RU2563504C1 - Method of producing granular modified soot, soot for high-modulus polymer compositions and polymer compositions using same - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method includes first mixing soot powder with an aqueous solution of a primary aromatic amine in the form of a prepared concentrated solution of metaphenylene diamine or metatoluylene diamine in chemically treated water, which is acidified to pH 3-6.5. Before feeding into a granulator, the mixture is diluted with chemically treated water to working concentration of 0.5-2.0, preferably 0.5-1.2 pts.wt per 100 pts.wt soot, and then fed through the nozzle of the granulator into a stream of dusty soot. The ratio of soot to the solution is 1:1. The obtained wet soot granules are dried at 220-260°C and air access. The granular modified soot contains 0.15-0.40% bound nitrogen, including 36-58% in amine form, and not less than 0.6% oxygen. The polymer composition contains the following components, wt %: synthetic or natural rubber 40-65; granular modified soot obtained using said method 25-40; target additives 1-10; process additives - the balance.

EFFECT: polymer composition based on said soot combines high wear resistance with low hysteresis losses.

3 cl, 15 tbl, 24 ex

Description

Technical field

This invention relates to granular modified soot for high modulus polymer compositions having improved processability and increased reinforcing ability, to a method for its preparation and to polymer compositions using it, combining high wear resistance with reduced hysteresis losses.

The prior art method

Modification of carbon black is carried out to change its surface activity in polymer compositions. Most often, nitrogen-containing compounds are used for this purpose.

The soot was initially treated with nitrogen-containing compounds in the gas phase under pressure (UK patent No. 1054620, publ. 1967.01.17, Japan patent No. 46-20886, publ. 1971.06.11).

Currently, it is carried out using hydrocarbon modifier solutions (Japanese application No. 20052053768, publ. 2002.02.19, Korean patents No. 06-43459 and No. 06-91730 - described in the report of HY Rhyoo. Carbon. Black World, 2006, 6-9 November, patent RU No. 2.272.055 C2, published 2006.03.20 with priority US 60 / 207.254 from 2000.05.26).

The processes of soot modification using solvents are fire hazardous, require the installation of special equipment for the complete removal and regeneration of solvents, and their implementation is impractical.

Processing in the solid phase is carried out with vigorous mixing or spraying of the modification agent on the soot surface (US patent No. 4,557.306, publ. 1985.10.12, patent RU No. 2.272.055 C2, publ. 2006.03.20).

It is believed that the modified carbon black is a physical mixture that promotes uniform polymer modification.

The activation of solid-phase modification processes is ensured by mechanochemical techniques, for example, when using the energy of mobile electromagnetic fields on working ferromagnetic particles (patents SU No. 475385, publ. 1975.06.30, SU No. 653896, publ. 1978.11.28, SU No. 707286, publ. 1979.09.07, SU No. 1392079, publ. 1988.04.30). The disadvantage of modification methods using mechanochemical activation is the increase in soot ash due to grinding from working particles and reactor walls above the permissible norm for use in the rubber industry (0.45% max). In addition, the modified carbon black is not granular, which complicates its practical use in a production environment.

From the point of view of industrial implementation, it is more affordable and promising to combine the process of soot modification with the stage of its wet granulation.

Known methods for treating soot with aqueous solutions or suspensions of a number of nitrogen-containing technical products that are not individual compounds (US patent 3.565.658, publ. 1971.02.23, SU 1120006, publ. 1984.10.23, US 4.764.547, publ. 1988.08.16) . The instability of the chemical composition of the technical products used, their insufficient solubility in water, and sensitivity to the effects of heat and oxygen lead to kinetic instability of aqueous solutions or suspension of the modifier, which negatively affects the uniformity of the modification product.

The use of individual amines for soot vaccination is more promising. In particular, primary aromatic amines are used together with nitrite and an excess of acid to modify soot through intermediate formations of diazonium salts (US patent No. 6.780.389, publ. 2004.08.24).

The closest in technical essence and the achieved technical result (prototype) is the patent RU 2211230 C2, publ. 2003.08.27. The primary amine used is of the formula AyArNH ₂ , where Ar is an aromatic or heteroaromatic radical, Ay is a substituent on said radical, for example, a functional group, a linear, branched or cyclic hydrocarbon radical. According to the patent, any soot, both dusting and pre-granulated, is used. Reaction conditions should ensure the stability of the resulting diazonium salt. Depending on the type of solvent — an aprotic or proton — the pH of the medium can range from 1 to 9. However, when modified at the wet granulation stage using water as the proton solvent, the pH of the medium must be acidic enough to form hydrogen bonds to stabilize the diazonium salt. Of greatest interest from the point of view of the target properties of carbon black is the treatment of carbon black with compounds corresponding to the formula Ar (CH ₂ ) _g Sk (CH ₂ ) _r Ar ', where Ar and Ar' can be the same or different, "k" is an integer from 1 to 8, “g” is an integer from 0 to 4, and “r” is an integer from 0 to 4 (aminophenyl sulfides: 4-aminophenyl disulfide, 4-aminophenyl tetrasulfide, 4-aminophenyl phenyl disulfide). Soot is treated with a wide range of dispersion and structure. For use in rubbers, the soot of the patent is treated with an unsubstituted aromatic diamine with the primary amino groups in the para position (experiments 137 and 138) and aminophenyl sulfides (experiments 80-84, 86-89, 118-120, 123-126, 129-133, 136 , 143-147, 150, 155-156, 158). The diazotization reaction is carried out in the presence of an excess of hydrochloric acid having a normality of 0.37 to 1.43, which, in accordance with the known dependence, corresponds to a HCl solution pH of 0.6 or lower (A. Gordon, R. Ford, Sputnik chemist. Per. from English Moscow: Mir Publishing House, 1976, p. 91-92).

In Example 17, the prototype described method of processing carbon black with a CTAB surface area of 133 m ² / g and structurally 190 cm ^3/100 g using a continuous pelletizer and sulfanilic acid as AyArNH ₂ compound. A soot with a speed of 100 parts per hour by weight, a 30% sodium nitrite solution with a speed of 16 parts per hour and a speed of 112 parts per hour, a suspension consisting of 85.9% water, 5.43 is loaded into a continuously working pin granulator at a time % concentrated nitric acid and 8.72% sulfanilic acid. The ratio of the amount of carbon black and the injected liquid phase is 1: 1.28. The obtained granular product is dried at a temperature of 125 ° C.

