RU2478666C1 - Curable rubber mixture for industrial rubber articles and tyres - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to curable rubber mixtures used to make industrial rubber articles and tyres. The composition of the curable rubber mixture includes, in solid output form as simultaneously an antioxidant, antiozonant and antifatigue agent, compounds from a group of N-alkyl-N'-phenyl-n-phenylenediamine derivatives with melting point from 49°C to 63°C in amount of 1.0-5 pts.wt.

EFFECT: invention increases wear resistance and fatigue strength of rubber, excludes or lowers the amount of additional antioxidants used in rubber mixtures.

2 cl, 6 tbl

Description

The invention relates to vulcanizable rubber compounds used for the production of rubber technical products and tires.

Known vulcanizable rubber compounds for the manufacture of rubber goods and tires, stabilized by derivatives of N-phenyl-N'-alkyl-p-phenylenediamine (PFDA), N, N'-diaryl-PFDA, N, N'-dialkyl-PFDA and / or mixtures thereof or by combinations of the aforementioned PFDA derivatives with aromatic monoamines (phenyl-β-naphthylamine (PBN) or Naphtham 2) oligomerized with 2,2 ', 4-dihydroquinoline (TMQ, Acetononyl H), which provide an increase in the effectiveness of PFDA derivatives as antiozonants and anti-haze agents [M.Yu. Tokareva, S.M.Kavun, A.S. Lykin. Ways to increase the effectiveness of stabilizing systems for tire rubbers. Thematic review. M., TsNIITENeftekhim. 1976; S.M.Kavun, Yu.M. Genkina. Rubber and Rubber, 2001, p. 26 .; Huntink, N.M. (2003) Durability of rubber products: development of new antidegradants for long-term protection, http://doc.utwente.nl/40689/1/thesis_Huntink.pdf].

In known vulcanizable rubber compounds, the alkyl substituents of the PPDA derivatives used in them are secondary or iso-alkyls, that is, hydrocarbon radicals attached to one, less often to two nitrogen atoms in the molecule at the secondary carbon atom, for example:

However, rubbers obtained from known rubber mixtures using the above and widely used PFDA derivatives (IPPD or 6PPD) with iso-alkyl substituents due to the relatively low molecular weight (226 and 268 respectively of these PFDA derivatives) tend to evaporate and leaching with water during the operation of rubber products [Lehocky P., Syrovy L, Machak I. // Int. Rubber Chemical and compounding conf. (Antwerp, 1999). Paper 5]. Therefore, to ensure the necessary resistance to heat aging, atmospheric ozone and the necessary fatigue endurance during dynamic loading of the resulting rubber products and tires from known vulcanizable rubber compounds, it is necessary to increase the dosage of the used PFDA derivatives and / or to use amine antioxidants less prone to evaporation (AO) ) other classes, for example, phenyl-β-naphthylamine (Naphtham 2), a mixture of oligomers 2,2 ', 4-dihydroquinoline (TMQ), produced in Russia under the trade name A ethonanyl H, mixtures of N, N'-diaryl- and dialkylaryl-substituted PFDA, for example, mixtures of N, N'-ditolyl-p-phenylenediamine with N, N'-diphenyl-p-phenylenediamine and N-tolyl-N'-phenyl p-phenylenediamine produced by a number of companies under the trade names Wingstay 100, Vulkanox 3010, etc. [Milner PW, et al. Tire Technology Int., 1993, p. 48-51], or a powder composition of the antioxidant N-2-ethylhexyl-N'-phenyl-p-phenylenediamine and mineral fillers (RU 2 385 335, publ. 03/27/2010, RU 2406720, published on December 20, 2010), produced by NPP Kvalitet LLC in the Russian Federation [S.M.Kavun, Yu.V. Vinokurov, A.A. Sokolovsky, Rubber and rubber. 2009, No. 5, pp. 12-18].

All of the classes of amine antioxidants listed above that are additionally introduced into known vulcanizable rubber compounds other than PFDA derivatives, while reducing the consumption of PFDA derivatives due to competition with them in the reactions of inhibition of thermal oxidation of rubber, are either not antiozonants or are very weak antiozonants, but in combination with by known antiozonants in known rubber mixtures of the IPPD and 6PPD types, they can increase the ozone resistance and fatigue resistance of rubbers obtained from known vulcanizable rubbers x mixtures, which, however, complicates the formulation and increases the cost of rubbers.

Vulcanizable rubber compounds are known containing derivatives of PFDA with secondary alkyl substituents at one or two nitrogen atoms with higher molecular weights (MM) than IPPD and 6PPD, for example, N-1-methylheptyl-N'-phenyl- p-phenylenediamine or N-1-ethyl-4-methylpentyl-N'-phenyl-p-phenylenediamine:

[Kavun S.M., Genkina Yu.M., Filippov B.C. “Modeling and prediction of the diffusion and solubility of class N, N'-substituted p-phenylenediamine antiozonants in technical rubber, Rubber and Rubber, 1996, No. 6, pp. 10-15, Determination of p-Phenylenediamine and Related Antioxidants in Rubber Boots by High Performance Liquid Chromatography. Development of an Analytical Method for N- (1-Methylheptyl) -N'-phenyl-p-phenylenediamine. Yoshiaki Ikarashi and Masaaki Kaniwa. Journal of Health Science, 46 (6), 467-473 (2000)], each of whose alkyl substituents in the technical literature is often and not entirely correctly called octyl, since they do not distinguish between isoalkyl and n-alkyl substituents when nitrogen atom.

Also known is N, N'-di-n-octyl-p-phenylenediamine [for example, Gorbunov B.N., Gurvich Y.A., Maslova I.P. Chemistry and technology of stabilizers of polymeric materials. Moscow, Chemistry, 1981. p.15], however, N, N'-dialkyl-p-phenylenediamines are much more expensive than N-alkyl-N'-phenyl-p-phenylenediamines and are often liquid products.

Known vulcanizable rubber compounds, including the listed derivatives of PFDA with higher MM, due to the reduced volatility (volatility) and leachability of these derivatives than IPPD and 6PPD, allow to obtain rubbers with better retention of properties during thermal aging, although to a greater extent this typical for N-alkyl-N'-phenyl-p-phenylenediamines, since N, N'-di-alkyl-p-phenylenediamines are prone to unproductive losses due to direct oxidation of atmospheric oxygen [Tokareva M.Yu., Kavun S.M. ., Lykin A.S. Ways to increase the efficiency of stub lysing systems for tire rubber. Moscow. CNIITENeftekhim. 1978. P. 42-48].

