DD263297A5 - Use of substituted N-trichloromethylthiodicarboximides in combination with N, n'-substituted bis- (2,4-diamino-S-triazin-6-yl) -oligosulphides in vulcanizable rubber mixtures and such rubber mixtures - Google Patents

Abstract

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

Description

R ⁷

with R ⁷ , R ⁸ = H, methyl,

R ⁵ and R ^{6 represent} an endo-CH ₂ or endo-O bridge, in combination with olsulfidic compounds of the formula:

: R ³ / R ³ R ⁴

lfN5T

in which mean

R ¹ , R ² = N, R ² = benzyl,

R ² , R ³ , R ⁴ = C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, the latter unsubstituted or substituted by 1-3 methyl groups, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or R ³ and R ⁴ ( together): C ₄ -C ₆ -AlkyIeη, - (CH ₂ -CHX) ₂ Y with X = H, CH ₃ , Y = O, S η = 2 or 4 or a mixture of compounds according to formula II, in which S _n corresponds to a mean random chain length with η = 4, characterized in that they are used in vulcanizable rubber mixtures as vulcanization retardants with crosslinking density-increasing effect.

2. Use of compounds according to claim 1, characterized in that they are used in combination with conventional benzthiazole or thiuram based accelerators.

3. Use of compounds according to claim 1, characterized in that they are in combination with organosilanes of the general formula

III

(RO) ₃ - Si - (CH ₂ ) _n

or CRO) ₃ -Si (CH ₂ ) _n -SH

with η = 2; 3, χ = 2-6, R = C ₁ -C ₆ alkyl, cyclohexyl or

(RO) ₇ - Si

with χ = 2-6, preferably 3,

be used in vulcanizable rubber mixtures.

4. Use of compounds according to claim 1, characterized in that they in combination with additional sulfur donors in vulcanizable rubber mixtures.

5. Vulcanizable rubber mixtures, characterized in that they contain 0.1-5 parts of substituted N-Trichlormethylthiocarboximide according to the formulas (I, Ia), and 0.1-10 parts of N, N'-substituted bis (2,4 -diamino-s-triazin-6-yl) -oligosulfides according to formula (II) and optionally 0.1-10 parts of sulfur, in each case based on 100 parts of rubber, wherein in the presence of the three components whose molar ratio is 0.3- 1.5: 1: 0.5-1.5, preferably 0.3-1.2: 1: 0.5-1.5, while in the absence of sulfur it is 0.3-1.5: 1 ,

Field of application of the invention

The invention relates to the use of substituted N-Trichlormethylthiodicarboximiden in combination with N, N'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides in vulcanizable rubber mixtures as Vulkanisationsverzögerer with a crosslinking density-increasing effect and Such rubber mixtures.

Characteristic of the known state of the art

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

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

In this case, η = 4 is both for tetrasulfides and for mixtures of compounds of formula II, in which S _{n is} a middle

statistical chain length with η = 4.

Benzothiazole-based mercaptans, disulfides and sulfenamides are the most important sulfur vulcanization accelerators. Similar effects on triazine-based compounds are described in DE-PS 1 669954 and DE-PS 1 298 706. The Kategorie, Ν'-substituted bis- (2,4-diamino-s-triazine-6 -yl) -oligosulfides (n = 4) according to formula II, described in patent application P, which in contrast to the abovementioned accelerators without the -.

Addition of free sulfur crosslink to form an -S, -S-S, -S-Sx-S crosslinking structure.

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

Their behavior usually differs in all 3 phases.

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

Technol. 50,570 [1977], Monsanto, US Pat. Nos. 3,427,319,3546,185, 3,752,824, 3,855,262) and, for benzothiazolyl disulphide, preferably N-phenyl-N- (trichloromethylsulfenyl) benzenesulphonamide (DE-OS 19574874) as effective agents.

