DD284007A5 - PROCESS FOR PREPARING MIXTURES COMPRISING N, N'-SUBSTITUTED BIS- (2,4-DIAMINO-S-TRIAKIN-6-YL) OLIGO SULPHIDES - 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

A process for the preparation of mixtures consisting of N, N'-substituted BiB- (2,4-diamino-s-triazine-6-yl) -01-oligosulfides

Field of application of the invention

The invention relates to a process for the preparation of mixtures consisting of N ₁ N'-substituted bis- (2,4-diamino-s-triazin-6-yl) -1-oligosulfides and sio-containing vulcanizable rubber chukmi loops.

Characteristic of the well-known Starides of technology

N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) disulfides are known; they are described in DE-PS 1 669 954. They are prepared from the corresponding N, N'-substituted 2,4-diamino-6-mercaptotriasines 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-ethyl-aminotriazin-6-yl) disulfide. Disulfides of this group can be used in rubber compounds as accelerators.

Object of the invention

The aim of the invention is to provide novel 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.

-6- 2 Ö 4

According to the invention, compounds of the general formula

R ³ R ⁴ R ³ R ⁴

N N

_Λ (D.

R ¹ II I II IR ¹

N ^ ^S x Si

manufactured, in which mean:

R ¹ , R ² = H, R ² = benzyl

R ² , R ³ , R ⁴ = C ₁ -C ₈ -alkyl, preferably C ₁ -C ⁴ -alkyl, branched

or unbranched, alkyl, C ^ -Cg-cycloalkyl, the latter unsubstituted or substituted with 1-3 methyl groups, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or

R ³ and R ⁴ (together): C.-Cg-alkylene, - (CH ₂ -CHX) ₂ Y with X = CH,

H; Y = 0, S

and S corresponds to a mean statistical chain length with χ = 4.

The inventive method is characterized in that compounds of the general formula

4 OO 7

in which R, R, R, and R have the same meanings as above, disproportionate without free sulfur being produced.

The process for preparing the pure tetrasulfides with a linear S chain between the two substituted triazine radicals is characterized in that an aqueous, alkaline solution of the corresponding N, N'-substituted 2,4-diamino-6-mercaptotriazine in a two-phase system with a SpClp solution in an inert organic solvent in which the reaction product is not or very slightly soluble, at temperatures between -5 ⁰ O - <+ 20 ⁰ C, preferably of + 10 ⁰ C, is reacted. It is advantageous to prepare an alkaline aqueous solution of mercaptotriazine which contains at least the stoichiometric amount of alkali hydroxide necessary for the reaction, preferably an excess of 1-20 mol%, based on the mercaptotriazine used.

This solution is treated with a solvent in which the end product of the reaction is not or slightly soluble, preferably with Ccj-CQ alkanes, CV-Cg-cycloalkanes, optionally substituted with 1 to 3 methyl groups and mixtures thereof. This mixture is stirred vigorously and cooled, preferably to + 10 ⁰ C.

284 0 0

Now a solution of S ₀ Cl ₂ in the solvent used is added dropwise to this mixture with good cooling. S ₀ Cl ₂ is used at least in the ratio 2 mol mercaptotriazine: 1 mol SpGl ₂ , but this ratio may also be 2: 1.1 - 1.2 depending on the excess alkali.

Under the given conditions, S ₃ Cl _{2 is} exclusively condensing.

The resulting product is separated by means of generally known measures and advantageously under vacuum (10 Torr) dried.

took separated and advantageous at temperatures up to + 50 ⁰ C.

These mixtures, hereinafter also referred to as 01igosulfides or disproportionates, since they are formed by disproportionation of compounds of formula II, can be represented in several ways.

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

A process is characterized in that the isolated compound according to formula I is heated above its melting point, preferably by 20-50 ^° C.

In a further process, the compounds according to formula II is dissolved in an inert organic solvent and the Disproportiünierungsreaktion leads in the temperature range between 20 ⁰ C (standing at room temperature) and boiling point of the solvent used through.

- ⁹ - 2 a 4 ο ο 7

A particularly elegant method consists in reacting an aqueous alkaline solution of the corresponding N, N'-substituted 2,4'-diamino-6-mercaptobriazines in a two-phase system with a solution of SpCIp in an inert organic solvent dissolving the resulting tetrasulfide. The resulting tetrasulfide is then immediately disproportionated in the sequence according to the invention, consisting of 01igosulfiden.

Suitable solvents are in particular chlorinated hydrocarbons, for example CHpCl _? and CHCl ,,, but also:

Ethers, esters and aromatic hydrocarbons and ketones are suitable for the disproportionation reaction according to claim 3. According to claim 4, they are useful when they form a biphasic mixture with water. The reaction conditions for the preparation of the disproportionates are otherwise identical to those for the preparation of compounds of formula II.

The invention likewise relates to the rubber mixtures themselves containing the compounds according to the invention,

The disproportionates prepared according to the invention, when used as crosslinkers or vulcanization accelerators, are clearly superior to the standard compounds used today.

The rubber industry has a wide range of accelerators available (J. van Alphen, Rubber Chemicals (1977, pp. 1-46)), preferably for sulfur vulcanization, for example, benzothiazolyl sulfenamides, benzothiazolyl disulfide and 2-mercaptobenzothiazole or their zinc salts. There are also

β 4 O 7

ea a number of special Verbindgengen such as thiuramides and peroxides, which act as crosslinkers without further additives of sulfur, but are often used in Korabination with sulfur as an accelerator. The type of use depends on the particular effect to be achieved.