A disadvantage of the known rubber compounds containing derivatives of PFDA with higher than the widely used IPPD and 6PPD, MM is the final form of these derivatives of PFDA (viscous liquids), which is inconvenient in the manufacture of known rubber compounds using existing systems for weighing and feeding ingredients to rubber mixing equipment at enterprises manufacturing rubber goods and tires.

In addition, rubbers obtained from known vulcanizable rubber compounds containing 6PPD and derivatives of PFDA with an even higher dosage than IPPD, MM in equilibrium with IPPD dosage, compared to rubbers with IPPD, due to the reduction of diffusion coefficients, measured or calculated according to the forecast equations [Kavun S.М., Genkina Yu.M., Filippov BC Rubber and rubber, 1996, No. 6, pp. 10-15], have lower fatigue resistance both due to the lower molar content of the more “heavy” PFDA derivative, and due to the fact that this PFDA derivative does not “manage” in such a way as quickly as IPPD, diffuse at the mouth of growing defects in rubber during fatigue and inhibit the growth of defects and destruction of rubber due to secondary decomposition reactions of hydroperoxides formed in the mouths of defects in reactions of breaking kinetic oxidation chains on antioxidants [Kavun S.M. Anti-fatigue // Chemical Encyclopedia. M: Publishing house "Soviet Encyclopedia", 1995. V.4. S.242-243].

Known vulcanizable rubber compounds containing, as stabilizer, bulk powder compositions of highly effective liquid amine AO for synthetic rubbers (SKI-3, SKD-ND, DSSK) - N-2-ethylhexyl-N'-phenyl-p-phenylenediamine (8PFDA), obtained from branched aliphatic alcohol 2-ethylhexanol and sold under the trade name Antioxidant C789 (Novantox 8 PFDA) [Kavun S.M., Vinokurov Yu.V., Sokolovsky A.A. Rubber and rubber. 2009., No. 5, p.], And one of these compositions, including kaolin as a mineral filler, is produced by LLC NPP Kvalitet under the trade name Qualistab 8PFDA-P [RU 2385335, publ. 03/27/2010, RU 2406720, publ. December 20, 2010].

A disadvantage of the known vulcanizable mixtures containing Qualistab 8PFDA-P is the need to introduce additional IPPD or 6PPD as an antiozonant in them, since Qualistab 8PFDA-P itself is not an antiozonant. Another disadvantage of the known vulcanizable mixtures with Qualistab 8PFDA-P is that its positive effect on the fatigue properties of rubbers is due not only to the effectiveness of Qualistab 8PFDA-P as such, but also to the anti-tiring effect of its decomposition products, which does not allow the full use of its protective resource actions from other types of aging.

The objective of the invention is to develop a composition of a vulcanizable rubber composition for rubber products and tires containing compounds from the group of derivatives of N-alkyl-N'-phenyl-p-phenylenediamine in a solid exhaust form, convenient for use in existing systems of hitching and transportation to rubber mixing equipment, which would be more effective without the use of additional antioxidants as both an antioxidant (antioxidant), an antiozonant, and a decongestant.

The technical result of the present invention is:

- ease of use in the manufacture of rubber compounds according to the invention for rubber technical products and tires due to the solid exhaust form;

- achieving high rates of ozone resistance and fatigue endurance of rubbers from mixtures according to the invention;

- the possibility of a general reduction in the dosage of the stabilizer, as well as the elimination or reduction of the dosages of additionally used antioxidants in the composition of the rubber compounds according to the invention due to the performance of the proposed composition of the vulcanized rubber mixture, along with the functions of the antioxidant and anti-fatigue functions of chemical and physical antiozonant;

- increase heat resistance (resistance to thermo-oxidative aging) rubbers from rubber compounds according to the invention;

- expanding the range of rubber compounds for the production of technical rubber with increased durability and performance.

To solve this problem, we propose a vulcanizable rubber mixture for rubber products and tires, which contains those obtained using primary aliphatic alcohols or their mixtures as an antioxidant, antiozonant and anti-tackifier in a solid outlet form of compound e from the group of derivatives of N-alkyl-N ' -phenyl-p-phenylenediamine, with a melting point from 49 to 63 ° C, in a dosage of from 1.0 to 5 parts by weight per 100 parts by weight rubber.

PFDA derivatives obtained using primary aliphatic alcohols with an MM of alkyl radical below C8, for example, amyl, hexyl, and also from fractions of C7-C9 and C8-C10 alcohols having a melting point below 49 ° C, are inconvenient in the production of vulcanizable rubber compounds at transportation, weighting and supply to rubber mixing equipment, and derivatives obtained from the fraction of alcohols below C7, in addition, are subject to rapid evaporation and leaching from rubber products during operation.

The difference between the proposed vulcanizable rubber composition and the known ones is that they use both N-alkyl-N'-phenyl-p-phenylenediamine derivatives with a linear structure of an alkyl substituent or a mixture of such substituents with a melting point of 49 to 63 as an antioxidant, antiozonant and anti-tackifier. ° C, instead of the N-alkyl-N'-phenyl-p-phenylenediamine derivative with a secondary alkyl substituent, such as the widely used IPPD or 6PPD, or its combinations with amine antioxidants (Naphtham 2, Acetononyl H) or derivatives N, N'-diaryl- (aralkyl) -p-phenylenediamines.

The indicated difference between the proposed vulcanizable rubber composition, comprising a compound from the group of derivatives of N-alkyl-N'-phenyl-p-phenylenediamine with a linear structure of an alkyl substituent or a mixture of such substituents at a nitrogen atom in a molecule in a solid outlet form, from known vulcanizable rubber mixtures comprising a derivative of N-alkyl-N'-phenyl-p-phenylenediamine with a secondary alkyl substituent (IPPD, 6PPD) in combination with amine antioxidants such as Naftam 2, Acetonanil N or derivatives N, N'-diaryl- (aralkyl) - shit or without them, allows to reduce the dosage of the main derivative of PFDA and / or to exclude or reduce the dosage of an additionally introduced amine stabilizer.

The use of the N-alkyl-N'-phenyl-p-phenylenediamine derivative with the linear structure of the alkyl substituent or a mixture of such substituents at the nitrogen atom in the molecule in the composition of the proposed vulcanizable rubber composition results in an unexpected effect — comparatively high values in the vulcanizable rubber composition rubber invention of the diffusion coefficient and solubility, which, in addition to its high efficiency as an antioxidant (antioxidant), provides rubbers higher than that of rubbers obtained from known res new mixtures with IPPD or 6PPD, thermo-oxidative stability and, at the same time, ozone resistance and fatigue resistance.

