Ν'-substituted 2 The 4-diamino-6-mercaptetriazine is reacted in a two-phase system with a solution of sulfur trichloride in an inert organic solvent in which the reaction product is insoluble or sparingly soluble, at a temperature ranging from -5 to <20 ° C, preferably at 10 ° C. *C. Preferably, an alkaline aqueous solution of mercaptotriazine containing an alkali hydroxide in at least a stoichiometric amount relative to the reaction is used. Preferably, the alkaline solution contains an excess of alkaline hydroxide of 1 to 20 molar based on the mercaptotriazine used.

This solution is mixed with a solvent in which the end product of the reaction is insoluble or sparingly soluble, preferably with C 5 -C 10 alkanes or C 5 -C 8 cycloalkanes optionally substituted with 1 to 3 methyl groups or mixtures thereof. The resulting mixture is vigorously stirred and cooled, preferably to + 10 ° C and sulfuric chloride in the solvent used is added dropwise while cooling. Sulfur trichloride is used in a ratio of at least 2 moles of mercaptotriazine per mole of sulfur trichloride, but depending on the excess of alkali, this ratio may also be 2: 1.1 to 1.2.

Under these conditions, sulfur trichloride (S ₂ Cl ₂ ) acts exclusively condensation.

The resulting product is separated by a known method and dried preferably at a temperature of up to 50 ° C under vacuum (1.3 kPa).

The compounds of formula (I) are used as crosslinking agents or vulcanization accelerators which significantly outperform standard compounds of the prior art.

The rubber industry has a wide variety of accelerators at its disposal (J. van Alphen, Rubber Chemicals (1977, pp. 1 to 46)), mainly used for sulfur vulcanization, for example benzthiazolylsulfonamides, benzthiazolyl disulfide and 2-mercaptobenzthiazole or zinc salts thereof. In addition, there are a number of special compounds, such as thiuram disulfides and peroxides, which act as crosslinkers even without the addition of sulfur, but are often used as accelerators in combination with sulfur. The method of use depends on the effect to be achieved in each case.

Benzthiazolylsulfenamides are currently of great importance in practical applications, including in particular the acceleration of vulcanization of elastomers.

Due to new production processes, new products and constant pressure on rationalization, the demands placed on accelerators have recently changed to such an extent that it can now be difficult to meet the qualitative requirements for the vulcanization process and vulcanizate properties using accelerators or crosslinkers. which are currently available for accelerated sulfur vulcanization.

Another disadvantage of some conventional accelerators (for example some sulfenamides and thiurams) is that they can release amines during the vulcanization process which, if nitrosatable, lead to the formation of nitrosamines in the vulcanizate. If these accelerators lead to the formation of toxic nitrosamines, the potential for their application can be expected to decrease over time.

A major disadvantage of benzthiazolyl accelerators, especially benzthiazolylsulfenamides, is their tendency to reverse, which is becoming more pronounced with increasing vulcanization temperature with often inevitable overheating of the vulcanizates, particularly using those types of rubber which are no longer prone to reversal, such as natural rubber and polyisoprene and mixtures thereof with synthetic rubbers. However, the situation is similar for synthetic rubbers of all kinds, unless the reverse process is covered by thermal sieving. Especially as the vulcanization temperature rises, the reversal rate increases so strongly that, firstly, even with optimum vulcanization, there is a noticeable decrease in crosslinking density; secondly, vulcanization optimum takes the form of peaks instead of plateau, In many cases the need for re-cannulation results in a decrease in the crosslinking density which cannot be avoided, which in particular in the case of thick-walled rubber products results in the crosslinking of the vulcanizate not being uniform.

At the same rate as the reversal, the properties of the vulcanizate, such as the modulus at 300% elongation or abrasion resistance, deteriorate.

To some extent, a reduction in the sulfur content and an increase in the accelerator content, i.e. the use of so-called Semi-EV systems (L. Bateman, 1963, The Chemistry and Physics of Rubber-Like Substances, p. 522 et seq.) reverse effects. However, attenuation of this reversal is achieved by measuring the structure of the crosslinking (-S-, -S-S- and -S- bonds) in favor of monosulfide crosslinking structures, which may adversely affect the properties of the vulcanizate. However, this is less effective the higher the vulcanization temperature is.

These disadvantages of benzthiazole accelerators limit their applicability at increasing temperatures and to some extent limit the effort of the rubber industry to increase productivity using higher vulcanization temperatures.

Surprisingly, it has been found that the N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides prepared according to the invention are compounds which, when used as accelerators in sulfur vulcanization, as crosslinkers, i.e., without the addition of sulfur, they impart an extremely high reverse stability, even at very high overheating, to the rubber compositions produced using them even at high vulcanization temperatures.

To the otherwise usual reverse process. their use either does not occur at all or to a small extent. In fact, the surprising fact that the cross-linking structures formed using the N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides prepared according to the invention are exceptionally reversible and thermally stable results in their use in rubber mixtures, even at high vulcanization temperatures, to achieve a high level of physico-mechanical properties of the vulcanizate after the cross-linking reaction and, on the other hand, to maintain a high level of physico-mechanical properties for a long time even with heavy overheating.

Together, these effects make it possible to increase productivity in the rubber industry by increasing the vulcanization temperature, without the loss of performance properties of the vulcanizate.

Not even about the same reverse stability can be achieved with commercially available R R lysulfides such as Robac P 25 (Robinson, dipentamethylenethiurametetrasulfide) and Tetron A (Du Pont, dipentamethylenethiuramhexasulfide) or with dibenzthiazolyltetrasulfide.

N, Ν '-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides of the formula I are suitable for prior art rubber mixtures containing natural rubber (NR), isoprene rubbers (IR ), butadiene rubbers (BR), styrene-butadiene rubbers (SBR), isobutylene-isoprene rubbers (IIR), ethylene-propylene terpolymers (EPDM), nitrile rubbers (NBR), halogen-containing rubbers and also epoxidized natural rubbers (ENR) . Of particular interest is the use of N, N ' -substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula I for those types of rubber which tend to reverse, such as natural rubber, isoprene and butadiene rubbers and mixtures thereof or mixtures thereof with other rubbers.

The N, N '-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides of the formula I are used as crosslinkers in rubber mixtures in an amount of 0.2 to 15 parts by weight, preferably 0.3 up to 8 parts by weight per 100 parts by weight. rubber.

