DD270302A5 - N, n'-substituted bis- (2,4-diamino-S-triazin-6-yl) tetra-sulfides and their disproportionation products, process for their preparation and their use in vulcanizable rubber mixtures - 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

Field of application of the invention The invention relates to a process for the preparation of N, N'-6substituted Ei6- (2,4-diamino-8-triazin-6-yl) tetrasulfides, process

for the preparation of their disproportionation products, the use of the tetrasulfides and the disproportionation products as crosslinkers or vulcanization accelerators in rubber mixtures, and vulcanizable compositions containing them.

The rubber mixtures of the invention are used in tire construction, for the production of conveyor belts, V-belts, molded articles, hoses with and without inserts, roll rubbers, linings, sprayed profiles, films, Shoe soles and tops, cables u. a. Characteristic of the known state of the art

Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) disulfides are known; they are described in DE-PS 1669 954. It is prepared from the corresponding Ν, Ν'-substituted 2,4-diamino-6-mercaptotriazines by oxidation, for example with iodine,

Sodium hypochlorite or hydrogen peroxide. The best known compound in this group is the bis- (2-ethylamino-4-di-

ethylamino-triazin-6-yl) disulphide. Disulfides of this group can be used in rubber compounds as accelerators.

The rubber processing industry has an extensive range of accelerators (J. van Alphen, Rubber Chemicals

[1977, pp. 1-46]), preferably for sulfur vulcanization, for example benzthiazolyl sulfenamides,

Benzothiazolyl disulfide and 1-mercaptobenzothiazole or their zinc salts. There are also a number of special connections such as Thiuram disulfides and ferric oxides, which act as crosslinkers even without further additives of sulfur, but often in Combination with sulfur can be used as an accelerator. The type of use depends on the particular effect to be achieved The most quantitatively important in practical application, especially in the accelerated Sulfur vulcanization accessible elastomers, today comes to Benzthiazolylsulfenamiden. However, new production processes, new articles and the need for constant rationalization in

In recent years, the mission requirements for accelerators have changed from earlier to such an extent that it is already today

Can provide difficulties, quality demands placed on the vulcanization process as well as the characteristics

the vulcanizates comply with the accelerators or crosslinkers available today for the accelerated sulfur vulcanization.

Another today no longer negligible disadvantage of some conventional accelerators (eg Sulfonamides, thiurams) is that during the vulcanization process amines can be released, the so far

they are nitrosatable - lead to the formation of nitrosamines in the vulcanizate, which - as far as they are toxic - permanently

Restricting the applications of these accelerators can be expected. A very significant disadvantage of the Benzthiazolylbeschleuniger, in particular the Benzthiazolylsulfenamide is their with

increasing vulcanization temperature increasingly pronounced tendency to reversion when inevitably often necessary

Overheating the vulcanizates, especially when using anyway reversion susceptible rubbers such as natural rubber and Polyisoprene and its blends with synthetic rubbers. The same applies to synthetic rubbers of all kinds,

unless the reversion process is covered by thermal crosslinking. Especially with rising

Vulcanization temperature increases the rate of reversion so much that, first, it is already noticeable Lowering of the crosslinking density even with optimal vulcanization per se, secondly, the vulcanization optimum

Instead of a plateau takes the form of a peak, which complicates the reproducible observance of optimal Vulkanisateigenschaftenungemein and thirdly in the necessary in many cases overvulcanization unavoidable drop in the

Crosslinking density occurs, which is particularly true for thick-walled rubber articles to cancel the uniformity of Networking in Vulkarvsat leads. As the reversion increases, so does the performance degradation Vulcanizates, e.g. in reduced 300% modulus and abrasion resistance, etc. To a certain extent, the reduction of sulfur and the increase of the accelerator fraction, i. H. the use of so-called Semi-EV systems (L Bateman, 1963 "The Chemistry and Phyics of rubber-like substances", p. 522 ff), to a mitigation of the

described reversion effects. This mitigation of the reversion is, however, achieved by a change in the crosslinking structure (ratio of -S _x -, -SS-, -S bonds) in favor of monosulfide crosslinking sites, which the

Vulcanizate properties may adversely affect. However, the higher the measure, the more ineffective this measure becomes Vulcanization temperature is set. These disadvantages of benzothiazole accelerators limit their utility with increasing vulcanization temperature and

The efforts of the rubber industry to increase productivity by using higher

Vulcanization temperatures have certain limits. Object of the invention

The aim of the invention is to provide compounds which improve the vulcanization behavior of rubber compounds and give their vulcanizates better properties.

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties and processes for their preparation.

According to the invention, compounds of the general formula

R ³ R ⁴ R ³ R ⁴ .

manufactured, in which mean:

R ¹ , R ² = H, R ² = benzyl R ² , R ³ , R * = C ₁ -Ce-AllCyI, preferably Cj-C ₄ alkyl, branched or unbranched, alkyl, Cr-Ce-cycloalkyl, the latter

unsubstituted or substituted with 1-3 methyl groups, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl

or R ³ and R ⁴ (together): CH ₂ -alkylene, - (CH ₂ -CHX) ₂ Y with X = CH ₃ , H; Y = O, S

The invention likewise provides a process for the preparation of these compounds. The process for producing the

pure tetrasulfides having a linear S ^ Ke-te between the two substituted triazine radicals is characterized in thatan an aqueous, alkaline solution of the corresponding Ν, Ν'-substituted 2,4-diamino-6-mercaptotriazine in a

Two-phase system with an 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 ⁰ C - <+ 20 ° C, preferably of + 1O ⁰ C, reacted. Advantageously, an alkaline aqueous solution of mercaptotriazine is prepared,

the at least the stoichiometric amount of alkali hydroxide necessary for the reaction, preferably a? r? Üoeiäcnüß von1-20Mol-%, based on the mercaptotriazine used.

This solution is treated with a solvent in which the end product of the reaction is not or slightly soluble,

preferably with Cj-C ^ alkanes, C ₆ -C ₈ cycloalkanes, optionally substituted with 1 to 3 methyl groups and their

Mixtures. This mixture is stirred vigorously and cooled, preferably to + 1O ⁰ C. Now allowed in this mixture under good Cooling a solution of S ₂ Cl ₂ in the solvent used dropwise. S ₂ CI ₂ is at least in the ratio 2 Mo! Mercaptotriazine: 1 mol of S ₂ CI ₂ used, but this ratio may also be 2: 1.1-1.2 depending on the excess alkali. 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 dried under vacuum (10 Torr).

The application further relates to mixtures consisting of compounds of the general formula

R ³ R ⁴ R ³ R ⁴

in which R ¹ , R ² , R ³ and R ^{4 have the} same meanings as in claim 1 and S _x corresponds to a mean statistical chain length with χ = 4.

These mixtures, also referred to in the following text as oligosulfides or disproportionates, as caused by disproportionation

Compounds according to formula I can be represented in several ways.

The reaction conditions are controlled so that no free sulfur is formed. A method is characterized in that the isolated compound of formula I beyond its melting point

heated, preferably at 20-50 ⁰ C.

In a further method, the compounds of the formula I are dissolved in an inert organic solvent and led

the disproportionation reaction in the temperature range between 2.O ⁰ C (allowed to stand at room temperature) and boiling point of the solvent used by.

A particularly elegant method consists in that an aqueous alkaline solution of the corresponding N, N '

substituted 2,4-diamino-6-mercaptotriazine in a two-phase system with a solution of S ₂ CI ₂ in an inert, the tetrasulfide developing organic solvents dissolves. The resulting tetrasulfide is then immediately disproportionated into the mixture according to the invention consisting of oligosulfides.