Object of the invention

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

-3- 263 Z97 Explanation of the essence of the invention

R ⁹ _CH - CO

The invention relates to the use of compounds of the general formula - Un - UU

NS-CCl ₃

in the mean

R ¹⁰ : H, Ci-Ci6-alkyl, undecenyl, or R ⁹ and R ¹⁰ form together with the standing in the 3- and 4-Stel ment carbon atoms of the dicarboximide a six-membered ring, saturated or mono- or triunsaturated, the one to May be substituted twice by a methyl group, in particular tetrahydrophthalimides of the type

F-S-GGIo da)

with R ⁷ , R ⁸ = H, methyl,

R ⁵ and R ⁶ an endo-CH ₂ bridge or an endo-O-bridge, in vulcanizable rubbers in combination with oligosulfidic compounds according to the formula

Are those in which

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, allyl, C 1 -C -cycloalkyl, the latter unsubstituted or substituted by 1 to 3 methyl groups, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, or R ³ and R "(together): C 6 -C 12 alkylene, - (CH ₂ -CHX) ₂ Y with X = CH ₃ , H; Y = 0.5

or a mixture of compounds of the formula (II) in which S _n corresponds to an average statistical chain length with η = 4.

The process for preparing the pure tetrasulfides having a linear S ₄ chain between the two substituted triazine radicals is characterized in that an aqueous, alkaline solution of the corresponding N, N'-substituted 2,4-diamino-6-mercaptotriazines 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 slightly soluble, at temperatures between -5 ° C to <+ 20 ° 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 Cs-C-io-alkanes or Cs-Cg-cycloalkanes, optionally substituted with 1 to 3 methyl groups, and mixtures thereof. This mixture is stirred vigorously and cooled, preferably to + 1O ⁰ C. Now one can in this mixture under thorough cooling, a solution of S ₂ CI ₂ in the solvent used is added dropwise. S ₂ Cl ₂ is used at least in the ratio of 2 mol of mercaptotriazine: 1 mol of S ₂ Cl ₂ , but depending on the excess of alkali, this ratio may also be 2: 1.1-1.2.

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

The resulting product is separated by means of generally known measures and advantageously dried at temperatures up to + 5O ⁰ C under vacuum (10 Torr).

Also used are mixtures consisting of oligosulfidic compounds of the general formula

R ³ R ⁴ R ³ R ⁴

Γ4

χ

R \

1 NN _r 1

• r ²

in which R ¹ , R ² , R ³ and R ^{4 have} the abovementioned meanings and S _n corresponds to a mean statistical chain length with η = 4~~.

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

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

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

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

A particularly elegant method consists in reacting an aqueous alkaline solution of the corresponding N, N'-substituted 2,4-diamino-6-mercaptotriazines in a two-phase system with a solution of S2CI2 in an inert organic solvent dissolving the resulting tetrasulfide. The resulting linear tetrasulfide is then immediately disproportionated into the mixture according to the invention.

Suitable solvents are, in particular, chlorinated hydrocarbons ₍ for example CH 2 Cl 2 and CHCl 3, but also ethers, esters, and aromatic hydrocarbons and ketones are suitable for the disproportionation reaction in the absence of water.) Otherwise they can be used if they form a biphasic mixture with water Reaction conditions for the preparation of the disproportionates are otherwise identical to those for the preparation of pure tetrasulfides.

To what extent the disproportionation reaction has progressed remains irrelevant to the suitability of the resulting mixture. There must not be any free sulfur in the disproportionation.

It can be seen that the substituted N-Trichlormethylthiodicarboximide used according to the invention in accordance with the formulas (I, la) in combination with the triazine compounds according to formula II not only excellent vulcanization retarder, but also at the same time change the vulcanization characteristic so that all the physical density data responsive to the crosslinking density, as the maximum torque (rheometer) or the tension values at 300% elongation are considerably increased.

Preference is given to using N-trichloromethylthio-phthalimide (VZa) and 1,2,3,6-tetrahydro-N- (trichloromethylthio) -phthalimide (VZb).

As further examples of the compounds which can be used according to the invention according to the formulas (I, Ia), mention may be made:

N-trichloromethylthio-succinimide (VZ c)

N-trichloromethylthio-dodecylsuccinimid

N-trichloromethylthio-7-oxabicyclo (2.2.1) hept-5-en-2,3-dicarboximide

N-trichloromethylthio-S-norbornene-i ^ -dicarboximid

These substances are known, some of them are manufactured on a large scale and used as fungicides in agriculture (Captan® and Folpet®). They are prepared from the corresponding dicarboximides and perchloromethylmercaptan = trichlorosulfenyl chloride in the presence of an acid acceptor (CHEVRON, U.S. Patent 2,553,770, 2,553,771, 2,553,776, Bayer, U.S. Patent 2,846,442, ZEFIROV and YUREF, CA 55.504 ).