In Examples 137 and 138 discloses a method of processing carbon black with an iodine number of 120 g / kg and structurally 125 cm ^3/100 g product diazotization of para-phenylenediamine. 4.87 and 2.43 g of para-phenylenediamine are dissolved in 250 ml of water containing 9.11 g of a 37% hydrochloric acid solution. In accordance with the known dependence of the pH of the water for dissolving the amine is 0.6. The solution was kept in an ice bath and 3.36 g of NaNO ₂ dissolved in 125 ml of water was added. The resulting blue-green solution is added in one portion to a rapidly mixed suspension of 225 g of carbon black in 2 l of water containing 280 g of ice. The suspension is stirred overnight and filtered. Then the product is washed with water, filtered again and dried at a temperature of 125 ° C to constant weight. In these examples, the concentration of para-phenylenediamine is 2.16 and 1.08 parts by weight per 100 parts by weight carbon black, the ratio of soot: aqueous phase is 1: 10.6, and the processing product is not granular.

Examples 80-84 describe a procedure for treating carbon black with aminophenyl sulfides. The process is multi-stage. In particular, in Example 80, concentrated HCl (16.2 g) is diluted with 40 g of water and 9.3 g of 4-aminophenyl disulfide is added, which corresponds to a pH of the medium for dissolving the modifier below 0.1. The mixture is stirred in an ice bath. A cold solution of 6.21 g of NaNO ₂ in 30 g of water is added with stirring, keeping the temperature below 10 ° C. In this case, 4-diazophenyl disulfodichloride is formed. This mixture is added to a prepared suspension of 250 g of granular carbon black in 1.3 L of water with stirring for 2.5 hours and maintaining a temperature of 10 ° C. In this case, interaction with soot is accompanied by the release of gas bubbles. In this example, the soot: liquid phase ratio is 1: 5.58. Then the product is filtered, washed with ethanol, additionally with water and dried at a temperature of 125 ° C to constant weight. After extracting the product in a Soxhlet apparatus with tetrahydrofuran overnight, analysis showed the presence of 1.75% bound sulfur in soot. According to examples 80-84, in the modified soot, the amount of sulfur varies from 1.32 to 1.97%, compared with 1.08% for untreated soot. At the same time, for 100 parts by weight soot is consumed from 2.34 to 3.72% of aminophenyl sulfides. The resulting product is not granular.

The disadvantages described in the prototype methods for processing soot with aromatic amines are:

- the use of concentrated mineral acids and acid-forming compounds, leading to premature corrosion of granulation and drying equipment;

- the need for a diazotization reaction at low temperatures up to the use of an ice bath to ensure the stability of the formed diazonium salts;

- expenditure of the primary amino group of the modifier on the formation of diazonium salts;

- multi-stage and duration of the process due to the need for preliminary preparation of a suspension of soot in water and diazotization products, their many hours of mixing, preliminary

filtering the reaction products, washing the target reaction product from by-products and an unbound modifier, and limiting the drying temperature of the reaction product to not higher than 125 ° C due to thermal decomposition of the azo compound.

The objective of the present invention is to develop a method for producing granular aminated carbon black with a high nitrogen content in the primary amino groups, simplifying the process, increasing its efficiency and increasing the service life of the equipment.

The problem is achieved in that in the method for producing granular modified carbon black, comprising mixing carbon black powder with a water-soluble primary aromatic amine, granulating the carbon black and subsequent drying of the granules at elevated temperature and air access, unlike the prototype, meta-phenylenediamine is used as the primary aromatic amine or meta-toluylenediamine, prepare its concentrated solution in chemically purified water, acidified to pH 3-6.5, before being fed into the granulator, mixed with chemically purified water Oh to a working concentration of from 0.5 to 2 (preferably 0.5 to 1.2) mass, parts per 100 mass.h. soot and introduced through the nozzles of the mixer-granulator into the flow of dusty soot at a ratio of soot: solution "= 1: 1, after which the drying of wet granules is carried out at a temperature of 220-260 ° C.

In the aminating agent used, the primary amino groups are in the meta position and, being first-order substituents, contribute to the double activation of one of the unsubstituted atoms of the aromatic ring, as a result of which it is possible to graft part of the diamine on the carbon black surface without consuming amino groups. Primary aromatic amines, including meta-substituted ones, are oxidative dyes and are prone to oxidation, due to which the amount of oxygen-containing functional groups increases on the surface of soot.

Examples 1-12 show the properties of the used base soot, the parameters of the amination process, and the results of physicochemical analysis of samples of modified soot (Table 1 is shown in the Appendix).

When calculating total and amine nitrogen and bound oxygen in modified carbon blacks, corrections were made for their amounts in base carbon blacks. The chemically purified water used to dissolve aromatic diamines is acidified with hydrochloric acid to a pH of 3 to 6.5 and concentrated solutions of diamines, for example, with a concentration of 25%, are prepared on it for subsequent dilution to a working concentration immediately before introduction into the granulator.

The laboratory continuous mixer granulator is a stationary drum having an internal diameter of 120 mm and a length of 400 mm. Inside the drum, a rotor rotates with the fingers mounted on it along a two-way helical line with a pitch of 100 mm. The distance between the fingers is 12 mm. The rotor drive is equipped with a frequency regulator. The body of the mixer-granulator is heated by an insulated spiral, through which an electric current of controlled power passes to maintain the temperature in the granulator 60-80 ° C. For processing, compacted dusting soot of various grades is used, and its processing is carried out at a ratio of “modifier solution: soot” = 1: 1 for a time sufficient to form granules. Wet granules are dried at a controlled temperature of 220-260 ° C, not exceeding the boiling point of the aminating agent. The dried samples of modified carbon black are extracted for 12 hours in a Soxhlet apparatus with isopropyl alcohol, after which the amount of total nitrogen is determined using the Kjeldahl method in the Terentyev variant (N.N. Lezhnev, A.P. Terentyev, I.S. Novikova, T.A. Kobzeva "Rubber and rubber", 1961, No. 11, pp. 21-27) and the amount of nitrogen in the amine form by non-aqueous titration (Gushchina IV, Listikova IV, Orekhina GA "Intensification of technical production carbon. ”Collection of scientific papers No. 3, Moscow, TsNIITEneftekhim, 1983, pp. 41-46). The total amount of bound oxygen on the soot surface is determined by the thermochemical method for pyrolytic decomposition of soot at a temperature of (1000 ± 50) ° C in an inert gas stream with absorption and quantification of the carbon monoxide and carbon dioxide released (Rivin D. "Chemistry and Technology", 1963 , v. 36, N 3, p. 729).