In addition, when N-alkyl-N'-phenyl-p-phenylenediamine is used as a derivative of the vulcanizable rubber composition of the invention with a linear structure of an alkyl substituent or a mixture of such substituents at a nitrogen atom in a molecule having a molecular weight starting from C14- C18, and rather high diffusion coefficients, their solubility in the rubbers obtained from the vulcanizable rubber composition according to the invention begins to decrease, and these homologs in behavior in rubbers resemble the effect of ozone-protective waxes, which is associated with etaniem on the surface to form a physical barrier to the ozone as a protective film. As a result, in rubbers obtained by vulcanization of the rubber composition according to the invention, including the PFDA derivative with a linear alkyl substituent, starting with C14-C18, it has a double function - a physical antiozonant - due to the formation of a protective film of a faded stabilizer from it, physically preventing the contact of ozone with the rubber surface , and - a chemical antiozonant, which owes its properties to the structure of the derivative of N-alkyl-N'-phenyl-p-phenylenediamine, which actively chemically destroys ozone molecules, after which the products are decomposed These derivatives of the quinoid structure are dimerized, trimerized, etc. on the surface of the rubber obtained from the rubber composition according to the invention, with the formation of a protective film of an oligomerized derivative of PFDA, which provides, due to these two functions, longer protection of the rubber.

Another difference and feature of the proposed vulcanizable rubber composition according to the invention is that its derivative N-alkyl-N'-phenyl-p-phenylenediamine with linear alkyl substituents at the nitrogen atom in the molecule or with their mixture, despite its relatively high the molecular weight is solid, in contrast to derivatives of PFDA with secondary alkyl substituents, comparable to MM, with a melting point not lower than that of the most widely used product 6PPD, which makes it used in industry with the manufacture of rubber compounds according to the invention, that is, transportation, weighting and feeding to rubber mixing equipment, is quite adaptable.

The indicated differences between the vulcanizable rubber mixture according to the invention, with the introduction of a compound from the group of derivatives of PFDA with linear alkyl substituents at the nitrogen atom in the molecule or their mixture in solid exhaust form, from known rubber compounds with widely used derivatives of PFDA, allow to obtain a technical effect, consisting:

- in ease of use, due to the solid graduation form with the existing technology of transportation, weighing and feeding to rubber mixing equipment at the enterprises of the rubber and tire industry;

- in increasing thermo-oxidative stability and fatigue endurance of rubber;

- to increase the working capacity, service life and durability of rubber by reducing unproductive losses (evaporation, leaching when the rubber comes into contact with water);

- to increase the resistance of rubber from the vulcanizable rubber composition according to the invention to ozone and atmospheric cracking, which eliminates the additional use of other antioxidants and antiozonants and more purposefully apply homologues of compounds in the composition of the vulcanizable rubber composition according to the invention from the group of derivatives of N-alkyl-N'-phenyl -p-phenylenediamine with linear alkyl substituents at the nitrogen atom in the molecule or from a mixture thereof with different MM depending on the purpose and operating conditions of the product.

The possibility of carrying out the invention is illustrated by the following examples.

Example 1. Obtaining introduced into the composition of the proposed vulcanizable rubber compound in dosages from 1.2 to 5 parts by weight per 100 parts by weight rubber N-n-octyl-N'-phenyl-p-phenylenediamine (8-o-PFDA) and other compounds derived from PFDA with linear alkyl substituents at the nitrogen atom in the molecule or mixtures thereof (Examples 2-5) are carried out by the method described in RU 2417981, publ. 05/10/2011, to obtain N-2-ethylhexyl-N'-phenyl-p-phenylenediamine, starting from the branched aliphatic alcohol 2-ethylhexanol in two stages.

Preparation of Potassium Alcoholate

199.2 g (1.5169 g mol) of 99% n-octanol are charged into a 0.5 dm ³ flask equipped with a stirrer and reflux condenser and heated to 90-100 ° C, then 19.0 g (0 3223 g mol) 95% potassium hydroxide. After loading the entire amount of KOH, the temperature is raised to 135-160 ° C and maintained with stirring for 30 minutes. Get a solution of potassium alcoholate with a concentration of 24.8%.

Alkylation step

In a 3-necked flask with a volume of 0.5 dm ³ , equipped with a stirrer, thermometer, heated by a reflux condenser with a downward refrigerator, allonge and receiver, 121.0 g (0.651 g mol) of technical 99% p-aminodiphenylamine (PADA) are charged. A coolant (glycerin) with a temperature of 90-95 ° C is supplied to the reflux condenser, and cold water is sent to the refrigerator. PADA with stirring is heated to a temperature of 200-209 ° C. At a melt temperature of 200-209 ° C for 3 hours at a rate of 85-90 ml / hour, a solution of potassium alcoholate obtained in the first stage with a temperature of 135 to 160 ° C is poured (dosed) with simultaneous distillation of the n-octanol azeotrope with water. In this case, the bulk of n-octanol is condensed in a reflux condenser and returned to the reaction flask, and the water formed as a result of the reaction in the form of azeotrope vapor with n-octanol enters the refrigerator, condenses, and flows into the water separator. The alcohol is separated and returned to the reactor for the next alkylation operation. The potassium alcoholate solution is dosed for 3 hours until the residual PADA content in the reactor is 5% of the initial one, calculating it from the determined current concentration taking into account the real volume of the reaction mass, after which the dosing is stopped, the temperature in the alkylation reactor is raised to 235 ° C with stirring dosing is started again until the potassium alcoholate solution is exhausted, after which the reaction mass is maintained at 235 ° C for 1 hour with stirring. After completion of the alkylation, the content of residual PADA is 0.2 wt.%. The total alkylation operation time is 5 hours. The total amount of distilled water was 17.2 ml, n-octanol was 14.5 ml (11.95 g).

The resulting alkylate with a temperature of up to 235 ° C is poured with stirring into a 750 ml 3-necked flask equipped with a stirrer and reflux condenser, into which 140 ml of water are pre-charged. The temperature of the resulting reaction mass during the addition of alkylate is maintained in the range of 85-90 ° C, after which the mass is stirred for 30 minutes, allowed to stand with the mixer turned off for 30 minutes and delaminate. The upper, organic layer contains n-octanol and the product of alkylation, the lower, aqueous - potassium salt of n-octanoic acid. The aqueous layer is separated. The organic layer is additionally washed 2 more times, adding 140 ml of water each time, stirred for 30 minutes at 85-90 ° C, settled for one hour with the agitator turned off and delaminated. The organic layer is sent to distill off n-octanol at a temperature of 250-270 ° C and under a vacuum of 5-10 mm Hg.