So far only the use of N-trichloromethylthip-phthalimide in combination with sulfenamides of benzothiazole, for example benzthiazolyl-cyclohexyl-sulfenamide or of benzothiazolyl-2-sulfenmorpholide (SU-PS 164.670, JJ Eitington et al.) With only weak retarding effect.

D1.3 Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) disulfides according to formula II are described in DE-PS 1669954, for example

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

Bis- (2-ethylamino-4-di-isopropylamino-s-triazin-6-yl) disulphide

Bis (2-n-propylamino-4-diethylamino-s-triazin-6-yl) disulphide

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

Examples of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) tetrasulfides and their disproportionates include:

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

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

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

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

D Bis (2-ethylamino-4-di-isobutylamino-s-triazin-6-yl) tetrasulfide

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

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

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

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

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

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

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

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

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

The substituted N-trichloromethylthio-dicarboximides to be used according to the invention as vulcanization retardants with crosslinking density-increasing effect in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) sulfides according to formula (II) Suitable for the rubber mixtures known from the prior art with natural rubber (NR), isoprene rubbers (IR), butadiene rubbers (BR), styrene-butadiene rubbers (SBR), isobutylene-isoprene rubbers (HR), ethylene-propylene terpolymers (EPDM), Nitrile rubbers (NBR), halogenated rubbers and also epoxidized natural rubbers (ENR) as well as their blends.

According to the invention, compounds of the formulas (I, Ia) in an amount of 0.1-5 parts and the Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) sulfides ( n = 4) according to formula II are used in an amount of 0.1-10 parts based on 100 parts of rubber. The molar ratio of triazine crosslinker to retarder is preferably 1: 0.3-1.5, preferably 1: 0.3-1.2. In this case, the mixture contains no free sulfur.

^ 6- Z63Z9 /

In the accelerated sulfur vulcanization, the substituted N-Trichlormethylthiocarboximide according to the formulas (1, Ia) in amounts of 0.1-5 parts, preferably 0.1-2 parts per 100 parts of rubber at sulfur levels of 0.1-10 parts , preferably 0.1-8 parts per 100 parts of rubber. Preference is given to molar ratios of accelerator, retarder, sulfur of 1: 0.3-1.5: 0.5-1.5, preferably 1: 0.3-1.2: 0.5-1.5, oligosulfides according to Formula II will then be in quantities of

0.1-10 parts used. '

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

Likewise, substitution is made in the use of the triazine compounds of formula (II) when operating without sulfur.

Likewise for kinetic reasons, it may prove expedient to use the N, N'-substituted bis (2,4-diaminos-triazin-6-yl) -oligosulfides according to formula II in admixture with conventional accelerators of the benzothiazole series and / or thiurams , for example, N-cyclohexylbenzothiazolesuifenamide, 2-mercaptobenzothiazole, benzothiazole disulfide, and their zinc salts, and tetramethylthiuram disulfide (see J. van Alphen, Rubber Chemicals [1977], pp. 1-46).

These dosing guidelines can be used to solve important vulcanization problems without it becoming a problem

Vulcanis property loss comes.

Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides according to formula II may advantageously together with

Organosilanes, for example '

(III)

(RO) ₃ Si -

I -S _x or - (RO) ₃ -Si (CH ₂ ) _n -SH ·.

with η = 2, 3, χ = 2-6, R =

CrL

(R-O), Si (CH 2) 3 2 η

with χ = 2-6, preferably 3,

, cyclohexyl

-S

^J 2

preferably bis (3-triethoxysilylpropyl) tetrasulfide (Si 69, Degussa AG) are used, namely in the sulfur-free Si 69 crosslinking (DE-PS 2536674), in sulfur vulcanization with Si 69 (DE-PS 2255577) and also in the preparation of reversion-stable vulcanizates by construction of equilibrium cure systems according to DE-PS 2848559. In all the cases mentioned substituted N-Trichlormethylthiodicarboximide according to formula (I, la) act as suitable vulcanization retardants with crosslinking density-increasing effect. ,

The vulkanisationsverzögernde effect of substituted N-Trichiormethylthiodicarboximide according to formula (I, la) also occurs when Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides according to formula (II) alone or in admixture with conventional accelerators and / or with conventional sulfur donors such as Sulfasan® R (morpholine disulfide).