Particularly suitable solvents are chlorinated hydrocarbons, for example CH ₂ Cl ₂ and CHCl ₃ , but also ethers,

esters as well as aromatic hydrocarbons and ketones are suitable for the disproportionation reaction. They are usable when they form a biphasic mixture with water. The reaction conditions for the preparation of

Disproportionates', ind otherwise identical to those for the preparation of compounds according to formula I.

Gegonstand invention is also the use of the claimed compounds in vulcanizable Kautschukmischungon and the erfindungogemäuen compounds containing rubber compounds themselves. Erfindungsgemäßsn tetrasulfides or their Disproportionate show its superiority over the standard compounds used today as clearly when they are used as a crosslinking agent or a vulcanization accelerator. Surprisingly, the Ν, Ν'-substituted bis (2,4-diamino-s-triazir-6-yl) tetrasulfides according to the invention and their disproportionation products prove both in terms of their use as accelerators in sulfur vulcanization and in their use as crosslinking agents , ie without the additional use of sulfur, as compounds which give the rubber mixtures produced therewith, even at high Vulkanisatinnemperaturen extremely high reversion stability-even with very strong overheating, characterized in that the otherwise usual in their use reversion process either does not occur or if, then only to a small extent. The surprising fact that the crosslinking sites produced by the ι, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates which are claimed according to the invention prove to be extraordinarily reversible and thermostable , When used in rubber mixtures even at high vulcanization temperatures to the fact that after completion of the crosslinking reaction on the one hand a high performance level of the vulcanizates is achieved and on the other hand, that even with strong overheating the high level of performance is maintained long.

Taken together, these effects combine to increase productivity in the rubber processing industry without increasing vulcanizate performance.

even approximately the same reversion resistance can not be achieved with commercially available polysulfides such as Robac® P25 (Robinson, Dipentamethylen-Thiuramtetrasulfid) and Tat ro n® A (Du Pont, Dpentamethylen-Thiuramhexasulfid) or with dibenzothiazolyl tetrasulfide.

The use of the claimed according to the invention Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides and their disproportionation comprises the known in the prior art rubber compositions based on natural rubber (NR) , Isoprene rubber (IR), butadiene rubber (BR) styrene-butadiene rubber (SBR), isobutylene-isoprene rubber (MR), ethylene-propylene gate polymer (EPDM), nitrile rubber (NBR), halogen-containing rubbers and also epoxidized natural rubbers (ENR) and their blends , Of particular importance is the use of the inventively claimed Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides and their disproportionation in the case of the reversion-prone rubber types such as natural rubber, isoprene and butadiene rubbers, as well as their blends with each other or with other rubbers.

The Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides claimed in accordance with the invention and their disproportionation products are used as crosslinkers in rubber mixtures in an amount of 0.2-15 T in., Preferably 0, 3-8 Gewichtstrtilen, used on 100 parts of rubber.

In the accelerated sulfur vulcanization, the inventively claimed Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionation as accelerators in amounts of 0.01-10TIn., Preferably 0,1-5TIn. based on 100Tie. Rubber, one at sulfur dosages of 0.1-10TIn. A molar ratio of the accelerators according to the invention to sulfur (Sg) of 1: 0.5-1.5 is preferred. In order to achieve a certain variation in the vulcanization kinetics, it may be expedient to use 2 or more Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates in a mixture, wherein to comply with the above Application levels, in particular the preferred accelerator / sulfur ratio, the substitution is to be made on a molar basis. The same applies when using the Ν, Ν'-substituted 3is - ((2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates as crosslinkers without sulfur.

Likewise, for kinetic reasons, it may prove expedient, the Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionation in admixture with conventional accelerators such. As sulfenamides and thiurams to use. These measures are sometimes prone to latency in comparison to the Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfide vulcanizates, but conversely have a positive effect on the reversion behavior when replacing conventional accelerators partially by Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates.

A further significant influence on the incubation time when using the compounds of the invention in rubber mixtures can be achieved by combination with commercial vulcanization retarders, such as Santoguard® PVI (N- (cyclohexlithio) -phthalimide), Vulkalent® E (N-phenyl-N-trichloromethylsulfenyD-benzenesulfonamide) become. As the most effective retarder, the Vulkalent "" E has proven. With increasing Vulkalent ^(RI Ε addition occurs a linear increase in the incubation time Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates containing mixtures.

When Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionation products as crosslinkers are used, compliance with the molar ratio of Ν, Ν'-substituted bis ( 2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates to Vulkalent E of 1: 0.5-1.5, preferably 0.8-1.2TIn. on 100Tie. Rubber proved to be useful.

Of more importance is the use of retarders, especially Vulcalent E, in accelerated sulfur vulcanization using Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetra-sulfides and their disproportionates and mixtures the same. In addition to the intended prolongation of the incubation time of the crosslinking reaction, occasionally a slight impairment of the crosslinking rate is observed, which can be absorbed by increasing the temperature and a slight decrease in the reversion resistance. It has also been found in this case, the molar ratio of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates to Vulkalent E to 1: 0.5-1.5, preferably 1: 0.8-1.2, wherein the sulfur content depending on the type of mixture between 0.1-10TIn., Preferably 0.5-8TIn. based on 100Tie. Rubber, is to hold.

With this dosing guidance, "I can solve many of the problems of vulcanization, without incurring substantial volcanic property loss contrary to the essence of the invention.

Mixtures containing only silica or carbon black / silica blends with higher silica contents than 15TIn./100TIn. Rubber, if at all, is difficult to crosslink with conventional sulfur vulcanization systems. On the one hand, they are particularly subject to reversion, on the other hand, they prevent the setting of the crosslink density, which is determined by the requirements of finished goods. This is one of the reasons why silicic acids are preferred in soling material and still relatively rare in dynamically stressed articles. Surprisingly, it is possible with bis (2,4-diamino-s-triazin-6-yl) -tetrasulfiren and their disproportionates in mixtures, the black / white blends with silica content of more than 15TIn./ '. 00 parts of rubber and also with silica-filled mixtures both when used as accelerators as well as crosslinkers (without sulfur) to practically eliminate the reversion and at the same time to increase the crosslinking density, which is expressed in a high for silicate mixtures stress level.

Another application of the N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides and their Disproportiorierui.gsprodukte ι is in combined use with oligosulfidic organosilanes, for example

(RO) ₃ - Si - (0H ₂ ) _n -

-S _x or

with χ = 2-6, R = Ct-Cp-alkyl »cyclohexyl

η = 2 or 3 respectively

(RO) ₃ Si - (0H ₂ ) _n -

with χ = 2-6, preferably 3,

Preferably, bis (3-triethoxysilylpropyl) tetrasulfide Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides and their disproportionates can be used both in sulfur-free organosilane crosslinking instead of in DE-PS 2536674 described advantageous to use as well as in the sulfur vulcanization described in DE-PS 2255577 with organosilanes and also in the production of reversion-stable organosilane-containing rubber mixtures by construction of equilibrium cure systems according to DE-PS 2848559.

This applies both to carbon black-filled mixtures and to mixtures containing carbon black / silica mixtures, as well as to mixtures which are built up only using silicic acids. The addition of mineral fillers has a disadvantageous effect in none of the mixtures mentioned. Rubber / filler bonds are formed in the presence of silica fillers or of blends of carbon black with silicic acids (rubber + rubber, plastics, volume 8,1977, pages 516-523, issue 10,1979, pages 760-765 and issue 4 , 1981), pp. 280-284) or in the presence of carbon black / rubber bond carbon blacks. The setting up of rubber / rubber crosslinking sites in the presence of carbon black or of the rubber / crosslinking sites in the presence of silica and both types of bonding in the case of carbon black / silica slices of all ratios is also possible if Ν, Ν ' substituted bis- (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates used alone or in admixture of several or in admixture with conventional accelerators together with conventional sulfur donors such as Sulfasan ^m> R (morpholine disulfide) become.