After cooling, a melt of N-n-octyl-N'-phenyl-p-phenylenediamine is obtained in an amount of 193.9 g with a melting point of 49 ° C, a basic substance content of 98.9%, p-aminodiphenylamine 0.20%. Yield 99.5%.

From the combined aqueous layer, after three steps of washing the potassium salt of n-octanoic acid after neutralizing it, 42.1 g (0.323 g-mol) of 28% hydrochloric acid to a pH in the range from 2 to 4, n-octanoic acid is isolated, which turns into organic layer. The aqueous layer contains potassium chloride. The organic layer is distilled and 16.1 g of purified n-octanoic acid are obtained with a mass fraction of the main substance of 98.5%.

The consumption of n-octyl alcohol is 0.610 kg per 1.0 kg of 8PFDA.

Example 2. The preparation of a mixture of Nn-octyl- and Nn-decyl-N'-phenyl-p-phenylenediamines (8-10 PFDA) is carried out according to Example 1 with the same parameters for the preparation of a mixture of potassium alcoholates from a mixture of aliphatic alcohols C8 -C10. Differences in the composition of alcohols, their loading size and others, from these indicators of Example 1 are presented in Table 1. A mixture of N-n-octyl- and N-n-decyl-N'-phenyl-p-phenylenediamines is obtained (8-10 PFDA ) in an amount of 200.0 g with a melting onset temperature of 44 ° C, a mass content of 8-10 PFDA - 98.7%, p-aminodiphenylamine - 0.25%. The yield is about 98.0%.

The consumption of the mixture of alcohols C8-C10 is 0.635 kg per 1.0 kg of (C8-C10) -PFDA.

Example 3. The preparation of a mixture of Nn-decyl- and Nn-dodecyl-N'-phenyl-p-phenylenediamines (10-12 PFDA) is carried out according to Example 1 with the same parameters for the preparation of a mixture of potassium alcoholates from a mixture of aliphatic alcohols C10 -C12. Differences in the composition of alcohols, their loading size, and others, from these indicators of Example 1 are presented in Table 1. A melt of 10-12 PFDA is obtained in an amount of 213.3 g with a melting onset temperature of 57.5 ° C, and a basic substance content of 97.7 %, p-aminodiphenylamine - 0.15%. The yield is about 97.0%.

Consumption of a mixture of alcohols С10-С12 - 0.640 kg per 1.0 kg 10-12 PFDA.

Example 4. Obtaining a mixture of N-n-hexadecyl- and N-n-octadecyl-N'-phenyl-p-phenylenediamines (16-18 PFDA) are according to Example 1 from a mixture of n-hexadecyl and n-octadecyl alcohols in a mass ratio of 49 : 47.5 (product Stenol 16-18) with a C16 content of about 49% and a C18 of 47.5% by alkylating PADA with a 22.5% solution of a mixture of potassium alcoholates in a mixture of alcohols and washing the resulting alkylate four times with 200 ml of water. Differences in the composition of alcohols, their loading size, and others, from these indicators of Example 1 are presented in Table 1.

A melt of 16-18 PFDA is obtained in an amount of 267.4 g with a melting onset temperature of 63 ° C, a basic substance content of 97.5%, p-aminodiphenylamine 0.2%. Yield 97.0%.

Example 5. The preparation of a mixture of Nn-tetradecyl, Nn-hexadecyl and Nn-octadecyl-N'-phenyl-p-phenylenediamines (14-18 PFDA) is carried out analogously to Example 1, but from a mixture of n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl alcohols in a mass ratio of 55:31:13, by alkylating PADA with a 23.5% solution of a mixture of potassium alcoholates in a mixture of alcohols and washing the alkylate four times with 200 ml of water. Differences in the composition of alcohols, their loading size, and others, from these indicators of Example 1 are presented in Table 1.

A melt is obtained (14-18 PFDA) in an amount of 240.9 g with a melting onset temperature of 52 ° C, a basic substance content of 97.5%, p-aminodiphenylamine 0.2%. Yield 97.0%.

Example 6. Obtaining a mixture of Nn-decyl- and Nn-dodecyl-N'-phenyl-p-phenylenediamines (10-12 PFDA) in an industrial reactor

The preparation of potassium alcoholate from a mixture of alcohols C10-C12 with a content of C10 of 75.0% and C12 of 24.5% and potassium hydroxide is carried out as described below.

In an industrial reactor with a jacketed volume of 4.0 m ³ equipped with a stirrer, reflux condenser, reflux condenser, thermometer and dispenser, 2577.2 kg of a mixture of С8-С10 alcohols (2996.7 dm ³ and 150 kg of caustic potassium are loaded and a solution of potassium alcoholate is prepared in a mixture of alcohols С10-С12 with a concentration of 16.9%. The resulting solution of potassium alcoholate with a concentration of 16.9% is stable at 125-160 ° C, crystallizes upon cooling. A solution of the alcoholate is dosed at a temperature of 145 ° C at a rate of 200 liters / hour in alkylation reactor volume, 6.3 m ³ jacketed, equipped with a stirrer, reflux condenser, t ploobmennikom, a sensor for detecting a temperature and a rotameter for measuring flow velocity alkoxide.

Preliminarily, 1210 kg of technical PADA, heated and melted with stirring, are loaded into the alkylation reactor before dosing of potassium alcoholate to 200 ° C. After the start of dosing of potassium alcoholate, the temperature in the alkylation reactor is maintained in the range of 200-209 ° C, the temperature of the azeotrope at the outlet of the reflux condenser is in the range of 90-100 ° C. The potassium alcoholate solution is dosed for 12.0 hours until the residual PADA content in the reactor is 5% of the initial one, calculating it from the determined current concentration taking into account the real volume of the reaction mass, after which the dosing is stopped, the temperature in the alkylation reactor is raised to 231 ° C- 235 ° C, at the same time nitrogen is fed into the mass at a speed of 4 m ³ / h and dosing is continued again until the potassium alcoholate solution is exhausted and the reaction mass is maintained at this temperature for 2 hours with stirring. After alkylation is completed, the residual PADA content is 0.15 wt.%. The total alkylation operation time is 16 hours.

The reaction mixture from the alkylation step is cooled to 130-140 ° C and transferred to a 6.3 m ³ jacketed reactor equipped with a stirrer under nitrogen pressure. 2000 l of water are pre-added to the reactor. The extraction of a mixture of potassium salts of acids C10-C12 is carried out at 90-96 ° C for one hour. After completion of the extraction, the aqueous layer containing the mixture of potassium salts of the mixture of carboxylic acids C10-C12, as well as the remains of unreacted caustic potassium are separated from the organic layer.