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

- amplification systems, i. Furnace carbon blacks, channel blacks, flame blacks, thermal blacks, acetylene blacks, electric arc blacks, CK 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 5-300 parts, per 100 parts of rubber,

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

- commonly used aging, ozone, fatigue protection agents ^ such as IPPD, TMQ etc. and also waxes as light stabilizers and their blends,

- any plasticizers, such as aromatic, naphthenic, paraffinic, synthetic plasticizers and their blends,. -

-. Optionally in the rubber industry organosilanes used in accordance with the prior art, such as ψ Chldrpropyltrialkoxisilane, vinyl trialkoxysilanes, γ-Mercaptoalkyltrialkoxisilane and Aminoalkyltrialkoxisilane, as well as their blends in an amount of 0.1-25, preferably 1-1OTeMe per 100 parts of fillers silanolgruppentragender such as silicas, silicates, clays, etc.

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

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

The scope of the N-ltrichlormethylthiol-dicarboximide in combination with Ν, Ν'-substituted bis (2,4-diamino-striazin-6-yl) sulfides according to the formulas (I), (la) and (II) .streckt on rubber compounds commonly used in tire manufacture, on technical articles such as blends for conveyor belts, V-belts, molded articles, hoses with and without inserts, roll rubbers, liners, sprayed profiles, free-hand items, films, shoe soles and tops, cables, solid rubber tires and tires their vulcanizates.

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

Example 1:

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

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

A solution of 137 g of S ₂ Cl ₂ in 100 ml of gasoline is allowed to run in within 20 minutes, care being taken that the temperature does not exceed + 5 ° C.

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 under vacuum / 12 torr at 40-45 ° C.

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

Analysis:

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

Mol wt. 516, Ci ₈ H ₃₂ N ₁₀ S ₄

calc. C 41,9 H 6.2 N 27.1 P 24,8 gef. C 41,8 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. To do this, you give 250ml of gasoline. The mixture is cooled to + 5 ° C after good stirring. Now let a solution of 13.5 g of S ₂ Cl _{2 run} in 30 ml of gasoline. A white precipitate forms immediately. At the end of the reaction, recycle example 1 is worked up. Quantity: 56g, corresponding to 89.2% of the theory

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

C 49.68 H 7.64 N 22.29 S 20.38

gef. C49.59 H 7.59 N 22.18 S 20.40

HPLC analysis: purity> 96%. ^:

Example 3:

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

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

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

Analysis: C ₂₄ H ₄₄ Ni ₀ S ₄ (molecular weight 600)

calc. C 48 H 7,33 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 turbined and cooled to ⁰ ° C.

Dissolve 14 g of S ₂ Ci ₂ in 50 ml of CH ₂ Cl ₂ and allowed to run this solution in the mercaptide solution.

The reaction product dissolves in CH ₂ Cl ₂ . At the end of the reaction the phases are separated and the CH ₂ CI ₂ operates on -i.ösung. This gives an amorphous powder with a softening point of about 110 ° C.

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

Analysis: C ₁₈ H ₃₂ N ₁₀ S ₄ (mol wt 516th)

N 27.1 S 24.8

gef. N 26.8 S 24.4

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

Example 5:

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

Example 6:

70.25 g of Σ-ΟνοΙοηβχνΙθΓηίηο-'ΐ-αίβΙπνΙβιΤΗηο-β-ΓηβΓΟαρΙοΐπθζίη is dissolved in 11 g of NaOH and 250 ml of water. Add 250ml of 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, the phase is separated and the chloroform layer is worked up. This gives 71.9 g of a white amorphous powder, corresponding to 92% of theory.