The use of the compound according to the invention is carried out in rubber mixtures which may contain further conventional components, such as, for example:

Customary reinforcement systems, d. H. Furnace carbon black, channel blacks, flame blacks, thermal blacks, acetylene blacks, electric 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 theirs Blends in quantities of 5-300TIn. every 100th. Rubber, particular preference is given to silicic acids and silicates,

- ZnO and stearic acid as promoters of vulcanization in amounts of 0.5-10TIn. Rubber,

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

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

- If necessary, further silanes such as -chloropropyltrialkoxisilanes, Vinaftrialkoxysulane, and Aminoalkyltrialkoxisilane and their blends in an amount of 0.1-15, preferably 1-10TIe. every 100th. Sila.iolgruppender fillers such as silicas, silicates, clays, etc.

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

The scope of the invention prepared according to the invention N.N'-substituted bis (2,4-diaMino-> trl .- 'zin-6-yl) -Tetrasulfide

covers rubber compounds commonly used in tire manufacture and technical articles, such as conveyor belts, V-belts, molded articles, tubes with or without inserts, roll rubbers,

Linings, spray profiles, freehand articles, foils, shoe soles and tops, cables, solid rubber tires and their Vulcanizates. As an example of compounds according to the invention, the following products may be mentioned: A Bi8- (2-ethylamino-4-di-isopropylamino-s-triazin-6-yl) tetrasulfide B Ris- (2-n-butylamino-4-diethylamino-s-triazine-6-yl) tetrasulfide C bis (2-isopropylamino-4-di-isopropylamino-E-triazin-6-yl) tetrasulfide D B! S- (2-ethylamino-4-di-i-butylamino-8-triazin-6-yl) tetrasulfide E 3is (2-ethylamino-4-di-n-propylamino-s-triazin-6-yl) tetra-9-sulfide 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 is i2-ethylamino-4-di-n-butylamino-s-triazin-6-yl) tetrasulfide K Sii-i'-isopropylamino ^ -di-isp'opylamino-s-triazine e-yD oligosulfide mixture L bis- (2-cyclohexylamino-4-dihydroxyamino-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 embodiments The invention is explained in more detail below with reference to some examples. Example 1: 454 g of 2-ethylamino-4-diathylamino-6-mercaptotriazine are dissolved in sodium hydroxide solution, which is obtained from 84 g of NaOH + 1.5 liters of H] O.

has produced.

The solution is placed in a 4 liter 3 tube flask, then add 1.5 liters of mineral spirits (bp 80-110 ° C) and cool the Mixture with vigorous stirring to ^{0 0} C from. Now allowed within 20min a solution of 137g S ₂ Cl ₂ in 100ml of gas enter, taking care that the Temperature +5 ⁰ C does not exceed. The tetrasulfide precipitates immediately. At the end of the reaction is stirred for 5min, then filtered with suction and washed. The snow-white fine powder is dried in a vacuum / 12 torr at 40-45 ⁰ C. Amount: 499.5 g, corresponding to 97.1% of theory F. 149-15O ⁰ C.

Analysis:

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

Mol wt. 516, Ci

calc. C 41,9 H 6.2 N 27.1 P 24,8 gef. C41.8 H 6.5 N 26.8 P 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. There are

250ml of gasoline. The mixture is cooled to +5 ⁰ C after good stirring. Now you can run _two in30ml gasoline, a solution of 13.5 g of S ₂ CI. It immediately forms a white precipitate. At the end of the reaction is worked up after Boispiel 1.

Quantity: 56g, corresponding to 89.2% of theory. Analysis: C ₂₆ H ₄₈ Ni ₀ S ₄ (molecular weight 628)

C 49.68 H 7.64 N 22.29 S 20.38

gef. C 49.59 H 7.59 N 22.18 S 20.40

HPLC analysis: purity> 96%. Example 3:

107.6 g of 2-i-propylamino-4-diisopropylamino-6-mercaptotriazine are dissolved in sodium hydroxide solution, which is prepared from 1/6 g of NaCH 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 one separates into one Separating funnel from the organic phase, dried and evaporated in vacuo. An amorphous powder is obtained; Softening point: 9O ⁰ C. Yield: 112.5 g, corresponding to 94% of theory. Analysis: C ₂₄ H ₄₄ Ni ₀ S ₄ (molecular weight 600)

C 48 H V, 33 N 23.3 S 21.3

gef. C 48.2 H 7.36 N 23.01 S 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 tumbled and cooled to 0 ° C. Dissolve 14g S ₂ Cl ₂ in 50ml CH] CI] and allows this solution enters the MercaptidlPsunu ι. The Renktionsprodukt dissolves in CH ₂ Cl ₂ . At the end of the reaction, the phases are separated and the CHjCl solution is worked up. you

thus receives an amorphous powder with a softening point of about 110'C.

Quantity: 46.7g, corresponding to 90.5% of theory. Analysis: C) ₈ H ₃₂ N ₁₀ S ₄ (mol. Wt. 516)

N 27.1 S 24.8

gef. N 26.8 S 24.4

According to TLC analysis, one finds: "a mixture of 4 oligosulfides, but no free sulfur. Example 5:

It is 50 g of bis (2-ethylamino-4-diethylamino-s-triazin-6-yl) tetrasulfide with a purity of 97.1% in a round bottom flask and heated in an oil bath for 1 hour at 160 ⁰ C. cold solidifies the melt amorphous. After TLC analysis, the product contains about 50% Ausgangsproduki 3 more oligosulfides.

Example 6:

70.25 g of 2-cyclohexaylamino-4-diethylamino-6-mercaptotriazine are dissolved in 11 g of NaOH and 250 ml of water. In addition you give 250ml

Chloroform. While stirring vigorously, a solution of 16.8 g of S ₂ Cl ₂ in 30 ml of CHCl _{3 is allowed to} run in. At the end of the reaction separates

the phase and working on the chloroform layer. This gives 71.9 g of a white amorphous powder, corresponding to 92% of the theory.

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

calc. C 50 H 7.05 N 22.4 S 20,51 gef. C 49,1 H 6,90 N 21.8 S 20

According to TLC analysis, the product is composed of about 30% linear S ₄ 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:

measured in

Tensile strength, breakage DIN 53504 MPa stretching and tension worth 6mm thick wrestling Shore A hardness DIN 53 505 - Firestone Ball Rebound AD 20245 % reversion DE-PS 2 848 559 Incubation time t; DIN 53 529 (Min) scorch ASTM D 2084 (Min)

In the application examples, the following names and abbreviations are used, the meaning of which is given below.