In accelerated sulfur vulcanization, the N, N ' -substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula I are used as accelerators in an amount of 0.01-10 and preferably 0.1-10. 5 parts by weight per 100 parts by weight. 0.1 to 10 parts by weight of rubber at a dosage of sulfur; The preferred molar ratio of accelerator of the invention to sulfur (Sg) is in the range of 1: 0.5 to 1.5. To augment the amount of variation in the vulcanization kinetics, it may be effective to employ in a mixture of two or more Ν, Ν-substituted bis- (2,4-diamino-s-triCS 276589 B6 azin-6-yl) tetrasulfides of formula I, while maintaining the abovementioned amounts, in particular the preferred accelerator / sulfur ratio, need to be replaced on one molar basis by one. The same applies to the use of N, N ' -substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula I as crosslinkers in the absence of sulfur.

Also, for reasons of kinetics, it may be expedient to use the Ν, Ν-substituted bis- (2,4-diamino-triazin-6-yl) oligosulfides of formula I in admixture with conventional accelerators, for example sulfenamides and thiurams. These measures are sometimes due to reverse stability as compared to vulcanizates whose vulcanization has been accelerated using the N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula I. the reverse behavior of the vulcanizates has a positive effect when N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula I are used instead of a portion of conventional accelerators.

Further substantial influence on the incubation time using the compounds prepared according to the invention in rubber compositions can be achieved by combining them with commercially available vulcanization vulcanization techniques such as Santoguard PVI (N-cyclohexylthio phthalimide) and E, N-phenyl-N- (trichloromethylsulfenyl) benzenesulfonamide vulcanent. Bayer AG's Vulcalent E has proven to be the most effective retarder, with the addition of Vulcalent E increasing the incubation time of mixtures containing N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides .

When N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides are used as cross-linking agents, it has proved useful to maintain the molar ratio of N, ,'-substituted bis- (2,4-diamino). -s-triazin-6-yl) tetrasulfides to vulcanent E at a value of 1: 0.5 to 1.5, preferably 1: 0.8 to 1.2 wt. parts per 100 parts by weight. rubber.

Of greater importance is the use of retarders, in particular Vulcalent E, in accelerated sulfur vulcanization using N, Ν '-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides or mixtures thereof. In addition to the intended increase in the incubation time of the crosslinking reaction, a slight decrease in the crosslinking rate is sometimes observed, but this can be compensated by an increase in temperature and a slight decrease in the reverse stability. In this case, the molar ratio of N, N ' -substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides according to the invention to Vulcalent E has also been found to be effective at a ratio of 1: 0.5 to 1, 5, preferably 1: 0.8 to 1.2, wherein the sulfur content is maintained between 0.1 and 10, preferably 0.5 to 8 parts by weight, based on 100 parts by weight, depending on the type of mixture. rubber.

Using the recommended dosage, many of these vulcanization problems can be solved without at the same time substantially deteriorating the properties of the vulcanizate that is foreign to the invention.

Mixtures containing only silicic acid or a mixture of carbon black and silicic acid with a proportion of silicic acid greater than 15 parts per 100 parts of rubber are difficult to crosslink with conventional sulfur-based vulcanization systems, if such crosslinking is even feasible. On the one hand, they are particularly reversible and, on the other hand, it is impossible to set the crosslink density to a predetermined requirement for the finished product. This is one of the reasons why silicas are preferably used in soles, but so far rarely in dynamically stressed products.

Surprisingly, the use of N, Ν'-substituted bis- (2,4-diamino-s-trlazin-6-yl) tetrasulfides of the formula I was achieved in mixtures containing black and white mixtures in which the proportion of silicic acid is more than 15 parts per 100 parts of rubber, and also for silica-filled compositions, virtually eliminating the reverse while increasing the crosslinking density, which, for silica-containing compositions, results in a high level of stress for silica-containing compositions. This effect is achieved when the compounds of the invention are used as both accelerators and crosslinkers (without sulfur).

A further possibility for the use of N, bis'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulphides of the general formula I lies in their combined application with oligosulphide organosilanes, for example compounds of the general formulas [(R-0) ₃ Si - (CH ₂ ) _n 3 ₂ . S _x or (RO) ₃ -Si (CH ₂ ) _n - SH where n is 2 or 3, x is 2 to 6, and

R is C 1 -C 6 alkyl or cyclohexyl;

wherein x is 2 to 6, preferably 3, and

R is methyl or ethyl, preferably with bis- (3-triethoxysilylpropyl) -tetrasulfide (Si 69, Degussa AG).

The N, N '-substituted bis- (2,4-amino-s-triazin-6-yl) tetrasulfides of the formula I can advantageously be used both in the organosilane crosslinking in the absence of sulfur instead of the accelerators described in DE patent no. 25 36 674 as well as in sulfur vulcanization in the presence of organosilanes according to DE Patent No. 2,255,577 and also in the production of reverse stable organosilane-containing rubber compositions by constructing equilibrium curing systems according to DE Patent No. 2,848,559.

This applies to both carbon black-filled mixtures and mixtures containing mixtures of carbon black and silicic acid, as well as mixtures made using only silicic acid. Also, the addition of mineral fillers does not adversely affect any of the above mixtures. In the presence of silicic fillers or mixtures of carbon black and silicic acid, they form rubber / filler bonds (Kautschuk + Gummi, Kunststoffe, Vol. 8, 1977, pp. 516-523, Vol. 10, 1979, pp. 760-765 and Vol. 4, 1981, pp. 280-284) or, in the presence of carbon black, rubber-rubber bonds.

The formation of rubber / rubber crosslinking sites, in the presence of carbon black or rubber / filler crosslinking sites, in the presence of silicic acid, or both, in the case of mixtures of carbon black and silicic acid in all proportions, occurs when N, Ν'-substituted bis The (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula (I) are used alone or in admixture with each other or in admixture with conventional sulfur scavengers together with conventional sulfur donors such as Sulfasan R (morpholinedisulfide).