The greatest amount in terms of quantity in practical application, in particular in the case of the elastomers which are accessible to accelerated sulfur vulcanization, is today attributed to the benzothiazolyl sulfenamides.

However, new production processes, new articles and the need for constant rationalization in recent years have changed the application requirements of xXir accelerators to such an extent that they can already present difficulties today, the quality requirements imposed on the vulcanization process and the properties of the vulcanizates to comply with the accelerators or crosslinkers available today for the accelerated sulfur vulcanization.

Another disadvantage of some conventional accelerators (eg, some sulfonamides, thiurams) is that during the vulcanization process, amines can be released, which, as far as they are nitrosatable, lead to the formation of nitrosamines in the vulcanizate , which - as far as they are toxic - can be expected in the long term to limit the possible uses of these accelerators.

A very significant disadvantage of Benzthiazolylbeschleuniger, especially the Benzthiazolylsulfonamide is their with increasing

Vulkanisationetemperatur increasingly pronounced tendency to reversion in the inevitably often necessary overheating of VuI kanisate, especially when using anyway reversion susceptible rubbers such as natural rubber and polyisoprene and their blends with synthetic rubbers. The same applies, however, to synthetic rubbers of all kinds, provided that the reversion process is not covered by thermal crosslinking. Particularly with increasing vulcanization temperature, the rate of reversion increases so much that, firstly, there is already a noticeable reduction in the crosslinking density even with optimal vulcanization, so that, secondly, the vulcanization optimum takes the form of a peak instead of a plateau, which makes the reproducible observance of optimal vulcanization properties immensely and that, thirdly, in the case of overvulcanization, which is necessary in many cases, an unavoidable drop in the crosslinking density occurs, which leads, in particular with thick-walled rubber articles, to the elimination of the uniformity of crosslinking in the vulcanizate. To the same extent as the reversion increases, there is a decline in the performance of the vulcanizates, which is z. B. expressed 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 Physics of Rubber-Like Substances, pp. 522 et seq.) leads to a mitigation of the above-mentioned reversion effects Crosslinking structure (ratio of -S-, -SS-, -S bonds) achieved in favor of nonosulfidischer crosslinking sites, which may affect the vulcanizate properties adversely.However, this measure becomes increasingly ineffective, the higher the Vulkanisationstempelatur is set.

-12- 26 4 0 07

These disadvantages of the benzothiazole accelerators limit their utility with increasing vulcanization temperature and set certain limits on the efforts of the Kautachuk industry to increase their productivity through the use of higher vulcanization temperatures.

Surprisingly, the N ₁ N'-substituted bis (2,4-dia! Ru.no-a-triazin-6-yl) tetrasulfides according to the invention and their disproportionation products prove both in 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 vulcanization temperatures extremely high reversion stability - even with very high overheating - characterized in that the usual in their use reversion usually does not occur at all or if, then only to a small extent. The surprising fact that the crosslinking sites resulting from the N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides or their disproportionates claimed by the invention prove to be extremely resistant to reversal and to thermostability, When used in rubber mixtures, even at high vulcanization temperatures, on the one hand a high level of performance of the vulcanizates is achieved on the one hand and, on the other hand, the high level of performance is maintained for a long time even under severe overheating.

Taken together, these two effects allow productivity gains in the rubber-processing industry to increase productivity without loss of VuIcanisate performance by increasing the VuI kani sation steraperatur.

An even approximately the same reversion resistance leaves

with commercially available polysulfides of Robac ^ P 25 Di

(R) pentamethylene thiuram tetrasulfide) and Tetron ^v 'k dipentamethylene thiuram hexasulfide) or with dibenzothiazolyl tetrasulfide can not be achieved.

The use of the claimed according to the invention Ν, Ν'-substituted Bis ~ (2,4-diamino-8-triazin-6-yl) ~ tetrasulfides and their Diaproportionierungseprodukte includes the known in the prior art rubber matsungen based on natural rubber (NR) , Isoprene rubber (IR), butadiene rubber (BR) styrene-butadiene rubber (SBR), isobutylene-isoprene rubber (HR), ethylene-propylene terpolymer (EPDM), nitrile rubber (NBR), halogen-containing rubbers and also epoxidized natural rubbers (ENR) and their blends , Of particular importance is the use of the N ₁ N * -substituted bis (2,4-diamino-s-triazin-6-yl) -oligo-sulfides prepared according to the invention in the case of the rubber types susceptible to reversion, for example natural rubber, isoprene and butadiene rubbers. rubbers and their blends with each other or with other rubbers.