Achievable technical result by the method

By using the distinctive features of the present invention in the method for producing granular modified carbon black, the following technical results are achieved:

- increasing the efficiency of the process by increasing the amount of bound nitrogen and the proportion of nitrogen in the amine form and increasing the drying temperature;

- reducing the staging process;

- rapid implementation of the process in the wet granulation systems operating at the plants;

- reduction of corrosion of granulation and drying equipment due to the process in a neutral or slightly alkaline environment;

- an increase in the surface activity of soot, providing high modulus polymer compositions.

Prior art for soot

Rubber modules at given extensions are a consequence of the limitation of the mobility of polymer chains due to the formation of a vulcanization network and the polymer-soot interaction, which determines the ability of rubbers to withstand external tensile forces. The compliance of the module value at 300% elongation of the reference rubber with the ASTM D1765 control standards confirms the validity of classifying soot to a particular brand. The value of the module at 300% elongation largely determines the performance of tire rubbers, since wear resistance, grip and tire rolling resistance depend on its value. The provision of an increased rubber module is most appropriate for tread rubber radial tires operating on roads with improved coating - bus and trolleybus tires, long-distance and international tires [A.M. Pichugin “Material science aspects of creating tire rubbers” // Scientific publication - Moscow, 2008, p. 47].

The modulus of 300% rubber, as can be seen from ASTM 1765, increases with increasing dispersion and, to the greatest extent, soot structure. However, with their simultaneous growth, the dispersion of carbon black is inevitably difficult, and in order to realize the potentially possible enhancing ability of soot, it is necessary to significantly increase the specific energy consumption for mixing [Lezhnev NN, Balan I.D., Alenina S.S. and others // "Pneumatic tires made of synthetic rubber." Sat scientific works of PIIT TTL. Moscow: TsNIITEneftekhim, 1979, p. 57-72]. At the same time, the technological properties of rubber compounds are also deteriorating. The relationship between the M300% value of rubbers and the structure of the compressed carbon black sample (ASTM method D3493) is functional, since their correlation coefficient is higher than 0.8 [Krushevskaya I.Ya., Shvarts A.G., Mizonov V.M. and others // "Rubber and rubber", 1974, No. 7, p. 20-23].

The so-called “improved” soot grades are known, obtained according to US patents No. 3.725.103 (publ. 3.04.1973) and US No. 3.799.788 (publ. 03/26/1974), reporting higher structural similarity and lower dispersion the level of the module due to the fact that they have a smaller aggregate size with a narrow size distribution, the aggregates are more open and branched, and the increased content of bound oxygen contributes to the disordering of the surface layers of soot and increase its surface activity [Toussaint UE "New Results on New Technology Black ”/ Intematio nal Rubber Symposium, Sept., 1-5, 1975, Gotvaldov].

The soot obtained by patent RU No. 2131766 C1, publ. 06/20/1999, on multichannel reactors, which are monodisperse, have increased surface activity and give an effect similar to soot "improved" [V.Yu. Orlov, A.M. Komarov, L.A. Lyapina "Production and use of carbon black for rubber." Yaroslavl Alexander Rutman Publishing House, 2002, p. 492-494].

The development of innovative reactor processes for the production of soot for high modulus rubbers requires the reconstruction of existing reactors, a large investment, and is difficult for industries that produce mainly ordinary soot from the ASTM D1765 range.

The soot rubber modulus is increased, manufactured according to traditional technology and modified at the post-treatment stage with nitrogen-containing compounds.

From the copyright certificate of the USSR No. 804660, publ. 02/12/1981, carbon black modified with urea, ethoxylated fatty acid alkylamide or the product of their interaction is known. The growth effect of the rubber modulus is negligible and is obviously a consequence of the improved dispersibility of soot.

From US patent No. 4,557.306 (publ. 10.12.1985) carbon blacks are known which are modified with aqueous suspensions of aromatic furazanoxides. However, in rubber based on natural rubber, a 300% module growth was not observed, unlike styrene-butadiene rubber.

Soot obtained according to SU 1.068.455 (publ. 23.01.84), when treated with diphenylguanidine, gives a greater modulus increase of 300% than aliphatic diamine-hexamethylenediamine (Japanese patent No. 46-20886, publ. In 1971). However, the release of such soot is possible only in dusty form. Soot obtained by treatment with a promoting agent, paranitrosodiphenylamine according to SU 1.068.455, significantly increases the modulus of 300% rubbers, but this product is prohibited for use due to its carcinogenicity.

A specific feature of the promoted reinforcement with the correct selection of the type, dosage of soot, and the amount of promoter introduced is the reduced value of the rubber moduli at low elongations and their high level at 300% deformation (J. Harris, R. Wise, “Elastomer Reinforcement Promoters”, Chapter 9 in Sat “Strengthening of Elastomers” edited by J. Kraus. Translated from English by Moscow: “Chemistry” Publishing House, pp. 211-232).

The closest in technical essence and the achieved technical result (prototype) is the patent RU 2211230 C2, publ. 08/27/2003, using carbon black modified by the reaction products of a primary amine of the general formula AyArNH ₂ (where Ar is an aromatic or heteroaromatic radical, Ay is a substituent on the indicated radical) with nitrite and acid through the intermediate formation of diazonium salts. The authors use as unsubstituted aromatic amine (para-phenylenediamine), as well as compounds of the formula Ar (CH ₂ ) _ρ Sk (CH ₂ ) _r Ar ', where Ar and Ar' can be the same or different, "k" is an integer from 1 to 8, "ρ" is an integer from O to 4, and "r" is an integer from 0 to 4 (aminophenyl sulfides: 4-aminophenyl disulfide, 4-aminophenyl tetrasulfide, 4-aminophenyl phenyl disulfide). The data on rubber stresses given in the patent for various elongations make it possible to distinguish an indicator of the soot's reinforcing ability from its effect on the degree of vulcanization. According to the methodology of Columbian (Ayala JA, Hess WM Kistler FD, Joyce CA "Rubber Chemistry and Technology", 1991, v. 64, No. 1, p. 19-39), the degree of amplification is estimated from the angle of inclination of the stress-strain curve »In a relatively linear region with a coefficient λ = 1-3.

In practice, the degree of soot reinforcement is estimated by the ratio of modules at 300% and 100% elongation (BS Grishin “Materials of the rubber industry. Information and analytical database.” Part 1. Kazan - KSTU. 2010, p. 319).