The compounds of the invention are used in rubber compositions which may contain other conventional components, such as, for example

- conventional reinforcing systems, ie retort carbon black, gas black, lamp black, thermal black, acetylene black, arc black, CK black, etc., but also synthetic fillers such as silicas, silicates, alumina hydrates, various types calcium carbonate and natural fillers such as clays, siliceous chalks, chalks, talc, etc., and silane-modified fillers and mixtures thereof in an amount of 5 to 300 parts per 100 parts of rubber, especially silicas and silicates;

zinc oxide and stearic acid as vulcanization promoters in amounts of 0.5 to 10 parts per 100 parts of rubber;

commonly used antioxidants, antiozonants and anti-fatigue agents such as IPPD, TMQ, etc. as well as waxes as light stabilizers and mixtures thereof;

- any emollients such as aromatic, naphthenic, paraffinic or synthetic emollients and mixtures thereof;

optionally other silanes such as γ-chloropropyl-trialkoxysilanes, vinyltrialkoxysilanes and aminoalkyltrialkoxysilanes, and mixtures thereof in an amount of 0.1 to 15, preferably 1 to 10 parts per 100 parts of fillers containing silanol groups such as silicas, silicates, clays, etc.;

- colorants and processing aids, if any, in the usual dosage.

The range of applications in which rubber compositions containing N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides may be used includes the use in tire manufacturing, in the manufacture of technical products such as conveying belts, V-belts, wrought products, hoses with or without liner, rolled rubber products, linings, injection molded profiles, foils, bottoms and uppers of shoes, cables and solid rubber tires.

Examples of compounds of the invention include the following products;

A bis- (2-ethylamino-4-diisopropylamino-s-triazin-6-yl) tetrasulfide,

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

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

D bis- (2-ethylamino-4-diisobutylamino-s-triazin-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

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

Example 1

454 g of 2-ethylamino-4-diethylamino-6-mercaptotriazine are dissolved in a sodium hydroxide solution prepared from 84 g of sodium hydroxide and 1.5 liters of water.

The solution is placed in a 4 liter three-necked flask, 1.5 liters of light gasoline (boiling point 80-110 ° C) are added and the mixture is cooled to 0 ° C with vigorous stirring.

137 g of sulfur trichloride (S ₂ Cl ₂ ) in 100 ml of petrol are added to the mixture over a period of 20 minutes, taking care that the temperature does not exceed + 5 ° C.

Tetrasulfide is precipitated immediately. After completion of the reaction, the mixture was stirred for a further five minutes and then the product was filtered off and washed.

The fine snow-white powder is dried at 40-45 ° C under a vacuum of 15 mm Hg.

Yield: 499.5 g (97.1% of theory);

Analysis:

bis- (2-ethylamino-4-diethylamino-s-triazin-6-yl) tetrasulfide, molecular weight 516, ^{C 13 H} 32 ^{N 10 S} 4 calculated C 41.9, H 6.2, N 27.1, S 24 Found: C 41.8, H 6.5, N 26.8, S 24.8.

TLC and HPLC analysis indicated that the product contained 97.1% linear tetrasulfide.

Example 2

56.6 g of 2-ethylamino-4-di-n-butylamino-6-mercaptotriazine are dissolved in a solution of 8.8 g of sodium hydroxide in 250 ml of water. 250 ml of gasoline was added to the mixture and the resulting mixture was cooled to 5 ° C with good stirring. A solution of 13.5 g of sulfur trichloride (30 ml) in 30 ml of petrol is then added. Immediately a white deposit is formed. After completion of the reaction, the reaction mixture was worked up as in Example 1. The yield was 56 g, corresponding to 89.2% of theory.

Analysis:

^C 26 ^H 48 ^N 10 ^S 4 (^^ Nominal weight 628): Calculated: C 49.68, H 7.64, N 22.29, S 20.38 Found: C 49.59, H 7.59, N 22.18, S 20.40.

HPLC-analysis: degree of purity> 96%.

Example 3

107.6 g of 2-i-propaylamino-4-diisopropylamino-6-mercaptotriazine are dissolved in a sodium hydroxide solution prepared from 17.6 g of sodium hydroxide and 600 ml of water and 600 ml of methylene chloride are added.

27 g of sulfur trichloride (S2Cl2) in 50 ml of methylene chloride are added to the mixture at 0-5 ° C. After completion of the reaction, the organic phase was separated in a separatory funnel, dried and evaporated in vacuo. An amorphous powder is obtained having a softening point of 90 ° C.

Yield: 112.5 g (94%).

Analysis:

^C 24 ^H 44 ^N 10 ^S 4 mass 600, calculated: C 48.0, H 7.33, N 23.3, S 21.3 / found: C 48.2, H 7.36, N 23.01, S, 20.95.

Test standards

The physical properties are tested at room temperature according to the following standards:

tensile strength, ductility and strain value on 6 mm thick rings hardness Shore-A ball rebound (reversion) incubation time ti compound vulcanization time

It is used in the application examples

RSS:

C0RAX ^(R) N 220:

Naftolen ^^ ZD:

Ingraplast ^(R> NS):

standard / regulation units DIN 53504 MPa DIN 53505 - AD 20245 % DE patent 2848559 DIN 53529 min ASTM D 2084 min

names and abbreviations having the following meanings: Ribbed Smoked Sheet (natural rubber) carbon black, surface area (BET) 120 m ² / g (Degussa) hydrocarbon softener naphthenic hydrocarbon softener

Vulkanox * ^R) 4010 NA: N-isopropyl-N ¹ -phenyl-p-phenylenediamine Vulkanox ^ ¹ HS: poly-2,2,4-trimethyl-1,2-dihydroquinoline Mesamoll ^: an alkylsulfonic acid ester of phenol and cresol Robac P 25: dipentamethylenethiuramtetrasulfide Tetrone A: dipentamethylenethiuramhexasulfide Protector ^(R) G 35: antiozonant wax Vulkacit ^ ^R ) MOZ: benzthiazolyl-2-morpholinosulfenamide Vulcacite ( ^R ) Mercapto: 2-mercaptobenzthiazole Vulcacite ^(R ) Thiuram: tetramethylthiurammonosulfide Vulcacite ^<R) CZ: N-cyclohexyl-2-benzothiazolesulfenamide Vulkalent ^(R) E: N-phenyl-N- (trichloromethylsulfenyl) benzenesulfonamide PVI: N-cyclohexylthiophthalimide Ultrasil ^(R) VN 3: precipitated silica (Degussa) grain. granulate V 143: bis- (2-ethylamino-4-diethylamino-s-triazin-6-yl) di sulphide Vulkacit * ^R ) NZ: benzothiazyl-2-tert-butylsulfenamide Example 4

Reverse Stability with N, Ν'-Substituted Bis- (2,4-Diamino-s-Triazin-6-yl) Tetrasulfides Sulfurized (without Sulfur) NR Mixtures Filled with N220

Mixture number 1 2 3 4 RSS 1, ML4 = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 50 50 ZnO RS 5 5 5 5 stearic acid 2 2 2 2 Naftolen ZD 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 Vulkacit MOZ 1.43 - - - V 143 - 1.29 - - Santoguard PVI - 0.4 - - (B) - - 3.34 - D - - - 4.10 sulfur 1.5 1.5 - - Reverse: ^ max D (max + 60 ') 30.1 8.6 2.3 2.1

D -D. max mxn at a vulcanization temperature of 170 ° C

When used as sulfur-free crosslinkers, the N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of the invention impart exceptional reverse stability to carbon black-filled NR (mixtures 3 to 4) in comparison with mixture containing semi-EV-system (mixture 1) or mixture containing bis- (2-ethylamine-4-diethylamine-s-triazin-6-yl) disulfide (V 143) (mixture

2).