Analysis: C ₂₆ H ₄₄ Ni ₀ 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

Voltage value 300% incubation time ^ Scorch time Shore A hardness

DIN 53504 DIN 53529 ASTM D 2084 DIN 53505 DIN 53529

MPa

min

min

Degree

nm

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

CORAX®N220:

Naftolen®ZD:

Vulkanox®4010NA:

Vulkanox®HS:

Mesamcll®:

Protector® G 35:

Vulkacit®MOZ:

! Vu kalent®E:

U trasil®VN3!:

Sulfasan®R

Ribbed Smoked Sheet (natural rubber)

Carbon black, surface area (BET) 120 m ² / g (Degussa)

Plasticizer made from hydrocarbons

N-isopropyl-N'-phenyl-phenylenediamine

Poly-2,2,4-trimethyl-1,2-dihydroquinoline

Alkyl sulfonic acid esters of phenol and cresol

Ozone protection wax

Benzothiazol-2-morpholinosulfenamid

N-phenyl-N- (trichlormethylsulfenyl) -benzenesulfonamide

N-Cyclohehexylthiophalimid

precipitated silica (Degussa)

granules

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

Bis (2-isopropylamino-4-diisopropylamino-s-triazin-6-yl) disulphide

morpholine

Example 7: Effect of VZ substances in combination with Ν, Ν'-substituted bis- (2,4-diamino-s-triazin-6-yl) -oligosulfides as accelerators in N 220-filled NR mixtures

1 2 3 4 5 6 7 RSS1, ML (1 + 4 = 70-80 100 100 100 100 100 100 100 CORAX N 220 50 50 50 50 50 50 50 ZnORS 5 5 5 5 5 5 5 stearic acid 2 2 2 2 2 2 2 NaftolenZD 3 3 3 3 3 3 3 Protector G 35 1 1 1 1 1 1 1 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 2.5 2.5 VulkacitMOZ 1.43 - - - - - - V143 - 1.29 1.29 1.29 - - - D - - - - 1.5 1.5 1.5 vza - - 0.4 - - 0.8 - VZB - - - 0.4 - - 0.8 sulfur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 D _m a * D _min (170 ° C), Nm 8.56 8.04 9.58 9.62 7.28 8.45 8.53 ti (170 ^° C.), min 4.5 3.7 4.8 4.9 2.9 4.3 4.2 crosslinking rate 2.5 2.3 2.5 2.5 3.4 3.1 3.1 (t90% -t10%), min ti (130 ^° C.), min 22.5 15.0 24.5 24.0 9.5 22.0 21.5 Vulcanizate data at 17O ⁰ C Voltage value 300%, 10.2 10.3 11.5 11.6 10.6 11.3 11.3

Example 7 demonstrates that the addition of N-trichloromethylthiophthalimides to di- and tetrasulfidic triazines results in scorch extension (mixtures 2-7) which raises the scorch time to the level of sulfenamide acceleration (mixture 1). Moreover, in soot - treated NR, there is no change in the crosslinking speed, but an improvement in the 300% voltage values.

-a-

Examples: Comparison of VZ substances to Vulcalent E in N 220 filled NR in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides as accelerators

8th 9 10 11 12 13 RSS 1, ML (1 +4) = 70-80 100 100 100 100 100 100 CORAX N 220 50 50 50 50 50 50 ZnORS 5 5 5 5 5 5 stearic acid 2 2 2 2 2 2 NaftolenZD 3 3 3 3 3 3 Protector G 35 1 1 1 1 1 1 Vulkanox4010NA 2.5 2.5 2.5 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 1.5 1.5 1.5 VulkacitMOZ 1.43 - - - - - N - 1.5 1.5 1.5 1.5 1.5 Vulcan E , - - 0.8 - - - vza - - - 0.8 - - VZB - - - - 0.8 - VZC - - - - - 0.8 sulfur 1.5 0.8 0.8 0.8 0.8 0.8 t, (170 ^° C.), min 4.5 2.9 3.8 4.3 4.2 4.3 t, (130 ^° C.), min 22.5 9.5 14.0 22.0 21.5 20.5 Vulcanizate data at 170X Voltage value 300% 10.2 10.6 10.7 11.8 11.3 11.2

Comparison of Vulkalent E (Blend 10) to VZ blends (Blends 11-13) shows that the VZ substances result in longer incubation time and higher stress at 300% elongation.