Table 2 shows the data on carbon black from the prototype obtained in examples 80, 81, 83 and 89 (examples 104, 105, 107 and a control example of the prototype).

With an increase in the content of bound sulfur in soot by 62%, the modulus of 300% of the vulcanizates increased by 39%, while the degree of enhancement increased by only 8%. Therefore, an increase in the amount of bound rubber in the mixtures by 58% and a specified increase in the modulus of 300% are due not so much to an increase in the degree of reinforcement as to an increase in the amount of sulfur in soot and an increase in the degree of vulcanization of rubbers.

Since for the safe processing of mixtures, the amount of sulfur in soot is normalized to not more than 1.1%, vulcanization of mixtures is inevitable.

The objective of the invention for carbon black is carbon black, suitable for producing high modulus polymer compositions, combining increased reinforcing ability and improved processability.

Soot disclosure

This object is achieved in that, in contrast to the prototype, the used granular modified carbon black contains on the surface from 0.15 to 0.40 bound nitrogen, including from 36 to 58% in amine form with the amount of bound oxygen not less than 0.6 %

The processability of soot is determined by its ability to disperse qualitatively, the viscosity of rubber compounds and their resistance to vulcanization. The dispersion quality is evaluated by the value of the specific volume electrical resistivity (Gembrola R.J. "Rubber Chemistry and Technology", 1983, v. 56, No. 1, p. 233-243) using an electrode device according to ed. testimonial. USSR No. 318884 (publ. 10/28/1971).

The presence of undispersed soot aggregates in direct contact mixtures is also evaluated by the intensity of the decrease in the complex shear modulus G * on the RPA2000 at 60 ° C and the increase in shear amplitude from 0.56 to 0.04%, which characterizes the so-called “Payne effect”.

Values of viscosity and kinetics of scorching are evaluated according to ASTM D1646, and strength indicators of vulcanizates are evaluated according to ASTM D412 on a low-inertia tensile testing machine with a stress – strain diagram.

The present invention is disclosed by the data of examples 13-18.

Example 13

A modified carbon black obtained in Examples 1 and 2 by a base carbon black with an iodine number of granulation 42 g / kg and oil absorption of 120 cm ^3/100 g 1.0 pbw meta- and para-isomers of phenylenediamine are introduced into a rubber composition of standard composition based on SKI-3 isoprene rubber. The characteristics of the soot used and the properties of the rubbers containing them are shown in Table 3. The introduction of meta-phenylenediamine directly in the manufacture of the rubber compound is presented as a control option.

Table 3 Indicators Soot as an example Counter. with neobr. soot one 2 Soot Properties Modifier 1 parts by weight m-fda in soot 1 parts by weight p-fda in soot m-fda introduced on rollers The total amount of nitrogen according to Kjeldahl,% 0.201 0.209 - The amount of nitrogen in amine form,% 0,081 0,052 - The proportion of amino nitrogen in the total amount of nitrogen,% 40.3 24.9 - The amount of bound oxygen,% 0.84 0.51 - Mixture Properties Beats about. electrical resistance, Ohm · cm 2.10 × 10 ¹¹ 1.78 × 10 ¹⁰ 1.93 × 10 ¹⁰ Viscosity at 100 ° C, units Mooney 38 42 47 Parameters of vulcanization at 121 ° C: τ ₅ min 10.9 10.6 9.3 τ ₃₅ min 15.6 14.3 11,2 Properties of vulcanizates (143 ° C - 15 min.) Deformation modulus 100%, MPa 3,5 3,7 4.4 300%, MPa 15.8 14.2 16.1 Amplification degree M300% / M100% 4,51 3.84 3.66

Example 14

The modified carbon black having an Iodine Number prior to treatment with 92 g / kg and structurally 113 cm ^3/100 g, 0.7 parts by weight of granular meta-phenylenediamine when dissolved in water with a pH of 6.1 (example 3) and 3.0 (example 4), is introduced into the rubber composition of a standard composition based on emulsion rubber SKMS-30ARK (ASTM D3191). The characteristics of the used carbon blacks and the properties of the rubber containing them are shown in Table 4. For comparison, the data of Example 109 of the prototype patent for rubber based on the same rubber of emulsion polymerization SBR 1500 with carbon black having a similar level of dispersion and structure treated with a diazotization product of 3.7 wt. hours 4-aminophenyl disulfide and containing 2.12% bound sulfur. Data on the technological properties of the mixtures in the prototype are missing.

Table 4 Indicators Soot as an example Soot according to example 85 in example 109 (prototype) 3 four Soot Properties Modifier 0.7 parts by weight meta-phenylenediamine 3.7 parts by weight 4-aminophenyl disulfide The total amount of nitrogen according to Kjeldahl,% 0.252 0.274 The amount of nitrogen in amine form,% 0.124 0.144 The proportion of amino nitrogen in the total amount of nitrogen,% 49.2 52,4 The amount of bound oxygen,% 0.78 0.95 Mixture Properties Beats about. electrical resistance, Ohm · cm 2.01 × 10 ⁸ 3.18 × 10 ⁸ Viscosity at 100 ° C, units Mooney 88.9 86.7 Vulcanization parameters at 130 ° C: τ ₅ min 17.9 20,4 τ ₃₅ min 23.8 27.6 Properties of vulcanizates (143 ° C - 50 min) Deformation modulus 100%, MPa 2,3 2,4 4.12 300%, MPa 11.1 11.8 19.3 Amplification degree M300% / M100% 4.83 4.92 4.68

In example 109 of the prototype, the sulfur content in soot (2.12%) significantly exceeds the maximum allowable level, as a result of which vulcanization of mixtures is inevitable.

Example 15

The modified carbon black having an Iodine Number prior to treatment with 104 g / kg and oil absorption of 114 cm ^3/100 g, treated according to Examples 6 and 7, with 2.0 pbw of granulation meta-phenylenediamine and meta-toluene diamine are introduced into a standard mixture based on SKMS-30ARK. The characteristics of the soot used and the properties of the rubber containing them are presented in table 5. The control variant is a mixture containing unmodified soot (example 5).