The N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) -oligosulphides prepared according to the invention are used as crosslinkers in rubber mixtures in an amount of 0.2-15 TIn., Preferably 0.3-8 Parts by weight, to 100 parts rubber, used «

In accelerated sulfur vulcanization, the N, N'-substituted bis- (2,4-diaminos-triazin-6-yl) -oligosulfides prepared according to the invention or their disproportionation products are used as accelerators in quantities of 0.3-8 parts, preferably 0.1- 5 parts, based on 100 parts of rubber, one in sulfur codings of OcO - 10 parts. A mo-

lares erfindungagemäßen ratio of accelerator to sulfur (Sg) of 1: 0.5 - 1.5 · In order to obtain a certain variation range of the vulcanization kinetics, this may be prove useful, 2 or more different N ₁ N'-substituted bis (2 To use, 4-diamino-s-triazin-6-yl) -01igo sulfides in Geraisch, wherein to comply with the above-mentioned application rates, in particular the preferred accelerator / sulfur ratio, the substitution is to be made on a molar basis. The same applies when using the N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligo sulfides as crosslinkers without sulfur ·

Likewise, for kinetic reasons, it may prove expedient, the N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -01igo sulfides in admixture with conventional accelerators such. As sulfenamides and thiurams to use. These measures are sometimes at the expense of reversion resistance compared to the N, N'-substituted 7i-bis (2,4-diamino-s-triazin-6-yl) -01igo sulfide vulcanizates, but inversely it has a positive effect in terms of the reversion behavior when replacing conventional accelerators partially by N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -01igo sulfides.

Another significant influence on the incubation time when using the compounds according to the invention in rubber mixtures can be achieved by combination with commercial vulcanization retardants, such as βantoguard ^v 'PVI (N- (cyclohexylthio) -phthalimide), Vulkalent ^ E (N-phenyl-N-ctrichloromethylsulfenyD-benzenesulfonamide), be achieved. The most effective retarder is Vulcalent ^v 'E. With increasing Vulkalent ^ ' E addition occurs a linear increase in the incubation time of N, N'-substituted bis (2,4-diamino-8-triazin-6-yl) -01igo sulfides containing mixtures.

- ¹⁵ - 2 θ 4 OO 7

When N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) -01-ol sulfides or their disproportionation products as crosslinkers are used, adherence to the molar ratio of N, N'-substituted bis (2-chloro) (2,4-diamino-s-triazin-6-yl) -01igo sulfides to Vulkalent E of 1 >. 0.5 - 1.5, preferably 0.8 -1.2 parts per 100 parts rubber proved to be useful.

Of more importance is the use of retarders, especially Vulcalent E, in accelerated sulfur vulcanization using N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -01-ol sulfides and mixtures thereof. Occasionally, in addition to the intended extension of the incubation time of the crosslinking reaction, a slight impairment of the crosslinking rate is occasionally observed, which, however, can be absorbed by increasing the temperature and a slight decrease in the reversion resistance. It has also been found in this Pail, the molar ratio of N, N »-substituted bis (2,4-diamino-s-triazin-6-yl) -01igo sulfides to Vulkalent E to 1: 0.5 - 1.5 preferably 1: 0.8 to 1.2, the sulfur content, depending on the type of mixture, being between 0.1 and 10 parts, preferably 0.5 to 12 parts relative to 100 parts of rubber.

With these dosage guidelines, many of the stated vulcanization problems can be solved without there being a 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 15 parts / 100 parts rubber are, if at all, conventional

Sulfur vulcanization difficult to crosslink. On the one hand, they are particularly subject to reversion, on the other hand, they prevent the setting of Vernetzunpsdichte, 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 bis (2,4-diamino-s-triazin-6-yl) -01igo sulfides in mixtures containing black / white blends with silica content of more than 15 parts / 100 parts of rubber and also with silica filled mixtures both when used as accelerators as well as crosslinkers (without sulfur) to virtually eliminate the reversion and at the same time to increase the crosslinking density, which is expressed in a high voltage level for silica mixtures.

Another application of the N, N'-substituted bis (2,4-diaminos-triazin-6-yl) -01igc sulfides is the combined use with oligosulfidic organosilanes, for example

I (RO) ₃ -Si - (CHg) _n -J -S _x or (RO) ₃ -Si (CHg) _n -SH

with χ = 2-6, R = C ₁ -Cg-AllCyI, cyclohexyl η = 2 or 3

or mr

(RO) ₃ J- Si - 6 (CH ₂ ) _n -7 ( 3, ^S x 2 with χ β 2 - , prefers

preferably bis (3-triethoxysilylpropyl) tetrasulfide (Si 69, Degussa AG). N, N * -substituted bis- (2,4-diamino-s-triazin-6-yl) -01igo sulfides can be used both in the sulfur-free organosilane crosslinking instead of the accelerator described in DE-PS 25 36 674 and also advantageous in the sulfur vulcanization described in DE-PS 22 55 577 with organosilanes and also in the production of reversion-stable organosilane-containing rubber mixtures by construction of equilibrium cure systems according to DE-PS 28 48 559.

This applies both to carbon black-filled mixtures and to mixtures containing carbon black / silica couplings, as well as to mixtures which are built up only using silicic acids. The addition of mineral PUIlstoffe adversely affects in any of the above mixtures. In the presence of silica fillers or of blends of carbon black with silicas, rubber / rubber bonds are formed (rubber + rubber, plastics, Issue 8, 1977, pages 516-523, Issue 10 »1979, pages 76O-765 and Issue 4, 1981), pp. 280-284) or in the presence of carbon black / rubber carbon blacks.