Examples: Temperature dependence of the mode of action of VZ substances upon acceleration of vulcanization with bis (2-ethylamino-4-diethylamino-s-triazin-6-yl) -disulfide in N 220-filled NR

14 15 16 RSS 1, ML (1 + 4) = 70-80 100 100 100 CORAX N 220 50 50 50 ZnORS 5 5 5 stearic acid 2 2 2 NaftolenZD 3 3 3 Vulkanox4010NA 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 Protector G 35 1 1 1 V143 1.29 1.29 1.29 vza - 0.8 - VZB - - 0.8 sulfur 1.5 1.5 1.5 ti, min: 145 ° C '9.2 17.0 17.5 160X 5.2 8.2 8.2 170X 4.0 5.2 5.7 180X 2.8 4.0 4.0 Vulcanization rate, min: (T90% t10%) 145 X 15.9 18.9 18.2 160X 4.1 5.4 5.2 170X 2.0 3.0 2.6 180X 1.3 1.6 1.6 vulcanizate: Voltage value 300%, MPa 145 X 10.6 12.3 13.1 170X 9.5 12.0 12.5 Shore A hardness: 145X 65 69 69 170X 63 68 68

The addition of VZ substances at processing temperatures of the mixtures (<145X) causes a considerable extension of the incubation time without significantly reducing the cure time at higher temperatures and in each case effectively increasing the 300% voltage value.

Example 10: Effect of VZ substances on the acceleration with bis (2-ethylamino-4-diethylamino-s-triazin-6-yl) tetrasulfide (N) in carbon black / silica filled NR

17 18 19 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 Protector G 35 1 1 1 Vulkanox4010NA 2.5 2.5 2.5 VulkanoxHS '1.5 1.5 1.5 VulkacitMOZ 1.43 - - N - 3 3 vza - - 0.8 sulfur 1.5 0.8 0.8 ti (170 ^° C.), min 4.6 3.8 4.7 t | (13O ⁰ C), min 33.3 16.8 32.0 Vulcanizate data (17O ⁰ C): Voltage value 300% 3.6 5.9 8.6

In N220 / silica-filled NR mixtures, the addition of VZa (mixture 19) shows an incubation time extension to reference level (mixture 17) and at the same time a 300% increase in voltage value to mixture 17 μM.

Example 11: Effect of VZa in carbon black-filled NR accelerated with a V143 / MOZ blend

20 21 22 RSS 1, ML (1 + 4) = 70-80 100 100 100 CORAX N 220 50 50 50 ZnORS 5 5 5 stearic acid 2 2 2 NaftolenZD 3 3 3 Protector G 35 1 1 1 Vulkanox4010NA 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 VulkacitMOZ 1.43 0.72 0.72 V143 - 0.75 0.75 vza - - 0.4 sulfur 1.5 1.5 1.5 D _ma x D _min , (170 ° C) Nm 8.56 8.24 8.87 t | (170 ° C), min 4.5 4.1 4.7 ti (130 ^° C.), min 22.5 15.0 19.3

When Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) sulfides are used together with commercially available suifenamide accelerators (mixture 21), the addition of VZa (mixture 22) also prolongs the incubation time ,

Example 12: Effect of VZb in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligosulfide / Si 69 in carbon black / silica-filled NR mixtures

23 24 25 RSS1, ML (1 +4) = 70-80 100 100 100 CORAX N 220 25 25 25 UltrasilVN3Gran. 2 ' 25 25 Si 69 3.75 3.75 3.75 ZnORS 5 5 5 stearic acid 2 2 2 NaftolenZD 3 3 3 Protector G 35 1 1 1 Vulkanox4010NA 2.5 2.5 2.5 VulkanoxHS 1.5 1.5 1.5 VulkacitMOZ 1.43 - - B - 1.66 1.66 VZB - - 0.8 sulfur 1.5 1.5 1.5 t, (170 ^° C.), min. 4.9 4.2 5.2 t | (130 ° C), min. 37.5 25.4 36.6

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

Example 13: Effect of VZb in a D-crosslinked, N220-filled NR mixture with sulfur donor

26 27 28 RSS 1, ML (1 + 4) = 70-80 100 100 100 CORAX N 220 50 50 50 ZnORS 5 5 5 stearic acid 2 2 2 NaftolenZD 3 3 3 Protector G 35 1 1 1 Vulkanox4010NA 2.5 2.5 2.5 VulkacitMOS 1.43 - - D - 1.76 1.76 VZB - - 0.8 sulfur 1.5 - - Sulfasane R - 0.7 0.7 ti (170 ^° C.), min. 4.5 3.2 4.8 t, (130 ^° C.), min. 22.5 11.5 21.0

Even when used in NR mixtures with sulfur donors together with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yloligosulfiden results, as mixture 28 shows, the VZb addition a significant Scorchverlängerung to the level the reference mixture with sulfenamide Beschieunigung and sulfur (mixture 26).