RSS: Ribbed Smoked Sheet (Natural Rubber) Carbon Black, Surface Area (BET) 120 mVg (Degussa)

CORAX®N220:

Naftolen®ZD: softeners made from hydrocarbons

lngraplast®NS: softening agent "- made of naphthenic hydrocarbons

Vulkanox * 3010 NA: N-isopropyl-N'-phenyl-p-phenylenediamine Vulcanox * HS: poly-2,2,4-trimethyl-1,2-dihydro-quinoline Mesamoll®: alkylsulfonic acid esters of phenol and cresol Robac Γ 25 dipentamethylenethiurametrasulifide Tetrone A dipentamethylene thiuram hexasulfide Protektor® Q 35: Ozone protection wax Vulkacit® MOZ: Benzothiazolyl-2-morpholino sulfenamide Vulkacit® mercapto: 2-mercaptobenzothiazole Vulkacit® thiuram: tetramethylthiuram monosulphide Vulkacit * CZ: N-Cyxclohexyl-2-benzothiazolesulfenamide Vulkalent®E: N-phenyl-N- (trichloromethylsulfenyl) benzenesulfonamide PVI: N-cyclohexylthiophthalimld UIUasil * VN3: precipitated silica (Degussa) Gran. Granules V143: Bis- (2-ethylamino-4-di-6-thylamino-8-razinazine-6-yl) disulfide Vulcacite * NZ: benzothiazyl-2-t <3-tert-butyl-sulfenamide Example 7: Reversal stability of 220, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides crosslinked, N 220-filled NR

(without sulfur)

1 2 3 4 RSS 1.ML4 = 70-80 100 100 100 100 CORAX N 220 50 50 50 50 ZnORS 5 5 5 5 stearic acid 2 2 2 2 NaftolenZD 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 VulkacitMOZ 1.43 - - V143 - 1.29 Santoguard PVI - 0.4 - - B - - 3.34 - D - - - 4.10 sulfur 1.5 1.5 Reversion: max (max + 60 ¹ ) D -D. 30.1 8.6 2.3 2.1 max min at 17O ⁰ C vulcanization

5 %) 2.5 6 7 RSS 1.ML4 = 70-80 100 100 100 CORAX N 220 50 50 50 ZnORS 5 5 5 stearic acid 2 2 2 NaftolenZD 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 Protector G 35 1 1 1 K 3.84 - L - 3.62 - M - - 4.0 Reversion: ^D max ~ ^D (max + 60 ·) ₍ D - D. 3.1 2.3 max min at 17O ⁰ C vulcanization

The Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -oligosulfides according to the invention turn out to be extremely stable for conversion into soot-filled NR mixtures (mixtures 3-7) when used as neat (without sulfur) ) compared to a somi-EV system (mixture 1) or to a bis (2-ethylamine-4-diethylamine-s-triazin-6-yl) -disulfide (V 143) -containing mixture (mixture 2).

Example 8:

Reversal stability of cross-linked with N, N'-substuierten Bi8- (2,4-diamino-8-triazin-6-yl) tetrasulflden!

N220 silicic acid-filled NR (without sulfur)

8th 9 10 11 12 RSS 1, ML {1 + 4) = 70-80 100 100 100 100 100 CORAX N 220 25 25 25 25 25 Ultra-part VN 3 Gran. 25 25 25 25 25 ZnOHS 5 5 5 6 5 stearic acid 2 2 2 2 2 NaftolenZD 3 3 3 3 3 Vulkanox4010NA 45 2.5 2.5 2.6 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 VulkicitMOZ 1.43 - - - - C - 3.48 - - - e - - 3.46 - - G - - - 3.62 - I - - - - 3.78 sulfur 1.5 - - - - Reversion: ^D max "° (max + 60 ') (· / \ A-,.  I A O A D - D \ " ) 47,1 1.8 2.4 3.3 D ₁ Z max min at 170X vulcanization

13 14 15 RSS 1, ML (1 + 4) = 70-80 100 100 100 CORAX N 220 25 25 25 UltrasilVN3Gran. 25 25 25 ZnORS 5 5 5 stearic acid 2 2 2 NaftolenZD 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 Protector G 35 1 1 1 K 3.48 - - L - 3.62 - M - _. 3.0 Reversion: max (max + 60 ¹ ) ( ^%) 2.5 3.1 4.7 D - D. max min at 70 ° C vuikanisaiiünsiemperatur

Siliceous NR mixtures show particularly strong repercussion even when using semi-EV systems (mixture 8). With the als, Ν'-substituted bis- (2,4-diamino-s-triazine-6-y-tetra- or -oligosuifiden (mixture 9-15) used according to the invention as crosslinkers, an almost no-change state is achieved with otherwise identical mixture composition.

Example. Reversion resistance of N, Ν'-substituted bls (2,4-diamino-s-triazin-6-yl) tetrasulfides accelerated N 220

filled NR

RSS1, ML (1 + 4) = 70-80CORAXN 220ZnORS

stearic acid NaftolenZO Vulkanox4010NA VulkanoxHS Protector G 35 VulkacitMOZ

SchwefelReversion:

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

"5 I ~ 5 '31.9 0.4 0.0 0.0 1.3

max min

at 17O ⁰ C

vulcanization vulcanizate

at 170 ° C, t95%

Tensile strength 23.0 22.6 24.1 21.3 20.8 Voltage value 300% 9.6 10.9 10.9 10.5 9.1 Continuation (1) Example 9: Reversion resistance of mltN.N'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetraeulphides accelerated N 220

filled NR

16 17 18 19 20 100 100 100 100 100 60 60 50 50 60 5 6 5 5 6 2 2 2 2 2 3 3 3 3 3 2.5 2.5 2.5 2.5 2.5 1.5 1.5 1.5 1.5 1.5 1 1 1 1 1 1.43 - - - - - 1.66 - - - - - 1.74 - - - - 1.76 - - - - - 1.73 1.5 0.8 0.8 0.8 0.8

21 %) 1.3 22 23 24 RSS 1, ML (1 + 4) = 70-80 100 100 100 100 CORAX N 220 50 50 50 50 ZnORS 5 5 5 5 stearic acid 2 2 2 2 NaftolenZD 3 19.9 3 3 3 Vulkanox4010NA 2.5 10.4 2.5 2.5 2.5 VulkanoxriS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 F 1.65 - - - G - 1.81 - - H - - 1.82 - I - - - 1.82 sulfur 0.8 0.8 0.8 0.8 Reversion: ^D max " ^D (max + 60 ') ₍ 1 O D - D. 2.0 * ' max min at 170 ^° C vulcanization Vulcanizate data at 170 ° C, t %% tensile strenght 22.1 22.0 23.2 Voltage value 300% 10.8 11.9 10.5

Example 9:

Reversion resistance of 220, Ν'-substituted bent- (2,4-diamino-s-trlazin-6-yl) -oligosulfides accelerated N 220 · filled NR

25 t 0.4 26 27 RSS 1, (ML 1 + 4) -70-80 100 100 100 CORAX N 220 50 50 50 ZnORS 6 5 6 Stearinsäii ^r e 2 2 2 NaftoienZD 3 22.9 3 3 Vulkanox4010NA 2.5 10.3 2.5 2.6 VulkanoxHS 1.5 1.5 1.5 Protector G 35 1 1 1 K 1.74 - - L - 1.81 _ M - 1.5 sulfur 0.8 0.8 0.8 Reversion: ^D müx " ^D (max + 60 ·), .. r \ - h 1.5 5.2 max min at 17O ⁰ C vulcanization Vulcanizate data at 170 ° C, t95% tensile strenght 24.2 22.2 Voltage value 300% 10.0 10.6

With equimolar acceleration dosage, the amount of sulfur can be reduced in the case of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetra-compounds. Nevertheless, higher 300% voltage values are achieved. The mixtures prepared with Ν, Ν'-substituents: bis (2,4-diamino-s-triazin-6-yl) tetra- or oligosulfides (mixtures 17-27) are extremely resistant to reversion to a semi-EV System (mix 16).