The construction of rubber / rubber crosslinking sites in the presence of carbon black or of rubber / filler crosslinking sites in the presence of silicic acid and both types of bonding in the case of carbon black / silica mixtures of all ratios is also successful if N, N'-substituted bis ( 2,4-diamino-s-triazin-6-yl) -01-ol sulfides, alone or mixed with several or in admixture with conventional accelerators together with conventional sulfur

(R)

Donors such as Sulfasan ^v 'R (morpholine disulfide) are used.

The use of the compound of the invention according to claims

to 5 takes place in rubber mixture © ^ which may contain other conventional components such as:

customary gain systems, d. H. Furnace carbon black, channel blacks, flame blacks, thermal blacks, acetylene blacks, carbon blacks, OK carbon blacks, etc., and synthetic fillers such as silicas, silicates, alumina hydrates, calcium carbonates, and natural fillers such as clays, silicates, chalks, talcs, etc. as well as silane-modified fillers and their Blends in quantities of 5 parts per 100 parts of rubber, particular preference is given to silicas and silicates,

ZnO and stearic acid as promoters of vulcanization in Kengen from 0.5 to 10 parts of 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, other silanes such as -chloropropyltrialkoxisilane, Vinaltrialkoxysulane, and Aminoalkyltrialkoxisilane and their blends in a Mer¬ e of 0.1 - 15, preferably 1-10 parts, per 100 parts silanolgruppentragender fillers such as silicas, silicates, clays, etc.

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

The scope of the N, N * -substituted bis (2,4-diaminos-triazin-6-yl) -01-ol sulfides extends to rubber blends

according to claims 6 to 10, containing fillers and other ingredients based on one or more natural and / or synthetic rubbers and characterized in that they

- 0.3 - 8 parts per 100 parts of rubber of N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligo sulfides and / or mixtures with conventional. Accelerators contain at sulfur dosages of 0.0-10 parts per 100 parts of rubber;

the retarder N-phenyl-N-cetrichloromethylsulfenylJ-benzenesulfonamide and N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligosulfides in a molar ratio of 0.5-1.5: 1 , preferably 0.8 to 1.2: 1, at a sulfur dosage of 0.1 to 10 parts by weight to 100 parts of rubber, preferably 0.5 to 8 parts based on 100 parts of rubber;

- The retarder N-phenyl-N- (tri-chloro-thylsulfenyl) benzene sulfonamide and N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides in a molar ratio of 0.5 to 1 , 5: 1 »preferably 0.8: 1.2: 1, contained per 100 parts of rubber at a sulfur dosage of 0.0 parts;

- Contain as fillers only silicas;

- contain, as filler except carbon black, more than 15 parts of silica per 100 parts of rubber normally used in tire manufacture and technical articles such as mixtures for conveyor belts, V-belts, molded articles, hoses with and without inserts, roll rubbers, linings, Spray profiles, freehand articles, foils, shoe soles and tops, cables, solid rubber tires and their vulcanizates.

Examples of compounds prepared according to the invention are the following products:

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

-oligosulfidgemisch bis (2-cyolohexylamino-4 ~ diethylamino-s-triazin-6-yl)

-oligosulfidgemisch bis- (2-ethylamino-4-diethylamino-s-triazin-6-yl)

-oligosulfidgemisch bis- (2-amino-4-diethylamino-s-triazin-6-yl). Exemplary embodiments

The invention is explained in more detail below with reference to some examples:

Example 1:

45 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. 200 ml of methylene chloride are added thereto. The mixture is turbined and cooled to 0 ^° C. One now dissolves 1'4 g of S ₃ Cl ₂ in 50 ml of CH ₂ Cl and allows this solution to run into the mercaptide solution.

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

Quantity: 46.7 g, corresponding to 90.5 % of theory. Analysis: C ^ KLgN ^ S. (Mol. 516)

N 27.1 S 24.8

gef. 26.8 24.4

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

Example 2;

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 % of the starting material 3 more oligosulfides.

Example 3:

70.25 g of 2-cyclohexylamino-4-diethylaraino-6-mercaptotriazine are dissolved in 11 g of NaOI and 250 ml of water. To this is added 250 ml of chloroform. With vigorous stirring, a solution of 16.8 g of SpCl in 'U) ml CHCIo run. At the end of the reaction, the phase is separated and the chloroform layer is worked up. This gives 71.9 g of a white amorphous powder, corresponding to 92 % of theory.

Analysis: L C 6 ^H 4 1 H \ 7 (Mol wt. 624) S 20 51 calc. 50 6 , 05 N 22.4 20 gef. 49, 90 21.8

2ö4 ο Ο 7

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

auditing standards

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

measured in

Tensile strength, breakage DIN 53 504 MPa stretching and tension worth 6 mm thick rings Shore A hardness DIN 53 505 - M-restone-ball rebound AD 20245 % reversion DE-PS 2 840 559 Incubation time t j DIN 53529 (Min) scorch ASTM D2084 (Min)

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

RSS: Ribbed Smoked S.'ieet (Natural Rubber)

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

(R) Naftols ^K ' ZD: Plasticizers from Hydrocarbons Ingraplast NS: Plasticizers from Naphthenic Hydrocarbons

materials

Vulkanox.RTM

(R)

NA: N-isopropyl-N'-phenyl-p-phenylenediamine

Vulkanox ^ HS: Meeamoll ^{v J} : Robac P 25 Tetrone A protector

fR)