Table 5 Indicators Soot by examples 6 7 5 Soot Properties Modifier 2.0 parts by weight m-fda 2.0 parts by weight m-tda - The total amount of nitrogen according to Kjeldahl,% 0.396 0.381 0.01 The amount of nitrogen in amine form,% 0.193 0.137 - The proportion of amino nitrogen in the total amount of nitrogen,% 48.7 36.0 - The amount of bound oxygen,% 0.93 0.62 0.36 Mixture Properties Beats about. electrical resistance, Ohm · cm 8.18 × 10 ⁷ 6.74 × 10 ⁷ 3.2 × 10 ⁷ Viscosity at 100 ° C, units Mooney 92.4 90.5 85.1 Vulcanization parameters at 130 ° C: τ ₅ min 12.0 14.1 13.6 τ ₃₅ min 17.7 23.3 20,4 Properties of vulcanizates (143 ° C - 50 min) Deformation modulus 100%, MPa 3,7 2.9 2,8 300%, MPa 16.1 11,2 8.9 Amplification degree M300% / M100% 4.35 3.86 3.18

Example 16

The modified carbon black having an Iodine Number prior to treatment with 102 g / kg and oil absorption of 94 cm ^3/100 g, treated according to Examples 8 and 9 during granulation 0.5 and 1.2 phr meta-phenylene diamine, is introduced into a mixture similar to that used in Examples 14 and 15. The control is one rubber containing carbon black grade N234, having an iodine value of 122 g / kg and oil absorption of 123 cm ^3/100 g and the amount of nonaqueous volatile defined by according to DIN 53552 - 3.4%., and the amount of bound oxygen - 2.7%. The test results are shown in table 6.

Table 6 Indicators Soot by examples Counter. (N234) 8 9 Soot Properties Modifier 0.5 parts by weight m-fda 1.2 parts by weight m-fda - The total amount of nitrogen according to Kjeldahl,% 0.150 0.317 The amount of nitrogen in amine form,% 0,087 0.170 - The proportion of amino nitrogen in the total amount of nitrogen,% 58.0 53.6 - The amount of bound oxygen,% 0.58 1,07 2.7 Mixture Properties Beats about. electrical resistance, Ohm · cm 1.27 × 10 ⁸ 1.42 × 10 ⁸ 3.17 × 10 ⁸ Viscosity at 100 ° C, units Mooney 73 74 71 Vulcanization parameters at 130 ° C: τ ₅ min 16.3 17.3 16,4 τ ₃₅ min 25.5 26.3 22.5 Properties of vulcanizates (143 ° C - 40 min) Deformation modulus 100%, MPa 2.5 3,1 3.15 300%, MPa 10.6 13.3 13,2 Amplification degree M300% / M100% 4.24 4.29 4.19

Example 17

The modified carbon black having an Iodine Number prior to treatment with 119 g / kg and oil absorption of 115 cm ^3/100 g, treated by 1.2 pbw Example 10 meta-phenylenediamine is introduced into a mixture similar to that used in examples 14-16. The control options are rubber base with an untreated carbon black and rollers inserted in the same number of meta-phenylenediamine, and the tires with carbon black N121, having an iodine value of 122 g / kg, structuring 134 cm ^3/100 g, the amount of nonaqueous volatile of 4.2%, and the amount of bound oxygen is 3.96%. The results are shown in table 7.

Table 7 Indicators Soot according to example 10 Counter. N121 amine introduced on rollers Soot Properties Modifier 1.2 parts by weight m-fda - The total amount of nitrogen according to Kjeldahl,% 0.342 - The amount of nitrogen in amine form,% 0.187 - The proportion of amino nitrogen in the total amount of nitrogen,% 54.6 - The amount of bound oxygen,% 1.91 - 3.96 Mixture Properties Payne effect on an RPA 2000 device with a shear amplitude of 0.56 to 40.04%, kPa 1037.2 2722.4 1703.4 Beats about. electrical resistance, Ohm · cm 7.86 × 10 ⁷ 3.6 × 10 ⁶ 7.18 × 10 ⁵ Viscosity at 100 ° C, units Mooney 104 120 111 Parameters of vulcanization at 130 C: τ ₅ min 26,4 12.7 23,2 τ ₃₅ min 35.5 21.5 32,5 Properties of vulcanizates (145 ° C - 40 min) Deformation modulus 100%, MPa 3.00 4.30 3.06 300%, MPa 17.37 19,20 16.53 Amplification degree M300% / M100% 5.79 4.47 5.40

Example 18

For comparison with the results of Example 217 prototype for use in rubber based on a combination of styrene-butadiene rubbers, solution polymerization NS-116 and NS-114 carbon black having an Iodine Number of 120 g / kg and structurally 125 cm ^3/100 g, the treated product diazotization 1 wt .h. para-phenylenediamine, the rubber indicators of Example 17 (as in Example 10), vulcanized in the mode (145 ° - 60 minutes), having a close modulus level at 300% elongation, are shown. The results are shown in table 8. Data on technological properties in the prototype are missing.

Table 8 Indicators Soot according to example 138 in example 217 (prototype) Soot according to example 10 in example 17 (vulcanizate 145 ° C - 60 min.) Deformation modulus 100%, MPa 4.11 3.52 300%, MPa 21.64 20.52 Amplification degree M300% / M100% 5.27 5.83 Tensile strength, MPa, calculated on the initial section 26.69 29.13 Elongation at break,% 323 394 Tensile strength, MPa, calculated per section at the time of rupture 112.9 143.9

Achievable technical result on soot

The advantage of the claimed soot over the prototype are:

- the preservation or improvement of the technological properties of the mixtures in comparison with the soot base and the introduction of the amine directly during mixing;

- module growth at 300% elongation of rubbers while reducing module at 100% elongation, i.e. achievement of the effect characteristic of promoted gain;

- the possibility of obtaining easily processed grades of carbon black with a simultaneous increase in the achieved degree of gain;

- the possibility of imparting high wear resistance to carbon black polymer compositions while reducing hysteresis losses.

BACKGROUND OF THE INVENTION OF SADFILLED POLYMER COMPOSITIONS WITH LOW HYSTERESIS LOSS

The hysteresis losses in carbon black filled rubber are due to the presence of a carbon black network with direct particle contacts, which is destroyed by dynamic loading of the rubber even at low strain amplitudes (Kraus G. "Mechanical Losses in carbon-black-Filled Rubbers. Journal of Applied Polymer Symposium. 1984 . Bd. 39, p. 75-92). The level of hysteresis losses by 90-95% determines the rolling resistance of the tires and their fuel economy (AM Pichugin “Materials science, aspects of creating tire rubbers. Scientific publication. Moscow, 2008, p. 17), and their dispersion in the deformable material leads to intense heat generation (Medalia. "Heat generation in elastomer compounds: causes and effect". Rubber Chemistry and Technology. 1991. V. 64, No. 3, p. 481-492).