Example 10:

Efficacy comparison of sulfenamide · with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfide acceleration in N

220-filled NR with the same S _e dosage

28 %) 31.9 29 RSS1ML (1 +4) = 70-80 100 100 CORAX N 220 50 50 ZnORS 5 5 stearic acid 2 2 NaftoienZD 3 3 Protector G 35 1 1 Vulkanox4010NA 2.5 2.5 VulkanoxHS 1.5 1.5 VulkacitMOZ 1.43 D - 1.76 sulfur 1.5 1.5 Reversion: max ~ (max + 60 ¹ ) D - 0 5.1 max min

at 17O ⁰ C

vulcanization

Vulcanizate data at 160 ° C, t95%

Voltage value 300%, MPa 10.6 12.8

Shore A hardness 63 64

Example 9 showed the comparison of MOZ against Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasiilfide or their disproportionation with different Schwefelkonzentraticn. If, on the other hand, the sulfur concentration is kept constant at an equimolar amount of accelerator, the difference in reviction is maintained, but the 3GO% voltage value increases considerably.

Example 11: Comparison of the Reversal Behavior of Commercial Oligosulfides and Dibenzylsulfazolyl-tetrasulfide versus N, N'-substituted Bis (2,4-diamino-s-triazin-6-yl) -ollgosulfide in N 220-filled NR.

30 31 32 33 RSS 1, ML (1 + 4) = 70-80 100 100 100 100 CORAX N 220 50 50 50 50 ZnORS 5 5 5 5 stearic acid 2 2 2 2 NaftolenZD 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 RobacP25 1.12 Tetrone A 1.3 Dibenzthiazolyltetrasulfid - 1.15 - M - - - 1.5 sulfur 0.8 0.8 0.8 0.8 Scorchzeit170 ° C 1.4 1.9 2.7 3.1 (t 10%), min Reversion: max (max + 60 ¹ ) ... OC "Ϊ 1o, 9 21.3 35.7 3.2 D - D. max min at 17O ⁰ C vulcanization Vulcanizate data at 170 ° C, t95% tensile strenght 23.1 21.2 18.9 23.6 Voltage value 300% 9.4 9.5 7.3 10.4

Commercially available oligosulfides (mixtures 30 and 31) as well as dibenzothiazolyl tetrasulfide (mixture 32) show in NR several times higher reversion than a Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) oligosulfide ( Mixture 33).

Example 12: Blend of N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfide with sulfur donor in N 220-filled NR

34 35

RSS1 ML (1 + 4) = 70-80 100 U) 30.6 100 CORAX N 220 50 50 ZnORS 5 5 stearic acid 2 2 NaftolenZD 3 3 Protector G 35 1 1 Vulkanox4010NA 2.5 2.5 VulkanoxHS 1.5 1.5 VulkacitMOZ 1.43 Sulfasane R - 0.7 D - 1.76 sulfur 1.5 - Reversion: ^D max "° (max + 60 ') D - 0. 2.1 max min at 17O ⁰ C vulcanization

Conventional sulfenamide Beschieunigung (mixture 34) results in the use of N.N'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfide with Sulfasan R as a sulfur donor (mixture 35) a clear Reversionsverbesserung.

Example 13: Blend of commercial accelerators with N.N'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetrasulfide in N220-filled NR

RSS 1, ML (1 + 4) = 70-80 CORAX N 220 ZnORS

Stearic Acid NaftolenZD Vulkanox4010NA VulkanoxHS Protector VulkacitMOZ VulkacitDM

sulfur

-D

(max + 60 ¹ )

36 37 38 39 40 100 100 100 100 100 50 50 50 50 50 5 5 5 5 5 2 2 2 2 2 3 3 3 3 3 2.5 2.5 2.5 2.5 2.5 1.5 1R 1.5 1.5 1.5 1 1 1 1 1 1.43 0.71 1.5 - - - - - 1.56 0.78 - 0.8 1.58 - 0.8 1.5 1.5 - 1.5 1.5

D -D. 28.7 X) 16.8 5.7 31.2 16.1 max min at 17O ⁰ C vulcanization vulcanizate at 170 "C Voltage value 300%, 195% 11.3 11.9 6.8 9.0 11.4 t95% + 90 ' 8.9 10.7 6.7 7.5 10.5 41 42 43 44 RSS 1, (ML 1 + 4) = 70-80 100 100 100 100 CORAX N 220 50 50 50 50 ZnORS 5 5 5 5 stearic acid 2 2 2 2 NaftoienZD 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 VulkacitDM 1.56 - - - Vulkacit Morkapto - 1.2 0.6 1.2 B 1.58 - 0.8 , 1.58 sulfur - 1.5 1.5 - ^D max ~ ^D (max + 60n

- D

4.1

28.7

4.5

min

at 170 ° C vulcanization temperature Vulkanisatdaten at 17O ⁰ C.

Voltage value300% t95% 7.0

t95% + 80 '6.9

7.8

6.5

5.9 5.9

The common combination of commercially available accelerators with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides (mixtures 37,40,41) leads to a clear improvement in the reversion behavior over the sole use of commercially available accelerators (mixtures 36, 39, 42). A further increase in the reversion resistance can be achieved by eliminating the sulfur (mixtures 38,41,44).

Example 14: Blend of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfide with Ν, Ν'-substituted bis (2,4-di8mino-s-triazine -6-yl) -oligosulfide in N 220-filled NR.

RSS 1, ML (1 + 4) = 70-80 CORAX N 220 ZnORS

Stearic Acid NaftolenZD Vulkanox4010NA VulkanoxHS

45 46 47 48 100 100 100 100 50 50 50 50 5 5 5 5 2 2 2 2 3 3 3 3 2.5 2.5 2.5 2.5 1.5 1.5 1.5 1.5

45 46 47 48

Protector G 35 1111 VulkacitMOZ 1,43 - - -

M 1.5 - 0.75

B - - 1, ββ 0,83

Sulfur 1.5 0.8 0.8 0.8

^D max ~ (max + 60 ¹ )

_{4 12}

D - D.

max min

at 17O ⁰ C vulcanization temperature

The combined use of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulflden with different reversion resistance results in a value image that lies between the pure substances (mixture 48).

Example 15: Reversion during acceleration with B in NR with soot / silica waste.

49  (%) 46.7 50 RSSIMLd +4) = 70-80 100 100 CORAX N 220 25 25 UltrasilVN3Gran. 25 25 ZnORS 5 5 stearic acid 2 2 NaftolenD 3 3 Protector G 35 1 1 Vulkanox4010NA 2.5 2.5 VulkanoxHS 1.5 1.5 VulkacitMOZ 1.43 B - 1.67 sulfur 1.5 0.8 ^D max " ^D (max + 60 *) f \ _ Γι 10.8 U U max min 170 ° C vulcanization

Replacement of the Suifenamidbeschieunigers (mixture 49) by Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfide (mixture 50) falls back the reversion drastically.

Example 16: Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetra and oligosulfides in N 220-filled SBR

51 X) 12.9 52 53 54 55 SBR1500 100 100 100 100 100 CORAX N 220 50 50 50 50 50 ZnORS 5 5 5 5 5 stearic acid 2 2 2 2 2 NaftolenZD 3 3 3 3 3 Protector G 35 1 1 1 1 1 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 VulkacitMOZ 1.43 - B - 1.66 - F - 1.58 K - - 1.5 M - - - 1.5 sulfur 1.5 1.5 1.5 1.5 1.5 ^D max ~ ^D (max + 60 ') ₍ D - D 11.3 11.5 9.2 12.5 max min at 17O ⁰ C vulcanization

51 52 53 54 55

vulcanization data in at 20.6 21.3 20.8 20.5 19.9 170 ^e C, t95% 10.0 11.6 12.2 12.1 12.3 tensile strenght 460 440 420 420 390 Voltage value 300% 61 63 63 63 64 elongation Shore hardness

At the same sulfur dosage, Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -tetra- or -oligosulfides (mixture 52-55) in SBR1 b00 show a significantly higher voltage value and slightly improved Reversion properties against a conventional acceleration (mixture 51).