Poly-2 _l 2,4-trimethyl-1,2-dihydro-quinoline Alkyl sulfonic acid esters of phenol and cresol Dipentamethylene thiuram tetrasulfide Dipentaethylene thiuram hexa sulfide G 35: Ozone protection agent

Vulkaoit ^v 'MOZ: Benzothiazolyl-S-morpholino sulfenamide Vulkacit ^K ' Mercapto: 2-mercaptobenzothiazole

(R) Vulkacit ^v 'Thiuram: tetramethylthiuram monosulphide

Vulkacit vulcalent

PVI:

Ultrasil Gran »V 143:

CZ:

e:

N-cyclohexyl-2-benzothiazolsulfenaraid

N-phenyl-N- (trichlorraethylsulfenyl) -bonzol-3ulfonamid

N-cyclohexylthiophthalimide precipitated silica granules

Bis- (2 "ethylamino-4-diethylamino-8-triasin-6-yl) disulphide

(R)

Vulcacit ^v ' NZ benzothiazyl-2-tert-butylsulfenamide

Example 4:

Reversion stability of N, N'-substituted bis (2,4-diamono-s-triazin-6-yl) oligo-sulfides crosslinked N 220-filled NR (without sulfur)

1 2 RSS 1, ML 4 = 70 - 80 100 100 CORAX N 220 50 50 ZnO RS 5 5 stearic acid 2 2 Naftolen ZD 3 3 Vulcanox 4010 NA 2.5 2.5 Vulcanox HS 1.5 1.5 Protector G 35 1 1 Vulkacit MOZ 1.43 - V 143 - 1.29 Santoguard PVI - 0.4 sulfur 1.5 1.5 Reversion: max - (max +60 ') 30.1 8.6 max ~ min at 170 ⁰ O

vulcanization

Continuation Example 4

0 3 3.84 - 4 5 100 - 100 100 RSS 1, ML 4 a 70 - 80 50 50 5o CORAX N 220 5 2.5 5 5 ZnO RS 2 2 2 stearic acid 3 3 3 Naftolen ZD 2.5 2.5 2.5 Vulcanox 4010 NA 1.5 1.5 1.5 Vulcanox HS 1 1 1 Protector G 35 - - K 3.62 - L - 4.0 M Reversion: 3.1 2.3 mas "(max +60") , <a \

D - D

 ma :: nan

* jei 170 ⁰ C vulcanization temperature

The N, N''-substituted bis (2,4-diamino-stria2.in-6-yl) -oligo sulfides according to the invention prove to be extremely resistant to reversal in soot-filled NR mixtures when used as a promoter (without sulfur) (US Pat. Compounds 3-5) compared to a semi-EV system (mixture 1) or to a bis (2-ethylamine-4-diethylamine-s-triazin-6-yl) -disulfide (V 143) -containing mixture (mixture Γ).

Example 5:

Reversal Stability of N, N'-substituted Bis (2,4-diamino-s-triazin-6-yl) -oligosulfides Crosslinked N 220 / Silicic Acid-Filled NR (without Sulfur)

6 7 8th 9 RSS 1, ML (1 + 4) = 70-80 100 100 100 100 OORAX N 220 25 25 25 25 Ultrasil VN 3 Gran. 25 25 25 25 ZnO RS 5 5 5 5 stearic acid 2 2 2 2 Naftolen ZD 3 3 3 3 Vulcanox 4010 NA 2.5 2.5 2.5 2.5 Vulcanox HS 1.5 1.5 1.5 1.5 Protector P 35 1 1 1 1 K - 3.48 " - L - - 3.62 - M - - 3.0 Vulcazite MOZ 1.43 - - - sulfur 1.5 - - - Reversion: ^D max " ^D (max + 60 ') (%) 47.1 2.5 3.1 4.7 D - D. max min at 170 ⁰ O

vulcanization

Siliceous NR mixtures show particularly strong reversion phenomena even when using semi-EV systems (mixture 6). With the N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) -oligosulfides used according to the invention as crosslinkers (mixture 7-9), an almost no-change state is achieved with an otherwise identical composition.

28 4 O

Example 6: Reversion resistance of N, Ν-substituted bis- (2,4-diamono-s-triaEin-6-yl) -oligosulfides accelerated N 220-filled NR

10 11 12 1.81 - 13 RSS 1 ₅ (ML 1 + 4) = 70-80 100 100 100 0.8 100 CORAX N 220 50 50 ' 50 - 50 ZnO RS 5 5 5 5 stearic acid 2 2 2 1.5 2 Nafetch ZD 3 3 3 3 Vulcanox 4010 NA 2.5 2.5 2.5 2.5 Vulcanox HS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 K - 1.74 - - L - - - M - - 1.5 sulfur 1.5 0.8 0.8 Vulcazite MOZ 1.43 - - Reversion: ^D max " ^D (raax + 60 ') (%) 31.9 0.4 5.2 max. "min at 170 ^° C

vulcanization

Vulcanizate data at

170 ⁰ C, t 95 %

Tensile strength 23.0 22.9 24.2 22.2 Tension 300 % 9.6 10.3 10.0 10.6

With equimolar accelerator dosing, the amount of sulfur delta can be reduced in the pail of N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) tetra- or -oligosulfides. Nevertheless, higher 300% voltage values are achieved. The mixtures prepared with N, N'-substituted bis (2,4-diamino-8-triazin-6-yl) oligosulfides (mixtures 11-13) prove to be extremely resistant to reversion to a semi-EV system (mixture 10 ).