Reducing the hysteretic losses of carbon black filled while maintaining or even increasing their wear resistance has always been and remains the most important task for researchers and practitioners of the rubber industry (Wolff H., Wolff S. status und global trends in rubber carbon black. // Kautschuk, Gummi, Kunststoffe. - 1990. - Bd. 43. N 2. s. 1082-1085).

The elastic hysteretic properties of carbon black filled rubbers and their wear resistance are determined (W. Niedermeier, J. Frohlich. H.D. Luginsland // Kautschuk, Gummi, Kunststoffe. 2002. Bd.55, N 7-8, s. 356-366):

- the size of the primary particles and the specific surface area of the carbon black, which, along with its dosage, determine the effective contact area between the carbon black and the polymer;

- structural and morphology of aggregates that limit the mobility of polymer chains during deformation;

- surface activity, which determines the ratio of polymer-carbon black and carbon black.

In research practice and literature, hysteresis losses for predicting rolling resistance are determined by the tg δ parameter in dynamic shear tests at an amplitude of 6% and 25% at a temperature of 50-70 ° C and a frequency of 1-110 Hz, a loss indicator (K / E) at 60- 100 ° C in symmetric alternating bending mode, as well as an indicator (100-E), where E is the elasticity at 60-100 ° C (F.E. Kuperman. New rubbers for tires. Priority requirements. Assessment methods. - Moscow - 2005 , p. 32-34).

Hysteresis losses in rubbers decrease with decreasing soot dosage (J.R. Wallace. 1987. Quoted from the book by I. A. Agayants “Natural rubber. In search of a recipe” - Moscow, 2005, p. 32-34).

Obtaining high-modulus rubbers with reduced hysteresis losses is possible by increasing the structure of soot while reducing its dispersion (Wolff S., Wang MJ, Tan EN "Kautschuk, Gummi, Kunststoffe". 1995, Bd. 48, No. 2, p. 1111-1117) . Such rubbers have a fairly high wear resistance.

An effective means of reducing hysteresis losses is the use of soot having a wider distribution of aggregates in size: patents US 4478973 (publ. 23.10.1984), US 4786677 (publ. 2.12.1987), US 4988493 (publ. 21.01.1991) and US 5593644 (published on January 14, 1997). With a narrow distribution of carbon black aggregates by size, in particular, obtained according to patent RU 2131766 C1 (publ. 06/20/1999), a significant increase in the modules of 300% rubbers is accompanied by some reduction in hysteresis losses, which allows to reduce the dosage of soot in rubbers.

A positive effect on both the hysteresis and strength properties of rubbers has a decrease in the soot porosity (application DE 4016475 A1, publ. 11.29.1990).

N. Hirakawa showed that improving the quality of dispersion of soot through the use of stiffer rubbers that increase shear forces during mixing and increasing the staging of the mixing process increase the amount of bound rubber that prevents soot from agglomerating, which reduces hysteresis losses with increasing level of rubber modulus ("Hysteresis Loss Mechanism of Carbon Black Filled Rubber "." Kautschuk, Gummi, Kunststoffe ". 1985. Bd. 38 No. 10, s. 898-900).

The contribution of the surface activity of soot to providing a balance between the reinforcing effect and the hysteretic properties of rubbers is realized in the so-called “inverse” soot with a nanostructure developed by Degussa. The soot produced by the patents: DE 19521565 A1 (publ. 16.01.1997) and DE 19839925 A1 (publ. 14.10.1999) have a microrough surface due to the presence in the surface layer of smaller and randomly arranged graphite-like crystallites, which increases the number of active centers and provides multiple adsorption of segments of polymer chains (Niedermeier W., Freund B. Nano-Stmcture Blacks // Kautschuk, Gummi, Kunststoffe. - 1999. Bd.52, N 10. s. 670-676). Such carbon blacks make it possible to obtain high modulus rubbers with low hysteresis losses.

To increase the interaction of carbon black with a polymer competing with the formation of a network structure of carbon black, additives of promoting agents are used. Aromatic derivatives of furazanoxide are used as promoters according to US patents US 4,557,306 (publ. 06/18/1984) and US 4751271 (publ. 1.04.1987). According to the patent US 5001171 (publ. March 19, 1991), promoting agents, including benzofurazanoxide, heterocyclic di-N-oxide, 1-hydroxy-benzimidozole-3-oxide, 1,3-dihydroxybenzimidazolinone, as well as aromatic nitroso compounds, are introduced together with carbon black and polymer in the form of a pre-made master batch. According to the patent US 7053137 B2 (publ. 30.05.2006) in a similar master batch used azodicarbonamide.

Each of the above methods of reducing the hysteresis properties of rubbers is not without drawbacks:

- the use of reduced dosages of soot not only reduces the modules and wear resistance of rubbers, but also leads to their cost increase;

- the use of soot with an adjustable distribution of aggregates by size is difficult from the point of view of quality control and can lead to a decrease in the reinforcing effect;

- the use of soot with a narrow distribution of aggregates in size is possible only with a decrease in their dosage, which increases the cost of rubber and eliminates their advantage in adhesion to the road;

- an increase in the staging process of the mixing leads to an increase in energy consumption for dispersion;

- the use of inversion soot with a nanostructure requires a fundamental restructuring of the reactor process and the development of the latest unique methods for assessing their quality (Donnet J.B., Wang TK International Rubber Conf., 1995, Kobe, Japan. Full Texts, p. 451-454);

- the use of promotional additives requires an additional stage of manufacturing a master batch, which is an exothermic process, after which the mixture needs to be cooled.

The closest in technical essence and the achieved technical result (prototype) is patent RU 2211230 C2 (publ. 08/27/2003), according to which the polymer composition contains carbon black modified by the reaction products of the primary amine of the general formula A _y A _r NH ₂ (where A _r - aromatic or heteroaromatic radical, A _y is a substituent on the indicated radical) with nitrite and acid through the intermediate formation of diazonium salts. Moreover, the amine can be either unsubstituted (para-phenylenediamine) or have the formula Ar (CH ₂ ) _p Sk (CH ₂ ) _r A _r ′, where A _r and A _r ′ can be the same or different, “k” is an integer from 1 to 8, “p” is an integer from 0 to 4, and “r” is an integer from 0 to 4 (aminophenyl sulfides). In accordance with the patent, the use of aminophenyl sulfides increases the amount of bound sulfur in soot above the permissible norm (not more than 1.1%), which leads to vulcanization of the mixtures. In addition, it turns out that the observed effect of increasing wear resistance is uniquely associated precisely with the amount of bound sulfur, which contributes to an increase in the degree of vulcanization. When using an unsubstituted amine (para-phenylenediamine) and sulfur-containing amines that are not polysulfides, the effect of increasing wear resistance is absent. In addition, the use of para-phenylenediamine is undesirable due to its carcinogenic activity.