Example 5

Reverse stability of NR-mixture filled with N220 silica and crosslinked

N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides (without sulfur)

Mixture number 8 9 10 11 12 RSS 1, ML (1 + 4 = 70-80) 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 25 25 25 25 25 Ultrasil VP 3 gran. 25 25 25 25 25 ZnO RS 5 5 5 5 5 stearic acid 2 2 2 2 2 Naftolen ZD 3 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 Vulkacit MOZ 1.43 - - - - C - 3.48 - - - E - - 3.46 - - G - - - 3.62 - X -  - - - 3.78 sulfur 1.5 - - - - reverse: ^D max ^D (max + 60 ')% 47.1 1,8 .2,4 3.3 6.2

at a vulcanization temperature of 170 ° C

The NR mixtures containing silicic acid show strong reversal effects even using semi-EV systems (mixture No. 8). When Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides (mixtures Nos. 9 to 12) are used as the crosslinking agent according to the invention, an almost identical composition of mixtures is obtained with almost the same composition Reverse suppression.

Example 6

Resistance to reversion of NR-mixtures filled with N 220 and accelerated by Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides

mixture number 16 17 18 19 Dec 20 May RSS 1, ML (1 + 4) = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 50 50 50

CS 276 589 B 6

mixture number 16 17 18 19 Dec 20 May ZnO RS 5 5 5 5 5 stearic acid 2 2 2 2 2 Naftolen ZD 3 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 Vulkacit MOZ 1.43 - - - - (B) - 1.66 - - - C - - 1.74 - D - - - 1.76 E - - - - 1.73 sulfur 1.5 0.8 0.8 0.8 0.8 ^D max ” ^D (max + 60 ') $ 31.9 0.4 0.0 0.0 1.3

D - D. max min at vulcanization temperature 170 c Properties of vulcanizate at 170 ° C,

t 95% tensile strength 23.0 22.6 24.1 21.3 20.8 stress at 300% elongation 9.6 10.9 10.9 10.5 9.1

Reverse Resistance to NR-Mixtures Filled with N220 and Accelerated by N, Ν'-Substituted Bis- (2,4-Diamino-s-Triazin-6-yl) Tetrasulfides

mixture number 21 22nd 23 24 RSS 1 ,. ML (1 + 4) = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 ⁵⁰ 50 ZnO RS 5 5 5 5 stearic acid 2 2 2 2 Naftolen ZD 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 F 1.65 - - - G - 1.81 - - H - - 1.82 - AND - - - 1.82 sulfur 0.8 0.8 0.8 0.8

mixture number

22 23 24 reverse:

^D max ^D (max + 60 ') _%

D - D. max mm at vulcanization temperature 170 C vulcanizate properties at 170 C, t 85% tensile strength stress at 300% elongation

1.3 2,0 1,2 2.1 19.9 22.1 22.0 23.2 10.4 10.8 11.9 10.5

At equimolar dosing of the accelerator, the amount of sulfur can be reduced for N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides. However, a higher stress value is achieved at 300% elongation. Mixtures made using N, N'-disubstituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides or -oligosulfides (mixtures 17 to 27) are exceptionally reverse stable compared to mixtures containing semi-EV -system (mixture no. 16).

Example 7

Comparison of the acceleration efficiency of sulfenamide and Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide in the case of N 220 filled NR mixtures at the same dosage S _g mixture number 28 29

RSS 1 ML (1 + 4) = 70-80 100

CORAX N 220 50

ZnO RS 5 stearic acid 2

Naphtholene ZD 3

Protector G 35 1

Vulkanox 4010 NA 2.5

Vulkanox HS 1.5

Vulcacit MOZ 1.43

D sulfur 1.5 reverse:

^D max ^D (max + 60 ') _% 31.9

D - D. max mm

100 ALIGN!

2.5

1.5

1.76

1.5

5.1 at a vulcanization temperature of 170 ° C

Properties of the vulcanizate at 160 ° C, t 95 '% stress at 300% elongation MPa 10.6

12.8 Shore-A hardness

Example 6 showed a comparison of MOZ with N, N '-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides, at different sulfur concentrations. If, on the other hand, the sulfur concentration is kept constant at an equimolar amount of the accelerator, the reversal difference remains, but the voltage value at 300% elongation increases significantly.

Example 8

A mixture of N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide with a sulfur donor in a NR mixture filled with N 220 mixture number 34 35

RSS 1 ML (1 + 4) = 70-80 100

CORAX N 220 50

ZnO RS 5 stearic acid 2

Naphtholene ZD 3

Protector G 35 1

Vulkanox 4010 NA 2.5

Vulkanox HS 1.5

Vulcacit MOZ 1.43

100 ALIGN!

2.5

1.5

Sulfasan R

D sulfur 1.5 reverse:

^D max ' ^D (max + 60') _% 30.6

D - D. max nun at a vulcanization temperature of 170 C

0.7

1.76

2.1

Compared to conventional sulfenamide acceleration (mixture 34), the use of N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide and the sulfur donor Sulfase nu R (mixture 35) is achieved improving reverse.

Example 9

A mixture of commercially available accelerators with N, N‘-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfide in NR-mixtures filled with N 220.

mixture number 36 37 38 39 40

RSS 1, ML (1 + 4) = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 50 50 50 ZnO RS 5 5 5 5 5 stearic acid 2 2 2 2 2 Naftolen ZD 3 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 2,

mixture number

Vulkanox HS

Protector G 35

Vulkacit MOZ

Vulkacit DM

B sulfur reverse:

1.5

1.43

1.5

1.5

0.71

0.8

1.5

1.5

1.5

1.58

1.5

1.56

1.5

1.5

0.78

0.8

1.5 ^D max ” ^D (max + 60 ')

28.7

16.8

5.7

31.2 16.1 max

D. mm at vulcanization temperature 170 c Properties of vulcanizate at 170 'c stress at 300% elongation, t 95% 11.3 t 95% + 90' 8.9

11.9

10.7

6.8

6.7

9.0

7.5

11.4

10.5

Mixture of commercially available accelerators with N, N'-substituted bis- (2,4-diaminos-triazin-6-yl) -tetrasulfide in NR-mixtures filled with N 220 mixture no.