The extraction of a mixture of potassium salts of carboxylic acids C10-C12 at 90-96 ° C is carried out 2 more times, adding 2000 l of water each time. After completion of the extraction, the aqueous layers containing a mixture of potassium salts of C10-C12 acids, as well as the remains of unreacted caustic potassium are combined.

The organic layer is sent to distill the mixture of alcohols C10-C12 at a temperature of 260-285 ° C and under vacuum 5-10 mm Hg The finished product is released upon cooling as a melt with a melting point of about 56.0 ° C. Get 2142.2 kg of melt mixture of N-alkyl- (n-C14-C16) -N'-phenyl-p-phenylenediamine with a basic substance content of 98.5%, residual PADA - 0.2%. The yield of the mixture N-alkyl- (n-C8-C10) -N'-phenyl-p-phenylenediamine to 100% PADA is 98.2%. The consumption of the mixture of alcohols C8-C10 is about 622 kg per 1 ton of the target product.

Examples 7-11 illustrate the achievement of the claimed technical result in the manufacture of rubber products and tires using the proposed vulcanizable rubber compound.

Example 7. Illustrates the high thermal oxidative stability of rubber obtained by vulcanization of the rubber composition according to the invention, including derivatives of PFDA obtained according to Examples 1 and 5.

On laboratory rollers at 75 ± 5 ° C, a standard rubber mixture of 2.5 kg mass is prepared on the basis of 100% NC, filled with P 701 carbon black (22 parts by mass), containing vulcanization accelerator, captax, 0, according to standard conditions. 6 parts by mass, sulfur — 2.0 parts by mass, zinc oxide — 5 parts by mass, stearic acid — 1.0 parts by mass. and other targeted additives to obtain, after vulcanization, soft rubber for shock absorber cushions. The mixture is divided into six parts, in one of which (reference), separately known stabilizers are introduced separately on rollers (Diafen FP (IPPD) and Acetononil H - TMQ analogue), the compound of the invention obtained in Examples 1 and 5 in two mixtures, and in the first part for comparison do not introduce stabilizers. The dosages of the introduced compounds and stabilizers and the properties of the obtained rubbers before and after thermooxidative aging at 100 ° C for 48 hours are shown in Table 2.

From the data of Table 2 it can be seen that rubber (1) without stabilizers is significantly inferior to all stabilized rubbers in maintaining strength and elongation after thermal (thermo-oxidative) aging at 100 ° C for 48 hours (conservation factors, respectively, K _ol = 0 , 70 and K _rel . _Unit = 0.57), while rubber (2) - the standard with known stabilizer systems is inferior in these indicators (0.79 and 0.62, respectively) to rubbers 4 and 5 obtained from vulcanized rubber mixtures according to the invention with the compounds obtained according to examples 1 and 5 (respectively, 1.16-1.19 and 0.80), but taken in smaller than the known stabilizers, mass dosages, and adding to the rubber composition of the invention to the compound obtained according to Example 1, the known antioxidant Acetonanil H either does not improve these indicators (rubber 3), which remain higher than for the reference rubber (2), or in the case of joining according to Example 5 increases them (rubber 6 according to the invention).

Unexpected and unique is a significant increase, rather than a drop, in the strength of rubbers (4) and (5) obtained from the vulcanizable rubber composition of the invention with the compounds of Examples 1 and 5 without the introduction of an additional antioxidant, after thermo-oxidative aging, while being better than reference rubber (2) with known stabilizers, maintaining elongation at break and less accumulation of permanent compression deformation in these rubbers.

Example 8. Illustrates a high resistance to thermal oxidation (thermal aging in air) and the effects of dynamic loads (fatigue) of rubber obtained from the vulcanizable rubber composition according to the invention.

On a laboratory roll at 75 ± 5 ° C, a standard uterine rubber mixture based on 85 parts by weight filled with technical carbon of grade P 803 (25 parts by weight) is manufactured according to standard conditions. rubber SKI-3 and 15 parts by weight SKD-2 rubber with the content of vulcanization accelerator, captax, 0.7 parts by mass, sulfur — 1.8 parts by mass, zinc oxide — 5 parts by mass, stearic acid — 2 parts by mass. and other targeted additives to obtain, after vulcanization, soft rubber for shock absorber cushions. The mixture is divided into four parts, in two of which, known rubber mixtures, are added separately to the rollers of the known stabilizers Diafen FP and Naphth-2 (phenyl-β-naphthylamine), Diafen FP and Novantox 8PFDA (N-2-ethylhexyl-N'- phenyl-p-phenylenediamine, which is a liquid antioxidant), the compound obtained in example 1 is added to the remaining two rubber compounds of the invention without additional antioxidants and in combination with Diafen FP. The dosages of the introduced compounds and antioxidants and the properties of the obtained rubbers before and after thermooxidative aging at 100 ° C for 72 hours are shown in Table 3.

From the data of table 3 it can be seen that rubbers (1) and (2) obtained from known rubber compounds with known stabilizer systems are noticeably inferior to rubbers obtained from the vulcanizable rubber mixture according to the invention with the compound obtained according to example 1, in terms of strength retention and elongation after heat (thermooxidative) aging at 100 ° C for 72 hours (K _pr from 0.75 to 0.83, K _otn.ud. - from 0.44 to 0.60 for rubbers (1) and (2 ) and K _ave from 0.88 to 0.90, K _otn.ud. - from 0.77 to 0.80 for rubbers (3) and (4), the tires (4) obtained from the vulcanizable rubber composition P of the invention with the compound obtained in example 1, without additional antioxidants surpasses rubbers obtained from known rubber compounds, including those with known stabilizer systems, in terms of fatigue resistance after repeated stretching after aging at 100 ° C for 72 hours.

Unexpected for rubber obtained from the vulcanizable rubber mixture according to the invention with the compound of example 1, is an increase in fatigue endurance without an additional anti-fatigue agent, despite the fact that the molar content of this compound in this rubber is lower than the total molar content of known stabilizers in rubbers (1) and (2) obtained from known rubber compounds.

Example 9. Illustrates the high resistance to ozone exposure to rubber obtained from the vulcanizable rubber composition according to the invention.