Example 17: Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetra- or -oligosulfide in N 220-filled isoprene rubber

56 57 58 59 Polyisoprene 3,4 100 100 100 100 CORAX M 220 50 50 50 50 ZnORS 5 5 5 5 stearic acid 2 2 2 2 NaftolenZD 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 Protecto-G35 1 1 1 1 VulkacitMOZ 1.43 - - B - 1.76 - L - - 1.6 M - - - 1.5 sulfur 1.5 0.8 0.8 0.8 Reversion: max (max + 60 ¹ ), D ~ D 21.0 2.1 0.0 0.0 max min at 17O ⁰ C vulcanization Vulcanizate data at 170 ⁰ C, Voltage value 300% 195% 7.9 6.6 6.3 6.4 t95% + 80 ' 6.2 6.8 6.3 7.1

In polyisoprene rubber, the use of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetra- or -oiigosulfides (mixtures 57-59) against conventional accelerators (mixture 56) also produces a achieved significant improvement in reversion. This improvement is also evident in the constancy of the vulcanizate data with significant overheating.

Example 18: N, N'-substituted bis (2,4-diaminotriazin-6-yl) tetra- and oligosultrides in N 220-filled EPDM

60 %) 3.3 61 62 BunaAP451 100 100 100 CORAX N 220 50 50 50 ZnORS 5 5 5 stearic acid 2 2 2 IngraplastNS 10 10 10 VulkacitThiuram 1 _ Vulkacit Mercapto 0.5 - - B - 2.93 - M - - 2.5 sulfur 1 1 1 ^D max " ^D (max + 60 ') ₍ D - D 0.0 0.0 max min at 16O ⁰ C vulcanization

Already highly reversion-resistant EPDM blends show a further reduction in reversion to zero when conventional accelerator blends (Blend 60) are substituted by Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetra- or oligosulfides be replaced (mixtures 61 and 62).

Example 19: Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetra and -oligosulfide in N 220-filled NBR

63 (X) 8.0 64 65 Perbunan N 3307 NS 100 100 100 CORAX N 220 60 60 60 ZnORS 6 6 5 stearic acid 1 1 1 Paraffin solid 1 1 1 mesamoll 10 10 10 VulkanoxHS 1.5 11.8 1.5 1.5 VulkacitCZ 1.5 68 1.5 1.5 D - 1.76 M - - 1.5 sulfur 1.2 1.2 1.2 Reversion: ^D max " ^D (max + 60 ') 5.4 5.6 D - D. max min at 17O ⁰ C vulcanization Vulcanizate data at 170 ^e C, t95% Voltage value 300% 14.0 14.6 Shore hardness 69 69

At the same sulfur content, the reference mixture (Mixture 63) is replaced by Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetra- or -oligosulfides (Mixtures 64 and 65). in NBR a strong increase of the stress value at 300% elongation with simultaneous reduction of the reversion.

Example 20: Reversion stability of Γ Ι, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides in N 220-filled BR

D - 0. 66 67 68 Buna CB10 max min 100 100 100 CORAX N 220 at 17O ⁰ C 60 60 60 ZnORS vulcanization 3 3 3 stearic acid Vulcanizate data at 2 2 2 NaftolenZD 170 ° C 15 15 15 Protector G 35 Voltage value 300% t 95% 1 1 1 Vulkanox4010NA t95 + 75 ' 1.5 1.5 1.5 VulkacitNZ 1.5 M - 1.5 - D - - 1.76 sulfur 1.5 1.5 1.5 reversion max imax + 60 ') , K 30.3 20.8 19 1 8.6 8.9 8.2 5.6 6.8 6.6

Because of the lower reversion of the M and D accelerated BR mixtures (mixtures 67 and 68), the drop in the 300% voltage value is markedly reduced with strong overheating compared to the reference mixture (mixture 66).

Example 21: Ν, Ν'-substituted bis- (2,4-diarryl: -s-triazin-6-yl) -tetra- and -oligosulfides in N 220-filled NR-BR / blend

V - · - »- *

69 70 71 72

RSS1, ML (1 + 4) = 70-80 70 70 70 70

Buna CB10 30 30 30 30

CORAX N 220 50 50 60 60

Znors 5 5 6 5

Stearic acid 2 2 2 2 NaftolenZO 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 Protector G 35 1111 VulkacitMOZ 1,43 - - -

C - 1.74 - -

D - - 1.76 -

M - - - 1.5

Sulfur 1.5 0.8 0.8 0.8 Reversion:

32.0 16.8 20.6 23.8

D * 0

max (max + 60 ¹ ) ....

D - D.

max min

at 170 ^e C VulkanisGtionstemperatur

Mixtures 70 to 72 show a significant reduction in the reversion when using Ν, Ν'-substituted bis (2,4-diaminos-triazin-6-yl) tetra and oligosulfides against a semi-EV system (mixture 69) in a blend of NR and polybutadiene.

Example 22: Crosslinking of 50% epoxied natural rubber (ENR 50) with N 220 filling with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetra- or -oligosulfide

ENR 50

CORAX N 220

stearic acid VulkanoxHS VulkacitMOZ VulkacitThiuram

sulfur

Reversion:

max (max + 60 ¹ ), "*

73 74 75 100 100 100 50 60 60 5 5 5 2 2 2 2 2 2 2.4 - - 1.6 - - - 4.6 - - - 4.0 0.3 0.3 0.3

6.7 0.0 0.0

D - D.

max min

at 15O ⁰ C

vulcanization Vulcanization data at

150 ⁰ Ct 95%

Tensile strength 18.7 23.9 24.6 Stress value 3C0% 18.0 18.4 18.9 Tear resistance 12 14 12 Shore hardness 75 76 78

At the same stress value at 300% elongation and significantly increased tensile strength, the replacement of a conventional acceleration (mixture 73) by Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetra- or oligosulfides (blends 74 and 75) for an additional improvement in reversion.

Example 23: Effect of Vuikalent E on sulfur-free NR crosslinking of N 220 and N 220 / silica-filled NR with Ν, Ν'-substituted bis- (2,4-diamino-s-uia2in-6-y! -) fito-et asu - - *!

-18- 80 270 302 100 81 25 100 25 25 5 25 2 6 3 2 2.5 3 1.5 2.5 I 1.5 !, 84 1 - 2.84 2.4

76 77 78 79

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

CORAX N 220 50 50 50 25

UitrasilVN3Gran. - - - 25

Znors 5 5 5 5

Stearic acid 2 2 2 2 NaftolenZO 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5

VulkanoxHS 1.5 1.5 1.5 1.5 Protector G 35 1111

VulkacitMOZ 1.43 - - 1.43

C - 3.79 3.79 -

Vulcan E - - 3,2 -

Sulfur 1,5 - - 1,5 - - Reversion:

max (max + 60 ') ₍ ".

_{0 D} 32.5 4.1 4.5 47.8 5.4 5.5 max min

vulcanization

ti170 ^e C, (min) 4.2 2.8 4.6 4.7 3.0 4.7

In N 220 and N 220 / silicic acid-filled and C-crosslinked NR, the Vulcalent Ε addition achieves the desired extension of the incubation time without adversely affecting the reversion.

Example 24: Delaying effect of Vulcalent E on N, N'-substituted bis (2,4-diamino-triazin-6-yl) tetra- and oliijosulfide-vulcanized N 220 / NR mixtures

82 83 84 85 86 RSS1, ML4 = 70-80 100 100 100 100 100 CORAX N 220 50 50 50 50 50 ZnORS 5 5 5 5 5 stearic acid 2 2 2 2 2 NaftolenZO 3 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 VulkacitMOZ 1.43 - - B - 1.66 1.66 - M - - - 1.55 1.55 Schwe'il 1.5 0.8 0.8 0.8 0.8 Vulcan E - - 1.2 1.2 Ti (min 3.8 3.0 4.4 ••!, 9 4.1 at 170 ° C vulcanizate at 170 ^° C, 195% Voltage value 300% 10.6 10.2 11.5 10.6 11.0

The addition of Vulcalent E to B and M accelerated mixtures (mixtures 84 and 86) leads to an increase in the incubation time ti above the level of the conventionally MOZ accelerated mixture (mixture 82).