Example 7;

Comparison of the Reversal Behavior of Commercial Oilgosulfides and Dibenzothiazolyl Tetrasulfide versus N ₉ N'-substituted Bis (2,4-Diaraino-s-triazin-6-yl) Oligosulfide in N 22O-Filled NR.

14 15 16 17

RSS 1, ML (1 + 4) = 70-80 100 100 100 100 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 Vulcanox 4010 NA 2.5 2.5 2.5 2.5 Vulcanox HS 1.5 1.5 1.5 1.5 Protector G 35 1 1 1 1 Robac P 25 1.12 - - - Tetrone A - 1.3 - - Dibenzthiazolyltetra sulfide - - 1.15 - M - - - 1.5 sulfur 0.8 0.8 0.8 0.8 Scorch time 170 ⁰ C 1.4 1.9 2.7 3.1 (t 10 %), min

~ ²⁹ "ü 8 4 ü 0 7

Reversion:

^D max " ^D (max + 60 ') (%) 18.5 21.3 35.7 3.2

max ~ min

at 170 ⁰ O vulcanization temperature

Vulcanizate data at 170 ^° C., t 95 %

Tensile strength 23.1 21.2 18.9 23.6

Voltage value 300 % 9.4 9.5 7.3 10.4

Commercially available oligosulfides (mixture 14 and 15) as well as Dibenzthiazolyltetrasulfid (mixture 16) show in NR more times higher than a reversion N ₁ N'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligosulfid (mix 17).

Example 8:

Mixture of N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetrasulfide with N, N'-substituted bis- (2,4-diaraino-striazin-6-yl) - oligosulfide in N 220-filled NR,

18 19 20 21

RSS 1, ML (1 + 4) = 70-80 100 100 100 100 GORAX N 220 50 50 50 50 ZnO RS VJL VJL VJL VJL stearic acid 2 2 2 2 Naftolen ZD 3 3 3 3

2 , 5 2.5 2 , 5 2.5 1 , 5 1.5 1 , 5 1.5 1 1 1 1 1, 43 - - 1 1.5 - 0.75 - - 1, 66 0.83 1 , 5 0.8 0 ,8th 0.8

28 4 υ U 7

Continued Example 8

Vulcanox 4010 NA

Vulkanox HS Protector G 35 Vulkacit MOZ

sulfur

Reversion:

^D max " ^D (max + 60") (#) _{30 1 2 3 Q. 1 2}

max. "min

at 170 ⁰ G vulcanization temperature

The combined use of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides with different reversion resistance results in a value image that lies between the pure substances (21 iiche).

Example 9:

N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligosulfides in N 220-filled SBR

SBR 1500 CORAX N 220

22 23 24 100 100 100 50 50 50

284 0 0

Continued Example 9

ZnO RS

Stearic Acid Naftols ZD Protector G Vulcanox 4010 NA Vulkanox HS Protector G Vulkacit MOZ

sulfur

Reversion:

^D max " ^D (max + 60") (%) 12.9 9.2 12.5

max ~ min

at 170 ⁰ O vulcanization temperature

Vulcanization data at

VJI VJL 5 2 2 2 3 3 3 1 1 1 2 , 5 · 2.5 2.5 1 , 5 1.5 1.5 1 1 1 1, 43 - - - 1.5 - - - 1.5 1 , 5 1.5 1.5

170 ^Q C, t 95% ao, 6 20.5 19.9 tensile strenght 10.0 12.1 12.3 Voltage value 300 % 460 420 390 elongation 61 63 64 Shore hardness

At the same sulfur dosage, N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) -tetra- or -oligosulfide (mixtures 23, 24) in SBR 1500 show a significantly higher voltage value and slightly improved reversion properties against a conventional acceleration (mixture 22).

Example 10;

N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides in N 220-filled isoprene rubber

Polyisoprene 3,4 OORAX N 220 ZnO RS

Stearic acid Naftolen ZD Vulkanox 4010 NA Vulkanox HS Protector G 35 Vulkacit MOZ L M Sulfur

Reversion:

^D max " ^D (max + 60 ') (%) 21.0 0.0 0.0

max ~ min

at 170 ⁰ C vulcanization temperature

25 26 27 100 100 100 50 50 50 5 5 5 2 2 2 3 3 3 2.5 2.5 2.5 1.5 1.5 1.5 1 1 1 1.43 - - - 1.6 - - - 1.5 1.5 0.8 0.8

264007

Vulcanizate data at 170 ⁰ O,

Voltage value 300 % t 95% 7.9 6.3 6.4 t 95 % + 80 '6.2 6.3 7.1

In polyisoprene rubber, the use of N, N'-substituted bis- (2,4-diamino-s-triazin-6-yl) -oligosulfides (mixtures 26,27) with conventional accelerators (mixture 25) also gives a clear Improvement of reversion achieved. This improvement is also evident in the constancy of the vulcanizate data with significant overheating.