On laboratory rollers at 75 ± 5 ° C, the standard mode is used to make filled with a combination of carbon blacks grades P 701 (50 parts by weight) and P 234 - 25 parts by weight uterine rubber mixture based on 70 parts by weight SKI-3 rubber and 30 parts by weight SKD-2 rubber with the content of vulcanization accelerator, Captax — 0.7 parts by mass, sulfur — 2.5 parts by mass, tetramethylthiuram disulfide (TMTD) —0.2 parts by mass, zinc oxide — 5 parts by mass, stearic acid — 2 parts by weight and other target additives to obtain after vulcanization of rubber for the protective sheath of the hoses. The mixture is divided into six parts, in two of which are known, the commonly used stabilizers are added separately on rollers (Diafen FP and Acetononil N, Diafen FP and Qualistab 8PFDA-P, which is a powder composition of the antioxidant N-2-ethylhexyl-N'-phenyl -p-phenylenediamine and kaolin with a basic substance content of 28%, manufactured by NPP Kvalitet LLC, Russian Federation), the four compounds obtained in Example 1, without additional antioxidants and in combination, are administered in four others, which are vulcanizable rubber compounds according to the invention reduced to 0.8 parts by weight with a dosage of Acetonanil N. The dosages of the compounds of the invention and known stabilizers and the properties of the obtained rubbers before and after thermooxidative aging at 100 ° C for 72 and 240 hours are shown in Table 4. It can be seen that according to the retention factors of strength and elongation of rubber, 3.4 obtained from vulcanizable rubber mixtures according to the invention, using the compound obtained in example 1, in combination with 0.8 parts by weight Acetononyl H, superior rubber from known rubber compounds (1) and (2) with known stabilizer systems.

The time until the formation of visible cracks during ozonation of rubbers (3) and (4) from the mixtures according to the invention with high concentration ozone (1.5 × 10 ^-3 %, volume), with a tensile strain of 15% and a test temperature of 40 ° C with the compound, obtained according to Example 1, in combination with 0.8 wt.h. Acetononyl H is higher than that of rubbers from known mixtures 1 and 2 with known stabilizer systems, as well as the strength retention and elongation coefficients.

Example 10. Illustrates high thermal oxidative stability, as well as high ozone resistance and fatigue resistance of rubber obtained from the vulcanizable rubber composition according to the invention, containing compounds according to Examples 1, 2 and 6, and when used for their production of alcohols corresponding to MM C14-C18 (according to Example 5) the possibility of partial replacement of ozone-protective wax.

According to Example 7, a uterine rubber mixture is made to obtain, after vulcanization, soft rubber for shock absorber pads. The mixture is divided into seven parts, in two of which (1, 2) the known system of stabilizers (Diafen FP and Acetononil N in dosages of 2.0 and 1.0 masses, respectively) is introduced separately on the rollers, and the other five which are vulcanizable rubber compounds according to the invention are the compounds obtained according to Examples 1, 2 and 6 (mixtures 3, 4, 5, respectively), without additional antioxidants in a dosage of 3.0 parts by weight, and in vulcanizable rubber mixtures 6 and 7 administer the compound obtained according to Example 5, in the amount of 5 parts by weight Protective wax is introduced into all rubber compounds in a dosage of 2 parts by weight, except for mixtures 2 (control) and vulcanizable rubber compounds (6 and 7) according to the invention, in which the content of protective wax is accordingly reduced to 1.0 parts by weight. or exclude it (mixture 7). The dosages of the introduced antioxidants, the compounds obtained according to Examples 1, 2, 5 and 6 and wax, as well as the properties of the obtained rubbers before and after thermo-oxidative aging at 100 ° C for 72 hours, and after atmospheric aging (by stretching the samples 20%, exposure on the roof of the building in the industrial district of Moscow from March 21 to May 31) are given in Table 5.

From the data of table 5 it is seen that in terms of resistance to thermo-oxidative aging at 100 ° C for 72 hours and fatigue resistance under repeated tension after aging, all rubbers obtained from the vulcanizable rubber compounds according to the invention are significantly superior to rubber obtained from the known rubber mixture with known stabilizers. Similarly, the weather resistance of rubbers (3-7) from vulcanizable rubber compounds according to the invention is superior to the weather resistance of rubbers (1) and (2) from known rubber compounds with known stabilizers. It can also be seen from the data in Table 5 that the decrease in the dosage of protective wax ЗВ-П in rubber (2) from a known rubber mixture caused a sharp decrease in weather resistance of this rubber with known stabilizers by half, while rubbers obtained from vulcanized rubber mixtures 6 and 7 according to the invention containing the compound obtained in example (5) from a mixture of aliphatic alcohols of fraction C14-C18 in dosages of 2 and 5 parts by weight, respectively, but with a reduced dosage of protective wax (rubber 6) or without it (rubber 7), showed comparable to vulcanize rubber rubber mixtures according to the invention 3-5 and better than control rubber (1 and 2), weather resistance, which confirms the performance of the compound obtained according to Example 5 from a mixture of alcohols corresponding to MM C14-C18, in rubber from a vulcanizable rubber mixture according to the invention , along with the functions of an antioxidant, an antiozonant and a decongestant, also a protective wax.

Example 11. Illustrates the performance of the stabilizer in the rubber sidewalls of tires made from the vulcanizable rubber composition according to the invention, the functions of an antioxidant, antiozonant and anti-fatigue.

Vulcanizable rubber compounds are made for the sidewalls of passenger radial tires based on a combination of SKI-3-SKD rubbers (50:50) and 50 parts by weight carbon black N 220, process oil ПН-6ш (8 parts by weight), zinc oxide (5 parts by weight), stearic acid (2.0 parts by weight), sulfenamide C vulcanization accelerator (1.1 parts by weight) .) and sulfur (1.3 parts by weight).

Known (reference) rubber mixture of the sidewall (1) contains as a stabilizing system 2 parts by weight Diafena FP, 2 parts by weight Acetononyl H and 2 parts by weight ozone-protective wax YaV-1. The control rubber mixture (2) does not contain stabilizers and ozone-protective wax.

In the test vulcanizable rubber composition, the sidewalls of the invention (3) use 1.9 parts by weight. the compound obtained according to Example 1, and 2 wt.h. Ozone-protective wax ЗВ-П.

The manufacture of mixtures is carried out in a closed laboratory mixer according to the following mode:

I stage

The temperature of the rubber mixer chamber is 90 ° C, the loading coefficient is 0.65-0.67, the rotor speed is 63 rpm

- rubbers, zinc oxide, stearic acid, 1/2 carbon black N 220 - at 0 minute;

- ½ carbon black N 220, PN-6 oil - for 90 seconds;

- unloading the mixture at a temperature not lower than 140 ± 5 ° C;

- total mixing time is 240-270 seconds.