RSS 1, (ML 1 + 4) = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 50 50 ZnO RS 5 5 5 5 stearic acid 2 2 2 2 Naftolen ZD 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 Vulkacit DM 1.56 - - - Vulkacit Merkapto - 1,2 0.6 1,2 (B) 1.58 - 0.8 1.58 sulfur reversal: ^D max ^D (max + 60 ') 1.5 1.5 % D - D. max mm at a vulcanization temperature of 170 ° C Properties of the vulcanizate at 170 ° C 4.1 28.7 14.9 4,5 stress at 300% elongation t 95% 7.0 7.8 11.3 5.9 t 95% + 80 ' 6.9 6.5 10.8 5.9

The combined use of commercially available accelerators with N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides (mixtures 37, 40, 41) results in a clear improvement in reverse behavior compared to the use of commercially available accelerators alone (mixtures 36, 39, 42). A further increase in reverse stability can be achieved by discharging sulfur (mixtures Nos. 38, 41 and 44).

Example 10

Reverse when accelerating with substance B in NR-mixtures filled with a mixture of carbon black and silicic acid mixture number 49 50

RSS 1 ML (1 + 4) = 70-80 100

CORAX N 220 25

Ultrasil VP 3 gran. 25

ZnO RS 5 stearic acid 2

Naphtholene D 3

Protector G 35 1

Vulkanox 4010 NA 2.5

Vulkanox HS 1.5

Vulcacit MOZ 1.43

B sulfur 1.5 reverse:

max max ^D (max + 60 ') _% 46.7

D - D. max mm

100 ALIGN!

2.5

1.5

1.67

0.8

10.8 at a vulcanization temperature of 170 c

When the sulfenamide accelerator (mixture 49) is replaced with N, Ν '-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfide (mixture 50), the reversion drops drastically.

Example 11

N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides in SBR-mixtures filled with N 220 mixture number 51 52 53

SBR 1500

CORAX N 220

ZnO RS stearic acid

Naftolen ZD

Protector G 35

Vulkanox 4010 NA

100 ALIGN!

2.5

100 ALIGN!

2.5

100 ALIGN!

2.5

Mixture No. 51 52 53

Vulkanox HS 1.5 1.5 1.5 Protector G 35 1 1 1 Vulkacit MOZ 1.43 - - (B) - 1.66 - P - - 1.58 sulfur 1.5 1.5 1.5 reverse: ^D max ^D (max + 60 ')% 12.9 11.3 11.5 D - D. max min at a vulcanization temperature of 170 ° C properties of vulcanisate at 170 C, t 95% tensile strength 20.6 21.3 20.8 voltage at 300% elongation 10.0 11.6 12.2 ductility 460 440 420 Shore hardness 61 63 63 At the same sulfur dosage, N, Ν'-substituted bis- (2,4- -diamino-s-triazine- -6-yl) tetrasulfides (mixtures 52 and 53) v SBR 1500 significantly higher voltage value and slightly better · Reversed properties versus conventional acceleration (mixture 51). Example 12 N, Ν'-substituted bis- (2,4-diamino-s-triazine-6- yl) tetrasulfides in mixtures isoprene rubber filled with N 220 mixture number 56 57 polyisoprene 3.4 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 ZnO RS 5 5 stearic acid 2 2 Naftolen ZD 3 3 Vulkanox 4010 NA 2.5 · 2.5 Vulkanox HS 1.5 1.5 Protector G 35 1 1 Vulkacit MOZ 1.43 - (B) - 1.76 sulfur . 1.5 0.8 reverse: ^D max ^ (max + 60 ') (%) 21.0 2.1

D - D. max mm at vulcanization temperature 170 c vulcanizate properties at 170 C stress at 300% elongation, t 95% 7.9 6.6 t 95 i + 80 '6.2 6.8

Even with polyisoprene rubber, the use of Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides (mixture 57) results in a significant improvement in the reversion compared to the mixture containing the conventional accelerator (mixture 56). . This improvement is also manifested in the stability of the vulcanizate properties under considerable overheating.

Example 13

N, N'-substituted bis- (2,4-diaminotriazin-6-yl) tetrasulfides in EPDM mixtures filled with N 220 mixture number 60 61

Buna AP 451 100

CORAX N 220 50

ZnO RS 5 stearic acid 2

Ingraplast NS 10

Vulkacit Thiuram 2

Vulkacit Mercapto 0.5

B sulfur 1

Djnax D (max + 60 ') _% 3.3

D - D. max min

100 ALIGN!

2.93

0.0 at a vulcanization temperature of 160 ° C.

EPDM mixtures, which are themselves reversible, exhibit a further reduction in reversion down to zero when the conventional accelerator mixtures (mixture 60) are replaced with N, N'-substituted bis- (2,4-diamino-s-triazine- 6-yl) tetrasulfides (mixture 61).

Example 14

Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides in NBR mixtures filled with N 220 mixture number 63 64

Perbunan N 3307 NS 100 100

CORAX N 220 60 60

5

1

1

ZnO RS stearic acid paraffin solid

mixture number 63 64 Mesamoll 10 10 Vulkanox HS 1.5 1.5 Vulkacit CZ 1.5 1.5 D - 1.76 sulfur 1,2 1,2 reverse: ^D max ^D (max + 60 ')% 8.6 5.4

D - D. max mm at a vulcanization temperature of 170 ° C.

Properties of vulcanizate at 170 ° C, t 95%

voltage at 300% elongation 11.8 14.0 Shore hardness 68 69

At the same sulfur content, there is a strong increase in the voltage value at NBR over the reference mixture (mixture 63) using N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides (mixture 64) in NBR. 300% elongation while reducing reverse.