An object of the present invention is to provide a carbon black filled high modulus polymer composition with an improved ratio of wear resistance and hysteresis loss.

This object is achieved in that the polymer composition, including synthetic or natural rubber, modified with primary aromatic amine carbon black, target additives and auxiliary additives, contains carbon black granulated with an aqueous solution of metaphenylenediamine or metatoluylenediamine in an amount of (0.5-2.0), preferably ( 0.5-1.2) parts by weight per 100 parts by weight carbon black containing from 0.15 to 0.40% bound nitrogen, including from 36 to 58% in amine form, with the amount of bound oxygen more than 0.6%, in the following ratio of components (in wt%):

- rubber-40-65;

- granular modified carbon black - 25-40;

- target additives - 1-10;

- technological additives - the rest.

As rubber, natural rubber or synthetic diene rubbers and their polar copolymers, including isoprene, styrene butadiene, butadiene nitrile and other polymers, are used.

The target additives are vulcanizing agents (sulfur, peroximon F), vulcanization accelerators (altax, Santokyur, thiuram, diphenylguanidine), vulcanization activators (zinc oxide, stearic acid and synthetic fatty acids), vulcanization inhibitors

 (phthalic anhydride), thermal and light stabilizers (paraoxyneozone, 4010NA, protective wax, anti-fatigue agents (santoflex)).

Softeners (GSH-6 oil, liquid paraffin), dispersing agents (rubrax, coumaronindene resins), mineral fillers (silicic acids) are used as technological additives.

Best embodiments of the invention in polymer composition

Example 19

A carbon black having an Iodine Number prior to treatment with 119 g / kg and structurally 115 cm ^3/100 g, treated in the granulation step 1.2 pbw meta-phenylenediamine containing a total amount of bound nitrogen of 0.342%, including 54.6% in amine form, and a quantity of bound oxygen of 1.91% (Example 10), are introduced on rollers into a mixture of the reference composition according to ASTM D3191 based on butadiene styrene rubber SKMS-30ARK. Parallel prepared and tested with the untreated carbon black rubber and rubber containing carbon black mark more active N121, having an iodine value of 122 g / kg and oil absorption of 134 cm ^3/100 g and containing 4.2% non-aqueous volatiles. Along with the soot reinforcing properties, the wear resistance index on the MIR-1 device for rolling with slippage of 14% is determined, the Pain effect of vulcanizates on the RPA2000 device at 100 ° C with an increase in shear amplitude from 0.56 to 40.04% and the tangent of the angle of mechanical losses with an amplitude of 6 and 25%. In addition, the level of hysteresis losses is estimated by the value (100 - Э _{60 ° C} ), where _{60 60 ° C} is the rebound elasticity indicator at 60 ° C, as well as by the heat generation rate upon repeated compression on a Goodrich flexometer. According to the Columbian method, the intensity of carbon black interaction with the polymer is estimated as the quotient of dividing the degree of amplification (M300% / M100%) by the tangent of the angle of mechanical losses at a shear amplitude of 25%. The degree of suitability of carbon black for producing high-modulus low hysteresis rubbers is estimated by the product of this indicator by the modulus at 300% elongation (Lyapina L.A., Ivanitsky M.A., Esikov B.M. “Features of reinforcing rubbers with highly active carbon blacks.” Materials XVIII Intern. Scientific and Practical Conference “Rubber Industry: Raw Materials, Technologies,” Moscow, May 21–25, 2012, pp. 95–97). The test results are shown in table 9.

Table 9 Indicators Counter. neobr. (reference) Soot according to example 10 The introduction of the amine on the rollers N 121 Properties of vulcanizates (143 ° - 40 min.) Modulus, MPa, during deformation one hundred% 2.48 3.0 4.30 3.06 300% 13.21 17.37 19,20 16.53 Amplification degree M300% / M100% 5.33 5.79 4.47 5.40 Tensile strength, MPa, calculated on the initial section 28,4 29.3 27.1 29.3 Elongation at break,% 509 448 413 485 True strength, MPa, calculated per section at the time of rupture 173.0 160.6 139.0 174.3 Wear index one hundred 126.7 124.8 128.1 Payne Effect Index, kPa 1201.1 1405.3 3285,1 2187.0 The tangent of the angle of mechanical losses at shear amplitude 6% 0.153 0.151 0.213 0.182 25% 0.166 0.169 0.257 0.199 Gain / t δ _25% 32.1 34.3 17.4 27.1 Suitability criterion for carbon black for producing high modulus low hysteresis rubbers M300% × Strength reinforced / tg δ 25% 424.2 595.8 334.1 448.6 Hysteresis losses in terms of elasticity (100-E _{60 ° C} ),% 51.5 52,2 59 58.8 Heat generation during multiple compression ΔТ, ° C 31 29th 37 34

Example 20

The carbon black obtained in example 10, is introduced into the tread mixture of the current formulation for passenger radial tires based on oil-filled styrene-butadiene rubber SKMS-30APKN-15 in an amount of 60 parts by weight per 100 parts by weight rubber. Simultaneously introduced N 234 carbon black with an iodine number of 122 g / kg, structure 127 cm ^3/100 g and a volatile content of 3.4% non-aqueous. The target properties of rubber compounds and vulcanizates are shown in table 10.

Table 10 Indicators Soot according to example 10 N 234 Technological properties of mixtures Payne effect, kPa 1762.11 2890.77 Viscosity at 100 ° C. units Mooney 61 71 Vulcanization time at 130 ° C: τ ₅ min 27.8 26.0 Properties of vulcanizates (155 ° C - 15 min) Abrasion, cm ³ / m · 10 ^-3 , on a Schopper-Schlobach device 2.0 2.0 Heat generation, ΔТ, ° C 51.3 57.7 Hysteresis loss indicators: (100-E _{60 ° C} ),% 58 61 K / E at 20 ° C 0.61 0.64 at 100 ° C 0.36 0.39 tg δ at 100 ° C and shear strain 6% 0.196 0.224 25% 0.175 0.199

Example 21

Table 11 shows data of the prototype of rubber properties based on SBR NS114 solution polymerization of Examples 104, 105, 107 and test case with carbon black, which had to granulation, the Iodine Number of 120 g / kg and structurally 125 cm ^3/100 g, the treated according to examples 80, 81 and 83 by various types of aminophenyl sulfides in an amount of from 2.3 to 3.7 parts by weight per 100 parts by weight carbon black and containing from 1.32 to 1.75% bound sulfur at 1.08% in base soot.