Example 11;

N, N'-substituted bis (2,4-diamino-triazin-6-yl) -oligosulfides in N 220-filled EPDM

Buna AP 451 CORAX N 220 ZnO RS

Stearic Ingraplast NS Vulkacit Thiuram Vulkacit Mercapto

Sulfur ^D max - ^D (max +60 »)

28 29 100 100 50 50 5 5 CVJ 2 10 10 1 - 0.5 - 2.5 1 1 3.3 0.0

max ~ min

at 160 ⁰ O vulcanization apero door

Ready high-conversion-resistant EPDM mixtures show a further reduction in reversion to zero when replacing conventional accelerator mixtures (mixture 28) with N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) 'oligobiprofides (Mixtures 29)

Example 12;

N, N'-substituted bis-i, 2,4-diamino-s-triazin-6-yl) -tetra- and -oligosulfides in N 220-filled NER

Perbunan N 3307 NS CORAX N 220 ZnO RS

Stearic acid paraffin fixed Mesamoll Vulkanox HS Vulkacit CZ

sulfur

Reversion:

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

30 31 100 100 60 60 5 5 1 1 1 1 10 10 1.5 1.5 1.5 1.5 - 1.5 1.2 1.2 8.0 5.6

max. "min

at 170 ⁰ C vulcanization temperature

Vulcanizate data at

170 ^V C, t 95% 11.8 14.6 Voltage value 300 % 68 69 Shore hardness

With the same sulfur elgeha? In the case of substitution by N, N-substituted-bis- (2,4-diamino-s-triazin-6-yl) -oligosulfides (Mixture 31) in NBR, there is a marked increase in the voltage value against the refining mixture (Mixture 30) at 300 % elongation with simultaneous reduction of reversion.

Example 13:

Reversion Stability N, N'-substituted bis- (2,4-diamino-striazin-6-yl) -oligo sulfides in N 220-filled BR

Buna CB 10 CORAX W 220 ZnO RS

Stearic Acid Naftols ZD Protector G Vulcanox 4010 NA Vulkacit NZ M Sulfur

Reversion: ^D max " ^D (max +60")

32 33 100 100 60 60 3 3 2 2 15 15 1 1 1.5 1.5 1.5 - - 1.5 1.5 1.5 30.3 20.8

D - D. max nan

at 170 ⁰ C Vulkaniaationsteniperatur

Vulcanizate data at

170 ⁰ G 300 % t + 95 % 8th, 6 8th , 9 voltage value t 95 % 75 ' 5, 6 6 ,8th

Due to the lower reversion of the M accelerated BR mixture (mixture 33), the decrease in the voltage value 300% is significantly reduced in the case of strong overheating compared to the reference mixture (mixture 32).

Example 14:

N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides in N 220-filled NR / HR blend

34 35 RSS 1, ML (1 + 4) = 70-80 70 70 Buna GB 10 30 30 GORAX in 220 50 50 ZnO RS 5 5 stearic acid 2 2 Naftolen ZD 3 3 Vulcanox 4010 NA 2.5 2.5 Vulcanox HS 1.5 1.5 Protector G 35 1 1 Vulkacit MOZ 1.43 - C - D - - M - 1.5 sulfur 1.5 0.8

Reversion:

^D max " ^D (max + 60 ') (%) 32.0 23.8

max ~ min

at 170 ^° C. vulcanization temperature ·

Mixture 35 shows a marked reduction in reversion when using N, N * -substituted bis- (2,4-di-amino-s-triazin-6-yl / oligosulfide against a semi-EV system (Mixture 34) in one Blend of NR and polybutadiene.

Example 15:

Crosslinking of 50% epoxidized natural rubber (ENR 50) at N 220 fill N, N'-substituted bis (2,4-diamino-striazin-6-yl) oligosulfide

- 60 ») (%) 36 37 ENR 50 100 100 CORAX N 220 50 50 ZnO RS 5 5 stearic acid 2 2 Vulkanox Hi 2 2 Vulkacit KOZ 2.4 - 1.6 - 4.0 0.3 0.3 6.7 0.0 Vulkacit thiuram M sulfur Reversion: max ~ (max π max ~ min

at 150 ⁰ G 18.7 24.6 vulcanization 18.0 18.9 Vulcanizate data at 12 12 150 ⁰ C, t 95 % 75 78 tensile strenght Voltage value 300 % WeiterreißvTiderstand Shore hardness

At the same stress value at 300 % elongation and significantly increased tensile strength, replacement of conventional acceleration (Blend 36) by N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides (Mixture 37) to an additional improvement of the reversion.

Example 16;

Delaying effect of Vulcalent E on N, N'-substituted bis (2,4-diamino-triazin-6-yl) -oli-gosulfide vulcanized N 2 20 / NR mixtures

RSS 1, ML 4 = 70-80 GORAX N 220 ZnO RS Stearic Acid Naftols ZD Vulkanox 4OIO NA Vulkanox HS

38 39 40 100 100 100 50 50 50 5 5 5 2 2 2 3 3 3 2.5 2.5 2.5 1.5 1.5 1.5

~ ³⁹ "

Continued Example 16

Protector G 35 1 ^Λ 1

Vulkacit MOZ 1.43

M - 1.55 1.55

Sulfur 1.5 0.8 0.8

Vulcalent E - · - 1,2

ti (min at 170 ^° C.) 3.8 2.9 4.1

Vulcanizate data at 170 ^° C., t 95 %

Voltage value 300 % 10.6 10.6 11.0

The addition of Vulcalent E in M accelerated mixtures (mixtures 39 and 40) leads to an increase in the incubation time ti above the level of the conventionally MOZ accelerated mixture (mixture 38).