Example 15

Reverse stability for BR-mixtures filled with N 220 containing N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides mixture number 66 68

Buna CB 100 100 100

CORAX N 220 60 60

ZnO RS 33 stearic acid 2 2

Naphtholene ZD 15 15

Protector G 35

Vulkanox 4010 NA 1.5 1.5

Vulkacit NZ 1,5

D - 1,76 sulfur 1,5 1,5

Dfliax 'D (min + 60') _% 30.3 19.1

D - D. max mm at vulcanization temperature 170 C vulcanizate properties at 170 ° C stress at 300% elongation t 95% 8.6 8.2 t 95% + 75 '5.6 6.6

Due to the lower reversion of the BR mixtures, whose vulcanization is accelerated by D (mixture 68), the voltage drop at 300% elongation under severe overheating is significantly reduced compared to the reference mixture (mixture 66).

Example 16

N, N'-substituted fully NR / BR based bis- NYCHA - (2,4-diamino-s-triazine- N 220 6-yl) tetrasulfides in mixtures mixture number 69 70 71 RSS 1, ML (1 + 4) = 70-80 70 70 70 Buna CB 30 30 30 CORAX N 220 50 50 50 ZnO RS 5 5 5 stearic acid 2 2 2 Naftolen ZD 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 Protector G 35 1 1 1 Vulkacit MOZ 1.43 - - C - 1.74 - D - - 1.76 sulfur 1.5 0.8 0.8 reverse: ^D max ~ ^D (max + 60 ')% 32.0 15.8 20.6

D - D. max mm at a vulcanization temperature of 170 C.

Compounds based on NR and polybutadiene (mixtures 70 and 71) show, using N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides as compared to mixtures containing the semi-EV system ( mixture 69) significantly reduced reversion.

Example 17 Crosslinking of natural rubber by N, Ν'-substituted epoxidized from 50% (ENR 50) filled with N 220 bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides mixture number 73 74 ENR 50 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 ZnO RS 5 5 stearic acid 2 2 Vulkanox HS 2 2 Vulkacit MOZ 2.4 - Vulkacit Thiuram 1.6 -

mixture number 73 74

C - 4.6 sulfur 0.3 0.3 reverse:

^D max ~ ^P (max + 60 ') _{% 6} , _{7 θθ}

D - D. max min at vulcanization temperature 150 c properties of vulcanizate at 150 ‘c, t 95%

tensile strength 18.7 23.7 voltage at 300% elongation 18.0 18.4 structural strength 12 14 Shore hardness 75 76

The use of Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides (mixture 74) leads to an improvement in reversion while maintaining the stress value at 300% compared to conventional accelerators (mixture 73). elongation and greatly increase the structural strength.

Example 18

The action of Vulcalent E in crosslinking NR-mixtures filled with N 220 and combinations

N 220 / silicic acid, which is carried out without sulfur by the action of Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides

mixture number 76 77 78 79 80 81 RSS 1, ML (1 + 4) = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 50 25 25 25 Ultrasil VP 3 gran. - - - 25 25 25 ZnO RS 5 5 5 5 5 5 stearic acid 2 2 2 2 2 2 Naftolen ZD 3 3 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 1 Vulkacit MOZ 1.43 - - 1.43 - C - 3.79 3.79 - 2.84 2.84 Vulkalent E - - 3.2 - - 2.4 sulfur 1.5 - - 1.5 - - reverse: Djnax ^D (max + 60 ') 32.5 4.1 4,5, 47.8; 5.4 5.5 D D. max - min at a vulcanization temperature of 170 c and 170 C (min) 4.2 2.8 4,5 4.7 3.0 4.7

CS 27S589 B6

With the addition of Vulcalent E, the NR-mixtures filled with N 220 and N 220 / silicic acid and crosslinked with substance C achieve the desired incubation time extension without impairing the reversion.

Example 19

The retarding effect of Vulcalent E on the vulcanization of NR-mixtures vulcanized with N, Ν'-substituted bis- (2,4-diamino-triazin-6-yl) tetrasulfide filled with N 220

mixture number 82 83 84 RSS 1, ML4 = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 50 ZnO RS 5 5 5 stearic acid 2 2 2 Naftolen ZD 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 Protector G 35 1 1 1 Vulkacit MOZ 1.43 - - (B) - 1.66 1.66 sulfur 1.5 0.8 0.8 Vulkalent E - - 1,2 t (min) at 170 ° C 3.8 3.0 4.4 vulcanizate properties at 170 ° C, t 95% voltage at 300% elongation 10.6 10.2 11.5

The addition of Vulcalent E to the accelerator B accelerated mixture leads to an increase in the incubation time t1 above that achievable with a conventional MOZ accelerated mixture (mixture 82).

Example 20

Effect of N, Ν '-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides with the addition of Vulcalent E in NR-mixtures filled with N 220 depending on the temperature of mixture No. 87 88 89

RSS 1 ML (1 + 4) = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 50 50 50 ZnO RS 5 5 5 stearic acid 2 2 2 Naftolen ZD 3 3 3 Protector G 35 1 1 1 Vulkanox 4010 NA 2.5 2.5 2,

mixture number

88 89

Vulkanox HS

Vulkacit MOZ

(B)

Vulcalent E sulfur reverse:

^D max ~ ^D (max + 60 ') _%

D - D. max min at test temperature 145 c at test temperature 160 * C at test temperature 170 * C at test temperature 180 ´C

1.5 1.5 1.5 1.43 - - - 1.66 1.66 - - 1,2 1.5 0.8 0.8

7.9 0.0 0.0 25.6 0.0 1.9 30.9 0.4 3.6 39.1 2.6 5.5

Example 20 shows that using pure N, čist'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides as accelerators (mixture 88) or mixtures thereof with Vulcalent E (mixture 89). ), a significant insensitivity of the temperature reversal is achieved compared to the use of conventional accelerators (mixture 87).

Example 21

Effect of Vulcalent E on NR-mixtures -s-triazin-6-yl) tetrasulfide and sulfur-bearing N, bis-substituted bis- (2,4-diamino-filled N 220)

mixture number 90 91 92 RSS 1, ML (1 + 4) = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! Ultrasil VP 3 gran. 25 25 25 CORAX N 220 25 25 25 ZnO RS 5 5 5 stearic acid 2 2 2 Naftolen ZD 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 Protector G 35 1 1 1 Vulkacit MOZ 1.43 - - D - 3.5 3.5 Vulkalent E - - 1,2 sulfur 1.5 0.8 0.8 the vulcanization time of the mixture at 130 ’C (min) 29.5 15.0 28.5 at 170 ° C (min) 4,5 3.4 4.4

Vulcalent E allows N, Ν'-substituted bis- (2,4-diamino) CS 276589 B6 to accelerate

-s-triazin-6-yl) tetrasulfides (mixtures 91 and 92) to set the vulcanization time of the mixture comparable to that of MOZ.