Example 25: N.N'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetrasulfides with volcu- larene E addition in N 220-filled NR as a function of temperature

87 88 89 RSS1MI (1 + 4) = 70-80 100 100 100 CORAX N 220 50 50 50 ZnORS 5 5 5 stearic acid 2 2 2 NaftolenZO 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 Vulcan E - - 1.2

Sulfur 1.5 0.8 0.8

^D max "° (max + 60 ')

D - D.

max min

at 145 "C, test temperature 7.9 0.0 0.0

at 160 ⁹ C test temperature 25.6 0.0 1.9

at 170 * C test temperature 30.9 0.4 3.6

at 18O ⁰ C test temperature 39.1 2.6 5.6

Example 25 shows with pure Ν, Ν'-substituted bis (2,4-diamino-8-triazin-6-yl) tetrasulfide acceleration (mixture 88) as well as with the addition of Vulkalent E (mixture 89) over conventional acceleration ( Mixture 87) a pronounced temperature sensitivity of the reversion.

Example 26: Effect of Vulkalont E on N, N'-substituted bis- (2,4-diamino-s-triazln-6-yl) tetrasulfide and oligosulfide crosslinked NR with N 220 / silica

90 91 92 93 94 RSS1, MU1 +4) = 70 -80 100 100 100 100 100 UltrasilVN3Gran. 25 25 25 25 25 CORAX N 220 25 25 25 25 25 ZnORS 5 5 5 5 5 stearic acid 2 2 2 2 2 NaftolenZD 3 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.6 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 VulkacitMOZ 1.43 - - D - 3.5 3.5 - - M - - - 3.0 3.0 Vulcan E - - 1.2 - 1.2 sulfur 1.5 0.8 0.8 0.8 0.8 Scorch at 130 ° C (min) 29.5 15.0 28.5 16.5 29.0 Scorch at 17O ⁰ C (min) 4.5 3.4 4.4 3.7 4.8

Vulcalent E can be used to accelerate with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetra- or • oligosulfides (mixtures 92 and 94) in a scorch behavior comparable to MOZ.

Example 27: Simultaneous Use of N, N'-substituted Bis- (2,4-diamino-s-triazin-6-yl) tetrasulfide and Si 69 with and without Vulkalent E in N 220 / VN 3-filled Nri

95 96 97 98

RSS 1, ML (1 + 4) = 70-80 100 O 19.6 100 100 100 100 CORAX N 220 25 '25 25 25 25 UltrasilVN3Gran. 25 25 25 25 25 Si 69 3.75 3.75 3.75 3.75 3.75 ZnORS 5 4.6 5 5 5 5 stearic acid 2 2 2 2 2 NaftolenZD 3 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 VulkacitMOZ 1.43 - - - - B - 2.2 2.2 1.66 1.66 Vulcan E - - 1.6 - 1.2 sulfur 1.5 0.8 0.8 Reversion: max (max + 60 ¹ ) (/ D -D. 0.0 0.0 0.0 0.0 max mm at 17O ⁰ C vulcanization ti at 17O ⁰ C (min) 4.2 5.7 4.2 5.2

When Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides and Si 69 are used together

Non-reversible mixtures with and without sulfur (mixtures 96, 98) are obtained against conventional accelerators with silane (mixture 95). The addition of Vuikaient E also leads in this case to an extension of the scorch time, without the reversion occurring again (mixtures 97 and 99 ").

Example 28: Crosslinking of N 220 / silica-filled NR with Ν, Ν'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide without

sulfur

RSS1 100 100 100 100 100 100 100

CORAX N 220 25 25 25 25 25 25 25 Ultr. VN 3 Gran. 25 25 25 25 25 25 25 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 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 1." 1.5 Protector G 35 1 1 1 1 1 1 1 VulkacitMOZ 1.43 - - - - - - D - 2 3 4 5 6 7 sulfur 1.5 - - - - - - max (max + 60 ¹ ) _{0 /} 44.7 3.2 2.0 1.3 3.1 2.8 2.6 D -D. max min at 170 "C vulcanization vulcanizate (t 95%) at 170 ^° C. Voltage value 300% 4.9 2.6 4.4 5.8 6.8 7.8 8.8

The sulfur-free reduction with Ν, Ν'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide leads in natural rubber with carbon black and silica filling to inhibit the reversion and at the same time to a quantity-dependent increase in voltage.

Example 29: Crosslinking of silica-filled NR with Ν, Ν'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide

RSS1 100 2.7 100 Ultr. VN 3 Gran. 50 50 ZnORs 5 5 stearic acid 2 2 NaftolenZD 3 3 Vulkanox4010NA 2.5 2.5 VulkanoxHS 1.5 1.5 Protector G 35 1 1 VulkacitMOZ 1.43 - D 7 sulfur 1.5 - ^D max " ^D (max + 60 ') I 33.0 & 7.8 D - D. Ό max now at 17O ⁰ C vulcanization vulcanizate (t 95%) at 170 ^° C. Voltage value 300% 4.3

The sulfur-free reduction with Ν, Ν'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide leads to a substantial reduction of reversion in natural rubber with silica filling and at the same time to an increase in the stress value at 300%.

Example 30: Acceleration of N 220 / silica-filled NR with Ν, Ν'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide

RSS1

CORAX N 220 Ultr. VN 3 Gran

 ZnORS stearic acid

100 100 100 100 100 100 100 25 25 25 25 25 25 25 25 25 25 25 25 25 25 5 5 5 5 5 5 5 2 2 2 2 CM 2 2

-21- 270 302 3 3 3 2.5 2.5 2.5 1.6 1.5 1.6 1 1 1 5 β 7 1.27 1.53 1.79

Example 30: NaftoienZD 3 3 3 Vulkanox 4010NA 2.5 2.5 2.6 2.5 VulkanoxHS 1.5 1.6 1.5 1.5 Protector Q 35 1111 VulkacitMOZ 1,43 - - -

B - 2 3

Sulfur 1.6 0.61 0.76 1.02

^D max " ^P (max + 60 ') _{c /}

• - ^{/ o} 44.7 3.2 1.7 0 0 0.8 1.7

D -D max min

at 17O ⁰ C

vulcanization vulcanizate

i «.95%) at 170 ° C

Voltage value 300% 3.6 3.5 5.5 7.0 8.3 9.2 9.8

Sulfur vulcanization with Ν, Ν'-substituted bis (2,4-diamino-triazln-6-yl) -tetrasulfide of N 220 / silica-filled NR reduces the reversion to 0% and leads to a strong increase in the voltage value.

Example 31: Acceleration of silica-filled NR with Ν, Ν'-substituted bis (2,4-diamino-triazi i-6-yl) tetrasulfide Ultr.VN3Gran. stearic acid NaftoienZD Vulkanox4010NA VulkanoxHS Protector G VulkacitMOZ

sulfur

^D max ~ ^D (max + 60 ¹ )

100 100 50 50 5 5 2 2 3 3 2.5 2.5 1.5 1.5 1 1 1.43 - - 7 1.5 1.79

ηTD * ³³ O 4.5

max min

at 17O ⁰ C

vulcanization vulcanizate

{T95%) at 170 ° C

Voltage value 300% 2.7 5.3

The sulfur vulcanization with Ν, Ν'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide of silica-filled NR succeeds almost without reversion and with increasing the 300% - pannungswertes.