Example 14: Influence of VZa in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligosulfides in N-330-filled BR

29 30 31 32 BunaCBIO 100 100 100 100 CORAX N 330 60 60 60 60 ZnORS 3 3 3 3 stearic acid 2 2 2 2 NaftslenZD 15 15 15 15 Protector G 35 1 1 1 1 Vulkanox4010NA 1.5 1.5 1.5 1.5 D 1.76 1.76 - - V 225 - - 1.5 1.5 vza - 0.8 - 0.8 sulfur 1.5 1.5 1.5 1.5 ti (165X), min. 4.3 5.7 6.8 9.7 Vulcanizate data at 165 ^° C. Voltage value 300% 7.1 9.8 6.0 8.8

Example 14 shows the incubation time extension of Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) di- and tetrasulfide-accelerated, N-330 filled polybutadiene and, at the same time, the significant 300% increase in voltage ,

Example 15: Effect of VZ a in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) -oligosulfiden as accelerators in NR / BR blend

37 38 39 40 41 70 70 70 70 70 30 30 30 30 30 50 50 50 50 50 5 5 5 5 5 2 2 2 2 2 3 3 3 3 3 1 1 1 1 1 1.5 1.5 1.5 1.5 1.5 2.5 2.5 2.5 2.5 2.5 1.43 - - - - - 1.76 1.76 - - - - - 1.5 1.5 - - 0.8 - 0.8 1.5 0.8 0.8 0.8 0.8 3.7 in 4.2 4.7 7.1

RSS 1, ML (1 + 4) = 70-80 BunaCBIO CORAX N 220 ZnO active Stearic Acid NaftolenZD Protector G 35 VulkanoxHS Vulkanox4010NA VulkacitMOZ

Sulfur t | (170 ° C), min.

12.9 6.6 14.0 22.3 45.0

Example 15 shows that even in the blend of NR with synthetic rubber, a clear gain in scorch safety can be achieved by adding VZ substances.

Example 16: Effect of VZb in combination with Ν, Ν'-substituted bis (2,4-diamino-s-triazin-6-yl) oligosulfides as promoters in N-330-filled NBR mixtures

33 34 35 36 Perbunan N 3307 NS 100 100 100 100 CORAX N 330 60 60 60 60 ZnO active 5 B. 5 5 stearic acid 1 1 1 1 mesamoll 10 10 10 10 Paraffin solid 1 1 1 1 VulkanoxHS 1.5 1.5 1.5 1.5 D 1.76 1.76 - - V225 * - 1.5 '1.5 VZB - 0.8 - 0.8 sulfur 1.2 1.2 1.2 1.2 D _m ax -D _min , (17O ⁰ C) Nm 9.23 12.95 8.18 ... 12.59 t, (170 ^° C.), min 3.5 4.9 4.8 8.4 vulcanization t90-t10%, min. 8.2 2.7 9.4 3.1 Vulcanizate data at 170 ^° C. voltage value 14.0 17.1 11.6 15.5

Addition of VZb to NBR mixtures in the presence of Ν, Ν'-substituted bis (2,4-diamino-s _: triazin-6-yl) oligosulfides will improve scorch safety while increasing the rate of vulcanization. Likewise, there is a considerable increase in the voltage value of 300%, despite the already very high output level.

Claims (1)

-1- ZÖ3 ZS / claims: 1. Use of compounds of the general formula R ⁹ - GH - GO N-S-CCl R ¹⁰ - CH - GC-in the mean
R ⁹ : H R ¹⁰ : H, C ₁ -C ₆ -alkyl, undecenyl, or R ⁹ and R ¹⁰ together with the 3- and 4-position carbon atoms of the dicarboximide form a six-membered ring, saturated or mono- or triunsaturated, der.ein - may be substituted by two times by methyl, in particular tetrahydrophthalimides of the formula *