Example 22

Concomitant use of N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfide and Si 69 with or without Vulcalent E in NR-mixtures filled with N 220 / VN

mixture number 95 96 97 ⁹⁸ 99 RSS 1, ML (1 + 4) = 70-80 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 25 25 25 25 25 Ultrasil VP 3 gran. 25 25 25 25 25 Si 69 3.75 3.75 3.75 3.75 3.75 ZnO RS 5 5 5 5 5 stearic acid 2 2 2 2 2 Naftolen ZD 3 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 Vulkacit MOZ 1.43 - - - - (B) - 2.2 2.2 1.66 1.66 Vulkalent E, - - 1.6 - 1,2 sulfur 1.5 - - 0.8 0.8 reverse: ^D max ^D (max + 60 ') _% 19.6 0.0 0.0 0.0 0.0 D “D. max mm at vulcanization temperature ti at 170 c (min) 170 ° C 4.6 4.2 5.7 4.2 5.2

Combined use of N, N ' -substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides and Si 69 yields a reversed plain mixture with or without sulfur (mixtures 96, 98). as opposed to a mixture with a conventional accelerator and a strong one (mixture 95). In this case, the addition of Vulcalent E leads to an increase in the vulcanization time without reversing again (mixtures 97 and 99).

Example 23

Crosslinking of NR-mixtures filled with the combination of N 220 / silicic acid using

Sulfur-free N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide

RSS 1 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 25 25 25 25 25 25 25 Ultr. VN 3 gran. 25 25 25 25 25 25 25 ZnO RS 5 5 5 5 5 5 5 stearic acid 2 2 2 2 2 2 2 Naftolen ZD 3 3 3 3 3 3 3

Vulkanox 4010 NA

Vulkanox HS

Protector G 35

Vulkacit MOZ

D

2.5 2.5 2.5

1.5 1.5 1.5

1 1

1.43

- 2 3

2.5

1.5 sulfur 1.5 ^D max ^P (max + 60 ') _% 3.2 2.0

D - D.

max mm at vulcanization temperature 170 ´C vulcanizate properties (t 95%) at 170 ‘C stress at 300% elongation 4.9 2.6 4.4

1.3

2.5

1.5

3.1

2.5

1.5

2.8

2.5

1.5

2.6

5.8

Crosslinking with N, Ν '-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide leads to suppression of reversal and an increase in the amount-dependent voltage value of natural carbon black and silica-filled rubber. crosslinking agents.

Example 24

Crosslinking of NR-based silicic acid mixtures with N, Ν'-substituted bis- (2,4 2,4-diamino-s-triazin-6-yl) tetrasulfide

RSS 1 100 ALIGN! 100 ALIGN! Ultr. VN 3 gran. 50 50 ZnO RS 5 5 stearic acid 2 2 Naftolen ZD 3 3 Vulkanox 4010 NA 2.5 2.5 Vulkanox HS 1.5 1.5 Protector G 35 1 1 Vulkacit MOZ 1.43 - D - 7 sulfur 1.5 - ^D max ” ^D (max + 60 ') _% 33.0 7,

D - D. max mm at vulcanization temperature 170 c vulcanizate properties (t 95%) at 170 ° C stress at 300% elongation 2,7 4,3

Sulfur-free crosslinking with N, Ν '-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide results in a significant reduction in reversion while increasing the value of tension at 300% elongation in silicic acid-filled natural rubber. .

Example 25

Acceleration of vulcanization of NR-based mixtures filled with N 220 / silica combination using N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfide

RSS 1 100 ALIGN! 100 ALIGN! CORAX N 220 25 25 Ultr. VN 3 gran. 25 25 ZnO RS 5 5 stearic acid 2 2 Naftolen ZD 3 3 Vulkanox 4010 NA 2.5 2.5 Vulkanox HS 1.5 1.5 Protector G 35 1 1 Vulkacit MOZ 1.43 - (B) - 2 sulfur 1.5 0.51 ^D max ” ^D (max + 60 ') 44.7 3.2

D - D. max min at vulcanization temperature 170 c vulcanizate properties (t 95%) at 170 c stress at 300% elongation 3,6 3,5

100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 25 25 25 25 25 25 25 25 25 25 5 5 5 5 5 2 2 2 2 2 3 3 3 3 3 2.5 2.5 2.5 2.5 2, 1.5 1.5 1.5 1.5 1, 1 1 1 1 1 - - - - - 3 4 5 6 7 0.76 1,02 1,27 1.53 1, ' 1.7 0 O 0.8 1, ' 5.5 7.0 8.3 9.2 9,

Sulfur vulcanization using N, Ν '-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfide results in a reduction of the reversion to 0% and a strong increase in NR-based mixtures filled with N 220 / silica voltage values.

Example 26

Accelerating the vulcanization of NR-based silica-filled mixtures with N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide

RSS 1 100 ALIGN! 100 ALIGN! Ultr. VN 3 gran. 50 50 ZnO RS 5 5 stearic acid 2 2 Naftolen ZD 3 3 Vulkanox 4010 NA 2.5 2.5 Vulkanox HS 1.5 1.5 Protector G 35 1 1 Vulkacit MOZ 1.43 - (B) - 7 sulfur 1.5 1.79

4,5

5.3 ^D max ~ ^D (max + 60 ') _% 33 O

D - D. max mm at vulcanization temperature 170 * C vulcanizate properties (t 95%) at 170 ´C stress at 300% elongation 2,7

Sulfur vulcanization using N, Ν '-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide proceeds almost non-reversed with NR-based silicic acid mixtures and increases the stress value at 300 % elongation.

Example 27

Acceleration of vulcanization of NR-based mixtures filled with N 220 / silicic acid mixtures with N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides in the presence of Si 69

RSS 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 25 25 25 Ultr. VN 3 gran. 25 25 25 Si 69 3.75 3.75 3.75 ZnO RS 5 5 5 stearic acid 2 2 2 Naftolen ZD 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 Protector G 35 1 1 1 Vulkacit MOZ 1.43 - - (B) - 2 3 sulfur 1.5 0.49 0.74 ^D max ^{- D} (max + 60 ') 18.1 0 0 D - D. max min at a vulcanization temperature of 170 properties of vulcanizate (t 95 voltage at 100% elongation *C %) at 170 ° C 1.4 1.6 2.4 voltage at 200% elongation 3.5 4.6 7.3 voltage at 300% elongation 7.1 9.5 13.9

Acceleration with N, N ' -substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide in the presence of Si 69 results in suppression of the reversion to 0% with a large increase in voltage value.