Example 32: Acceleration of N 220 / silica-filled NR nit Ν, Ν'-substituted bis (2,4-diamino-triazin-6-yl) -exetrasulfide in Presence of Si

CORAX N

Ultr.VN3Gran. stearic acid NaftoienZD Vulkanox4010NA VulkanoxHS Protector G VulkacitMOZ

sulfur

100 100 100 25 25 25 25 25 25 3.75 3.75 3.75 5 5 5 2 2 2 3 3 3 2.3 2.5 2.5 1.5 1.5 1.5 1 1 1 1.43 - 2 3 1.5 0.49 0.74

Example 32:

^D max ~ ^D (max + 60 ¹ ) max min

at 17O ⁰ C

Vulcanization temperature vulcanizate data (t 95%) at 17O ⁰ C voltage value 100% voltage value 200% voltage value 300%

% 18.1

1.4 3.6 7.1

1.6 4.6 9.5

2.4

7.3

13.9

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

Example 33: Acceleration of silica-filled NR with Ν, Ν'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide in the presence

from Si 89

RSS1 100 100 100 100 Ultr.VN3Gran. 50 50 50 50 Si 69 7.5 7.5 7.5 7.5 ZnORS 5 5 5 5 stearic acid 2 2 2 2 NaftolenZD 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 VulkacitMOZ 1.43 - - - B - 2 3 4 sulfur 1.5 0.49 0.74 0.99 ^D max " ^D (max + 60 *) D -D. ^% 16.6 0 0 0 max min at 17O ⁰ C vulcanization Vükanisatdaten (t 95%) at 170 "C Voltage value 100% 1.5 1.7 2.5 , 3.2 Voltage value 200% 3.4 4.3 6.6 8.3 Voltage value 300% 6.3 8.2 12.3 15.0

Also in the case of pure silicic acid filling NR is vulcanized in the presence of Si 69 with N, N '- substituted bis- (2,4-diamino-triazin-6-yl) -tetrasulfide and sulfur without reversion, while the level of stress is increased very much.

Example 34: The sulfur-free crosslinking of N 220 / silica-filled NR with Ν, Ν'-substituted B ^! j- (2,4-diamino-triazin-6-yl) -

tetrasulfide in the presence of Si 69

RSS1 100 100 100 100 100 CORAX N 220 25 26 25 25 25 Ultr.VN3Gran. 25 25 25 25 25 Si 69 3.75 3.75 3.75 3.75 3.75 ZnORs 5 5 5 5 5 stearic acid 2 2 2 2 2 NaftolenZD 3 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 VulkacitMOZ 1.43 - D 1 2 3 4 sulfur 1.5 _ -

"max" (max + 60 ¹ ) " 3.5 O 0 O O D -D. max min 7.1 beiWC vulcanization vulcanizate (T95%) at 170 ° C 2.6 4.9 6.5 8.6 Voltage value 200% 5.8 10.2 12.9 16.0 Voltage value 300%

The sulfur-free crosslinking of N, N'-substituted bis- (2,4-dinaminopropyx- ^s- 6-yl) tetrasulfide leads in natural rubber with carbon black and silica filling even with the addition of Si 69 to a simultaneous prevention of reversion and men vigorous quantity-dependent voltage value increase.

Example 35: The sulfur-free cross-linking of silica-saturated NR with Γ, Ν'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide in Presence of Si 69

RSS1 100 100 100 100 100 Ultr. Vn 3 gran. 50 50 50 50 50 Si 69 7.5 7.5 ., Ti 7.5 7.5 ZnORS 5 5 5 5 5 stearic acid 2 2 2 2 2 NaftolenZD 3 3 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 VulkanöxHS 1.5 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 1 VulkacitMOZ 1.43 - - - D - 1 2 3 4 sulfur 1.5 - - - - ^D max " ^D (max + 60 ')., 16.6 0 0 0 0 D -D. max min at 17O ⁰ C vulcanization vulcanizate (t 95%) at 170 "C Voltage value 200% 3.4 2.8 3.9 5.0 7.6 Voltage value 300% 6.3 5.0 7.6 11.3 13.9

Crosslinking with N.N'-substituted bis (2,4-diamino-triazin-6-yl) tetrasulfide of natural rubber with

Pure silicic acid filling in the presence of Si 69 also succeeds without reversal and simultaneously leads to strong

Voltage value increase.

Claims (10)

1. A process for the preparation of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides of the general formula > 4 in which mean: R ¹ , R ² = H, R ² = benzyl, R ² , R ³ , R ⁴ = C ₁ -C ₈ -AllCyI, Cy-Ca-cycloalkyl, the latter unsubstituted or with 1-3 methyl groups substituted, 2-Hydroxiethy !, 3-Hydroxipropyl, -2-Hydroxipropyl or R ³ and R ⁴ (together): C ₄ -C ₆ -AlkYIe ^ - (CH ₂ -CHX) ₂ Y with X = H, CH ₃ , Y = / O, S characterized in that an aqueous alkaline solution of the corresponding N, N'-substituted 2,4-diamino-6-mercaptotriazine in a two-phase system with a solution of S ₂ -Cl ₂ in e'nem inert, the resulting tetrasulfide little or no dissolving, organic solvent. 2. A process for the preparation of tetrasulfides according to claim 1, characterized in that one uses the necessary at least for the implementation of stoichiometric amount of alkali metal hydroxide. 3. The method according to claim 1 and 2, characterized in that one uses an excess of 1-20 mol .-%, based on the mercaptotriazine. 4. Process according to claims 1 to 3, characterized in that sodium or potassium hydroxide and as a solvent, C ₅ -C ₁ O alkanes or C ₅ -C ₈ cycloalkanes, optionally substituted by 1-3 methyl groups. 5. vulcanizable, fillers, sulfur and other conventional constituents containing mixtures based on one or more natural and / or synthetic rubber (s) (S), characterized in that the 0.01-10Tle, preferably 0.1-STIe ., per 100Tie. Rubber of the compounds according to claims 1-4 and mixtures thereof and / or mixtures with conventional accelerators contain at sulfur dosages of 0.1-10TIe. per 100 parts of rubber. 6. Vulkanisierbare mixtures according to claim 5, characterized in that they donor retarder N-phenyl-N-trichlormethylsulfonylJ-btnzolsulfonamid and the compounds according to claims 1-4 or mixtures thereof in a molar ratio of 0.5-1.5: 1, preferably 0.8-1.2: 1, at a sulfur dosage of 0.1-10 parts by weight per 100 parts of rubber, preferably 0.5-8 parts based on 100 parts of rubber. 7. Vulcanizable, fillers and further customary constituents, sulfur-free mixtures based on one or more natural and / or synthetic rubbers, characterized in that they contain 0.2-15 parts, preferably 0.3-8 parts, of the compounds or their Mixtures according to claims 1-4 to 100 parts of rubber or mixtures with conventional accelerators. 8. Vulcanisable mixtures according to claim 7, characterized in that they contain the retarder M-phenyl-N - ((rir, hlormethylsulfenyl) benzenesulfonamide and the compounds according to claims 1-4 or mixtures thereof in a molar ratio of 0.5-1.5 : 1, preferably 0.8-1.2: 1, contained on 100 parts of rubber. 9. Vulcanisable mixtures according to claims 5 to 8, characterized in that they contain as fillers only silicic acids. 10. Vulcanizable mixtures according to claims 5 to 8, characterized in that they contain as filler except carbon black more than 15 parts of silica per 100 parts of rubber.