II stage

The temperature of the rubber mixer chamber is 70 ° C

- masterbatch - at 0 minute;

- sulfur and accelerators - at 30 seconds;

- unloading at a temperature of 100-110 ° C;

total mixing time is 120-140 seconds.

The vulcanization of the mixtures is carried out at 155 ° C for 25 minutes.

The properties of the reference and experimental rubbers obtained from the known, control (without stabilizers) and experimental vulcanizable rubber compound (according to the invention) with the compound according to Example 1 are shown in table 6.

From the data of table 6 it is seen that the replacement in the vulcanizable rubber composition (2) according to the invention of 2.0 parts by weight Diafena FP and 2.0 parts by weight Acetonanil H on the compound obtained according to Example 1, in a dosage of 1.9 mass, h, which is in a molar ratio lower than the dosage of Diaphen alone FP by 35%, led to higher than that of rubber obtained from the known (reference ) a rubber mixture with a commonly used system of stabilizers, thermal oxidative stability, almost equivalent to a standard fatigue endurance rubber with repeated stretching of specimens subjected to preliminary heat aging (48 hours at 100 ° C), and to better preservation of the initial strength properties in after atmospheric aging for 95 days (from May 1 to August 6, 2011) with a tensile strength of the samples by 20% with a complete absence of cracking of both experimental and reference rubbers. For comparison, in control rubber, where there are no stabilizers and ozone-protective wax (3), significantly lower retention of strength properties after thermo-oxidative aging, as well as fatigue endurance and preservation of properties after atmospheric aging, are obtained, and atmospheric cracking due to atmospheric ozone (multiple small cracks are oriented perpendicular to the axis of tension of the samples), are detected on the 6th day of exposure of the samples.

Example 12. Illustrates unexpectedly high values of diffusion coefficients (D, cm ² / s) in the tire sidewall rubber made from the vulcanizable rubber composition of the invention, with the compounds of Examples 1 and 4 in comparison with D for the known and widely used 6PPD.

According to Example 10, a uterine rubber mixture is made for the sidewall of passenger radial tires based on a combination of SKI-3-SKD rubbers (50:50) and 50 parts by weight carbon black N 220, process oil PN-6sh (8 parts by mass), zinc oxide (5 parts by mass), stearic acid (2.0 parts by mass), a sulfenamide C vulcanization accelerator (1.1 parts by mass) .) and sulfur (1.3 parts by weight) in an amount of 1.3 kg. The masterbatch is divided into four parts and in each of them, except the fourth, stabilizers are introduced on the rollers:

- in the first part (known rubber compound), a known rubber stabilizer 6PPD is introduced in a dosage of 4.0 parts by weight (N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine);

- in the second vulcanizable rubber mixture according to the invention, the compound obtained according to Example 1 is introduced in a dosage of 4.0 parts by weight;

- in the third vulcanizable rubber composition according to the invention, the compound obtained in Example 5 is added in the same dosage.

Ozone-protective wax is not introduced into all rubber compounds.

From the obtained rubber compounds at a temperature of 155 ° C, standard plates 2 ± 0.1 mm thick were vulcanized for 40 minutes.

From the obtained rubber compounds at a temperature of 155 ° C, standard plates 2 ± 0.1 mm thick were vulcanized for 15 minutes.

To determine the diffusion coefficients of stabilizers, the gravimetric method is used [Kavun SM., Genkina Yu.M., Filippov BC Rubber and Rubber, 1996, No. 6, pp. 10-15], based on periodic measurement of the mass of a sample of a vulcanized plate in the shape of a 2 × rectangle 3 cm, cut from a standard rubber plate without a stabilizer with an initial weight of about 1.4 g, brought into tight contact with two rubber samples of the same shape with the studied stabilizer, applied to the sample without a stabilizer on both sides in the form of a “sandwich” clamped on along with other “studied sandwiches” with other stabilizers, in a thick-walled (with a plate thickness of 1 cm) steel clamp placed in an air thermostat, where the temperature is maintained at 38 ± 1 ° C. Mass measurements of the central sample as a function of time are carried out on an analytical balance with an accuracy of ± 0.0002 g for 120-180 hours until the mass gain reaches a constant level, which requires, depending on the diffusion rate of the stabilizers, from 120 to 180 hours. Further, in grams is plotted against the square root of weight gain in time to ^1/2 and determine the tangent slope of this linear portion depending - tgα [g / s ^1/2], then the equation D = (πd ^2/16) × (tg ² α / Δm ² _∞ ), where d is the thickness of the rubber plate without the stabilizer, measured by the thickness gauge to the nearest 0.001 cm and Δm _∞ is the equilibrium mass gain of the same rubber sample, the diffusion coefficient of the stabilizer under study D is determined in units of cm ² / s. The D values for the stabilizers in the rubbers from the known rubber compound and from the vulcanizable rubber compound according to the invention are obtained, which are presented in Table 7. As can be seen in the table, the D values of the compounds obtained in Examples 1 and 5 in the rubber from the vulcanizable rubber compound according to the invention above than for the stabilizer 6PPD in rubber obtained from the known rubber compound (4.45 × 10 ^-8 , 6.60 × 10 ^-8 and 5.8 × 10 ^-8 cm ² / s, respectively), despite being larger than in 6PPD, MM in both compounds of the invention.

Table 1 The conditions for the synthesis of compounds from the group of N-alkyl-N'-phenyl substituted-p-phenylenediamine introduced into the compositions of the vulcanizable rubber composition according to the invention No.
ditch Alkylation step Finished product

The specific consumption of alcohol per 1 ton of the target product, tons Residual PADA in the reaction mass, wt.%

one 2 3 four 5 6 7 8 one

0.610 0.20

193.9 / 99.5 2

0.635 0.25

200.0 / 98.0 3

0.640 0.15

213.3 / 97.0 four

0.700 0.20

267.4 / 98.1 5

0.635 0.2

240.9 / 97.0 6 ^*)

622 0.15

2142.2 / 98.2 ^*) In an industrial reactor. In column 2, the denominator, in column 5, the number and in column 8, the numerator in kg; in column 3 the numerator in liters / hour, in column 4 the denominator in liters.