Example 28

Accelerating the vulcanization of NR-based silica-filled mixtures with N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide in the presence of Si 69

RSS 1 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! Ultr. VN 3 gran. 50 50 50 50 Si 69 7.5 7.5 7,5 - 7.5 ZnO RS 5 5 5 5 stearic acid 2 2 2 2 Naftolen ZD 3 3 3 3 Vulkanox 4010 NA 2,5, 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 Vulkacit MOZ 1.43 - - - (B) - 2 3 4 sulfur 1.5 0.49 0.74 0.99 ^D max ~ ^D (max + 60 ')% 16.6 0 0 0 D - D. max mm at a vulcanization temperature of 170 *C vulcanizate properties (t 95 %) at 170 ° C voltage at 100% elongation 1.5 1.7 2.5 3.2 voltage at 200% elongation 3.4 4.3 6.6 8.3 voltage at 300% elongation 6.3 8.2 12.3 15.0

Even in the case of only silica filling, the NR-based compounds are vulcanized in the presence of Si 69 with sulfur and N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetra sulfide without reversing, at the same time, the voltage levels will increase strongly.

Example 29

Crosslinking of NR-based mixtures filled with N 220 / silicic acid in the absence of sulfur using N, Ν'-disubstituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfide in the presence of Si 69

RSS 1 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! CORAX N 220 25 25 25 25 25 Ultr. VN 3 gran. 25 25 25 25 25 Si 69 3.75 3.75 3.75 3.75 3.75 ZnO RS 5 5 5 5 5 stearic acid 2 2 2 2 2 Naftolen ZD 3 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 1.5

Protector G 35 1 1 1 1 1 Vulkacit MOZ 1.43 - - - - D - 1 2 3 4 sulfur 1.5 - - - - ^D max ^D (max + 60 ') % 18.1 0 0 0 0 D - D. max mm during vulcanization temperature 170 *C vulcanizate properties (t 95 %) at 170 'C voltage at 200% protaženi 3.5 2.6 4.9 6.5 8.6 voltage at 300% stretching 7.1 5.8 10.2 12.9 16.0

Sulfur-free crosslinking with N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfide results in both carbon black-filled and silicic acid-based mixtures with the addition of Si 69 to simultaneously remove reverse and a strong increase in the voltage value, which is dependent on the amount of crosslinker.

Example 30

Crosslinking of NR-based silicon-filled mixtures in the absence of sulfur with N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetrasulfides in the presence of Si 69

RSS 1 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! Oltr. VN 3 gran. 50 50 50 50 50 Si 69 7.5 7.5 7.5 7.5 7.5 ZnO RS 5 5 5 5 5 stearic acid 2 2 2 2 2 Naftolen ZD 3 3 3 3 3 Vulkanox 4010 NA 2.5 2.5 2.5 2.5 2.5 Vulkanox HS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 Vulkacit MOZ 1.43 - - - - D - 1 2 2 4 sulfur 1.5 - - - - ^ max D (max + 60 ') % 16.6 0 0 0 0 D - D. max min at a vulcanization temperature of 170 'C vulcanizate properties (t 95 %) at 170 C voltage at 200% elongation 3.4 2.8 3.9 5.0 7.6 voltage at 300% elongation 6.3 5.0 7.6 11.3 13.9 N, pomocí'-substituted bis- (2,4-diamino-s-t riazi

For example, in the case of a mixture based on natural rubber filled with silicic acid only, in the presence of Si 69, it also proceeds without reversing and at the same time leads to a strong increase in the vulcanizate stress values.

Claims (9)

PATENT CLAIMS N, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of formula I wherein: R 6 represents a hydrogen atom, R is hydrogen or benzyl, each of R 1, R 1 and R 1 is C 1 -C 8 alkyl, allyl, C 3 -C 8 cycloalkyl optionally substituted with 1 to 3 methyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or R ² and R ⁴ together represent an alkylene group having 4 to 6 carbon atoms or a group of the formula - (ch ₂ -chx) ₂ y, where X is methyl or hydrogen; and Y represents oxygen or sulfur. A process for the preparation of N, N * -substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides of the general formula X according to claim 1, characterized in that an aqueous alkaline solution corresponding to N, Ν'- Substituted 2,4-diamino-6-mercaptotriazine is reacted in a biphasic system with a solution of sulfur trichloride in an inert organic solvent in which the tetrasulfide formed does not dissolve or little dissolves. 3. The process of claim 2 wherein the alkali hydroxide is used in an amount of at least stoichiometric relative to the reaction being performed. 4. The process according to claim 3, wherein the alkali hydroxide is used in an excess of 1 to 20 mole% based on mercaptotriazine. 5. Process according to claim 2, characterized in that sodium hydroxide or potassium hydroxide is used as the alkali hydroxide and C5 to C10 alkanes are optionally substituted with 1 to 3 methyl groups. Use of the tetrasulphides according to item 1 as accelerators in vulcanizable mixtures based on one or more natural and / or synthetic rubbers, these mixtures containing fillers, sulfur and other conventional components and optionally containing further compounds according to claim 1 or conventional accelerators, in particular sulfenamides, dibenzthiazolyldisulfide and / or thiurams, sulfur donors and / or retardants and / or organosilanes. Use of the tetrasulphides according to item 1 as crosslinking agents in vulcanizable mixtures based on one or more natural and / or synthetic rubbers, said mixtures being free of sulfur, containing fillers and other conventional components and optionally containing further compounds according to claim 1 or conventional accelerators, in particular sulfenamides, dibenzthiazolyldisulfide and / or thiurams, sulfur donors and / or retardants and / or organosilanes. Vulcanizable mixtures based on one or more natural and / or synthetic rubbers, containing fillers, sulfur and other conventional components, characterized in that they contain per 100 parts by weight. 0.01 to 10 parts, preferably 0.1 to 5 parts by weight of rubber; tetrasulfides according to claim 1 and mixtures thereof and / or mixtures thereof with conventional accelerators at a sulfur dosage of from 0.1 to 10 parts by weight. per 100 parts by weight. rubber. Vulcanizable mixtures based on one or more natural and / or synthetic rubbers, containing fillers and other conventional components, but not containing sulfur, characterized in that they contain per 100 parts by weight. rubber 0.2 to 15 parts, preferably 0.3 to 8 parts of the compounds according to claim 1 or mixtures thereof or mixtures thereof with conventional accelerators.