Example 17;

Effect of Vulcalent E on N, N'-substituted bis (2,4-diamino-8-triazin-6-yl) -glysulfide crosslinked NR with N 220 / silica

41 42 43

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

Ultrasil VN 3 Gran. 25 25 25

OORAX Ii 220 25 25 25

ZnO RS 5 5 5

Stearic acid 2 2 2

Naftolen ZD 3 3 3

Continuation Example 17

Vulcanox 4010 N / A (Min) 2 , 5 2.5 2.5 Vulcanox HS (Min) 1 , 5 1.5 1.5 Protector G 35 1 1 1 Vulkacit MOZ 1, 43 - - M 3.0 3.0 VulcanHint E - - 1.2 sulfur 1 , 5 0.8 0.8 Scorch at 130 ⁰ o 29 , 5 16.5 29.0 Scorch at 170 ⁰ C 4 , 5 3.7 4.8

Vulcalent E can be used to accelerate with W, N'-substituted bis (2,4-diaminophenyls-triazin-6-yl) oligosulfides (mixtures 42 and 43) to give a comparable MOZ scorch behavior.

Claims (9)

264 Pa t ο α 111 αη οrüc he 1st Ver. for the production of chemical, consisting only. Compounds of the general x'ormel R ³ R ⁴ R ³ R ^{4 L} (I) 2. The method according to claim 1, characterized in that one heats the T'etrasulfiue ^ e.aiiß formula II beyond its melting point. ² / \ H ² in which mean R ¹ , α ² β K, R ² = benzyl, R ² , R ³ , R ⁴ = O ₁ -C ₈ -alkyl, allyl, C ₃ -C ₃ -cycloalkyl, the latter unsubstituted or substituted 1-3 Liethyl ^ ruppeu, 2-Kydroxiethyl, 3-Hydroxipropyl, -2-Hydroxipropyl or R ³ and R ⁴ (together): C 1 -C 4 -alkylene, - (CH ₂ -CIiX) ₂ Y with X «H, CH ₃ , Y a O, S _; ,
and> j corresponds to a mean statistical chain length with χ = 4, 3. The method jvemäß claim 1, characterized, in that the:,: et L'iiCLili'ide according Poivael 11 dissolves in einara inert organic solvent / .iittel and Disproprtionierungsreaktion in Jemper ^ turboroic'i between 20 and boiling point of ⁰ G of the solvent 11 e 1 sa oil au f ο η 1;. 4. Demonstrate according to claim 1b, characterized> _. > .. iu. · anzeichnet that one S ι as LOiJiUIg _{1 1} UII, οΐ chlorinated hydrocarbon ο, iituor odor j'iscor and aromatic hydrocarbons and ketones ο used which are insoluble in water. 5. Volcanizable fillers containing all usual constituents, on the basis of one or more natural and / or synthetic chewable gums (e) (d), which are characterized 0,3 - c3 ΐοϋο, per 100 χ hile of rubber, the compounds (emä !? claim 1 to '3 and / or mixtures with conventional accelerators contain in sulfur doses of 0.0 to 10 parts per 100 parts of rubber. 6. Vulkaninierbc / .re i.iischuaßen _o ernäß claim 5, characterized in that it comprises the retarder xJ-phenyl-Il- (trchlcumethylsulfenyl) -benzolaulfoauniicl and the compounds ^ eniäß to claims 1 - ο in the I-iolvorhältnis 0.5 - 1.5: 1, preferably 0.8 - 1.2: 1, at a Schvvefeldoaierung of 01, - 10. Gev.'iclit3te.ilen to 100 'X'eile rubber, preferably 0.5 to 3 parts based on 100 parts of rubber. 7 »vulcanizable blends according to claim 5 and G _9, characterized in that they the retarder if-phenyl-rl-ctriclilomethyl3ulfenyl) -benzolsulfonaniid and the compounds according to claims 1-5 in i.Iolverhältnis 0.5 - 1.5: 1, preferably 0.8 to 1.2: 1, contained on 100 parts of rubber, at a sulfur dosage of 0.0 parts. 8. Vulcanizable mixtures according to donAnsprüchea 5 to 7, characterized in that they contain as fillers only silicic acids. 8 4 O Q 7 characterized, ^ ^ιν ·· ^: a) Connections of the rdl ^ ewänen l'Ormol R ³ R ⁴ R ³ R ⁴ N. W "N <I H V / V in Λ, .ί, K and U ⁴ have the same Jiedeutun ^ on as above, ltißt disproportionate. oiuie that free sulfur arises, or b) the oiu'i in the reaction of an aqueous alkolischon LogLUi ^ the corresponding iT, L-substituted 2,4-diamino-b-mercaptotriazine in a υ / η Zwo-iphüsensyatern with a solution of S ₀ Gl ₀ in an inert disproportionate organic Lösutiijöiiiittel forming j'etrasulfide, which are soluble in the organic solvent. 9. Vulcanisable mixtures according to claims 5 to 7, 28400; It is true that they contain more than 15 parts of oleic acid per mole of rubber as aluminum in the form of aluminum.