table 2 The test results of the compounds of examples 1 and 5 in the formulation of vulcanizable rubber for shock absorber pads based on 100% NK and carbon black P 701 (to Example 7) Indicator The composition of the group of compounds (parts by weight) b / a Diafen FP (2.0) + Acetononil N-1.0 According to example 1 (1,2) + Acetone-nil H-1,0 The compound of example 1 (1,2) The compound of example 5 (1,6) The compound of example 5 (1,6) + Acetan-1,0 one 2 3 four 5 6 Conditional stress at 300% elongation 3.8 4.4 4.2 4.4 3.9 3,5 Conditional tensile strength, MPa 22.5 24.2 22.8 23.0 21,4 21.9 Relates elongation at break,% 700 740 710 730 670 700 Tear resistance, kN / m 41 42 44 44 46 44 Shore Hardness 45 49 45 48 45 44 Rebound elasticity 40 40 40 41 41 40 Residual deformation of compression,% 52.3 50.1 50.1 44,4 39.9 36.1 The aging coefficient at 100 ° C, 48 hours strength 0.70 0.79 0.97 1.13 1.16 1.19 The aging coefficient at 100 ° C, 48 hours relative elongation 0.57 0.62 0.73 0.81 0.80 0.94

Table 3 The test results of the compounds obtained according to example 1, in the formulations of vulcanizable rubber shock absorber pads based on 85% SKI-3, 15% SKD-2 and carbon black P 801 (25 parts by weight) (to Example 8) Indicator The composition of the group of stabilizers (parts by weight) Diafen FP (1.0) + Naphtham-2 (2.0) Diafen FP (1.0) + 8PFDA (2.0) ^*) Diafen FP (1.0) + Connection according to example 1 (2.0) The compound of example 1 (3.0) one 2 3 four Conditional voltage. At 300% elongation 6.0 9.0 7.1 8.6 Conditional tensile strength, MPa 20.8 21.3 20.8 24.6 Relates elongation at break,% 590 600 540 640 Shore A / ISO 43/42 43/42 45/44 45/45 Properties of rubbers after aging, air, 100 ° С, 72 hours Conditional Strength Preservation Factor 0.75 0.83 0.88 0.90 Elongation retention coefficient 0.44 0.60 0.77 0.80 Shore A hardness change after aging (air, 100 ° C, 72 hours) +3 +3 +2 +2 Fatigue endurance during repeated stretching (ε = 100 ± 20%) after aging (air, 100 ° С, 72 hours), Kts 43,4 66.1 48.9 59.7 ^*) Liquid N-2-ethylhexyl-N'-phenyl-p-phenylenediamine

Table 4 Properties of shell rubber hoses based on 70 parts by weight SKI-3 and 30 parts by weight SKD with the replacement of the system of known stabilizers Diafen FP + Acetonanil N with Qualistab 8PFDA-P ^*) and according to the invention obtained according to Example 1 (to Example 9) INDICATORS The composition of the stabilizing group in rubber mixtures, parts by weight one 2 3 four Diafen FP (2.0) + Acetononil N (1.0) Diafen FP (1.5) + Qualistab 8PFDA-P (2.25) The compound of Example 1 (1,2) + Acetononyl H (1,0) The compound of Example 1 (2.0) + Acetononyl H (1.0) Rubber properties at optimum vulcanization (30 'at 143 ° C) Conditional tensile strength, 22 ° C, MPa 15.3 16,2 15.3 13.9 Elongation at break,% 409 440 403 380 Residual elongation,% 9 19 12 eleven Rubber properties after aging at 100 ° C, 72 hours / coefficient Conditional tensile strength, MPa 12.52 / 0.82 13.77 / 0.85 13.8 / 0.90 13.2 / 0.95 Elongation at break,% 230 / 0.56 260 / 0.59 257 / 0.70 277 / 0.73 Residual elongation,% 6 9 8 eleven Rubber properties after aging at 100 ° C, 240 hours / coefficient Conditional tensile strength, MPa 10.39 / 0.68 11.78 / 0.73 11.7 / 0.75 11.47 / 0.85 Elongation at break,% 140 / 0.34 162 / 0.37 180 / 0.45 180 / 0.50 Residual elongation,% four four four four Ozone resistance after heat aging at 100 ° C, 72 hours. Conditions: 40 ° C, [O ₃ ] = 1.5 × 10 ^-3 %, volumetric, tensile 15%, test time 6 hours Time to cracking, min 120 163 240 250 Preservation of strength,% 0 15,5 14.0 14.6 Preservation of elongation at break,% - 31.8 33.7 33.0 ^*) Powder composition 8PFDA (28%) and kaolin

Table 6 The effect of the compounds of Example 1 and known stabilizers on thermal oxidative stability, fatigue resistance and atomosphere resistance (resistance to atmospheric ozone cracking) of the tire sidewall rubber made, respectively, of the known rubber composition and of the vulcanizable rubber compound for the sidewall of the invention (to Example 11). INDICATORS Composition and dosage of stabilizers (parts by weight) Diafen FP (2) + Acetononil N (2) + wax YaV-1 (2) (standard) The compound of example 1 (1.9) + wax YaV-1 (2) Without stabilizers and wax (control) one 2 3 Conditional stress at 300% elongation, kgf / cm ² 9.7 9.7 8.5 Conditional tensile strength, kgf / cm ² 19,4 19.6 20.7 Relative extension, % 550 560 580 Tear resistance, kN / m 60 69 64 The coefficient of thermal aging at 100 ° C × 72 hours by: - conditional strength; 0.77 0.83 0.68 relative elongation 0.60 0.67 0.51 Fatigue endurance during repeated stretching, ε = 100 ± 20%, after heat aging 100 ° С × 48 h, Kts 270 275 140 Tensile strength 20% from May 1 to August 6, 2011 The coefficient of atmospheric aging by: - conditional strength; 0.88 0.92 0.59 relative elongation 0.86 0.93 0.72 Cracking pattern No cracks No cracks cracking over the entire surface on day 12 ^{*) *)} The appearance of the first cracks - on the 6th day.

Claims (2)

1. A vulcanizable rubber mixture for rubber products and tires, which contains those obtained using primary aliphatic alcohols or their mixtures as both an antioxidant, antiozonant and anti-tackifier in a solid exhaust form of a compound from the group of derivatives of N-alkyl-N'-phenyl-p -phenylenediamine with a melting point from 49 to 63 ° C in a dosage of from 1.0 to 5 parts by weight per 100 parts by weight of rubber. 2. The vulcanizable rubber composition according to claim 1, in which the compounds from the group of derivatives of N-alkyl-N'-phenyl-p-phenylenediamine obtained using primary aliphatic alcohols with a molecular weight of alkyl radicals from C 14 to C 18 or mixtures thereof in solid exhaust form in an amount of from 2.0 to 5 parts by weight per 100 parts by weight of rubber, they simultaneously perform, along with the functions of an antioxidant and anti-fatigue agent, the functions of a chemical and physical antiozonant.