Table 11 Indicators Soot prototype examples 89 83 81 80 in examples counter. 107 105 104 The amount of bound sulfur,% 1,08 1.32 1,56 1.75 Amplification degree M _200% / M _100% 2.67 2.71 2.90 2.85 Module 300%, MPa 14.1 15,2 - - Relative extension, % 385 372 274 290 Tensile strength, MPa 18,4 19.6 16.7 19.5 tg δ at 70 ° C 0.173 0.170 0.137 0.114 Wear Resistance Index,% one hundred 103 114 122

These data indicate that a decrease in hysteresis losses and an increase in the wear resistance of rubbers are associated not with an increase in the degree of reinforcement, but with the amount of bound sulfur in the modified soot, which increases the degree of vulcanization of the rubbers.

Example 22

A carbon black having an Iodine Number prior to treatment with 42 g / kg and structurally 120 cm ^3/100 g, treated by the 1st Example 1.0 pbw meta-phenylenediamine containing a total amount of nitrogen of 0.201%, including 40.3% in amine form, with an amount of bound oxygen of 0.84%, is introduced into the mixture for lining a conveyor belt of the following composition (parts by weight):

- SKI-3 - 50.0;

- SKMS-30ARK - 50.0;

- sulfur - 0.2;

- Tiuram - 2.0;

- Altax - 0.8;

- zinc oxide - 12.0;

- soot - 50.0;

- petroleum jelly - 10.0;

- indencumarone resin - 8.0;

- synthetic fatty acids (C ₁₇ ÷ C ₂₀ ) - 2.0;

- Rubrax - 7.0;

- paraoxynozone - 2.0;

- phthalic anhydride - 1.0.

When replacing untreated soot with soot in Example 1, the amount of zinc oxide, which is a vulcanization activator, is reduced from 12 to 7 parts by weight. The test results are shown in table 12.

Table 12 Indicators Modif. carbon black, 7 parts by weight zinc oxide Neobr. carbon black, 12 parts by weight zinc oxide Parameters of vulcanization at 121 ° C τ ₅ min 6.9 7.0 τ ₃₅ min 11.1 11.8 Modulus at 300% elongation, MPa 3.2 3.8 Tensile strength, MPa 10,4 9.3 Relative extension, % 798 695 Shore hardness, units 59 59 Abrasion on the device MIR-1, cm ³ / kW · h 174 195 Wear Resistance Index,% 112.1 one hundred Hysteresis losses (100-E _{60 °} C),% 43 48

Example 23

The carbon black obtained in example 1 is introduced in an amount of 40 parts by weight into the rubber mixture based on nitrile butadiene rubber SKN-26M with a peroxide vulcanizing agent of the following composition (mass.h):

- SKN-26N - 100;

- zinc oxide - 5.0;

- soot - 40.0;

- Peroximon F-40 - 1.5.

In another embodiment, an additional 10 parts by weight of the mixture are added. reactive oligomer - oligoester acrylate TGM-3. The mixture was vulcanized at 160 ° C for 30 minutes. The properties of rubber compounds and vulcanizates are given in tables 13 and 14.

Table 13 Indicators Soot according to example 1 Counter. (untreated soot) Viscosity at 100 ° C. units Mooney 46 65 Vulcanization parameters at 121 ° C τ ₅ min 8.2 6.7 τ ₃₅ min 17.3 20.3 Modulus, MPa, during deformation one hundred% 4.8 4.0 200% 16.5 7.8 300% 21.9 15.9 Gain (M _300% / M _100% ) 4,56 3.98 Tensile strength, MPa 26.0 17.3 Relative extension, % 370 310 Hysteresis losses (100-E _{60 ° C} ),% 33 38

Table 14 Indicators In the presence of 10 parts by weight TGM-3 Modif. soot (as in example 1) Counter. (untreated soot) Viscosity at 100 ° C. units Mooney 40 33 Vulcanization parameters at 121 ° C τ ₅ min 4,5 8.4 τ ₃₅ min 8.9 14.6 Modulus, MPa, during deformation one hundred% 5.3 4.9 200% 17.6 15.7 M _200% / M _100% 3.32 3.20 Tensile strength, MPa 28.0 23.8 Relative extension, % 275 225 Hysteresis losses (100-E _{60 ° С} ),% 36 37

The effect of the modified carbon black decreases when there are reactive oligomers in the mixture that compete with the polymer in interaction with the carbon black surface and the vulcanizing agent.

Example 24

The carbon black obtained in example 10 is introduced into the tread mixture of the current formulation for CMC truck tires based on natural rubber in a dosage of 55 parts by weight For comparison, carbon black N121 is introduced in the same dosage. The properties of rubber compounds and vulcanizates are shown in table 15.

Table 15 Indicators Soot according to example 10 N121 Mixture Properties Viscosity, units Mooney at temperature 100 ° C 76 75 130 ° C 55 55 Parameters of vulcanization at 130 ° C: τ ₅ min 15,5 14.8 τ ₃₅ min 16 15,5 Properties of vulcanizates (155 ° C - 15 min) Module 300%, MPa 11.8 12.0 Tensile strength, MPa 22.0 23.8 Relative extension, % 468 491 Shore hardness, units 69 68 Hysteresis loss indicators: 100-E _{100 ° C} 51 56 K / E at temperature: 200 ° C 0.45 0.47 100 ° C 0.34 0.37 ΔТ, ° C 40.7 42.7 Abrasion on a Schopper-Schlobach device, cm ³ / m · 10 ^-3 2.07 2.22

Achievable technical result on polymer compositions

The advantages of the claimed polymer compositions over the prototype are:

- ensuring the resistance of high-modulus rubbers to vulcanization by improving the quality of dispersion of soot, the absence of bound sulfur in the modified soot and increasing the amount of bound oxygen;

- an increase in the contribution of soot to the magnitude of the rubber modulus by increasing the level of interaction of soot with the polymer, as assessed by the degree of amplification;

- reduction of hysteresis losses of high-modulus rubbers without deterioration or with an increase in their wear resistance due to increased interaction of carbon black with the polymer and the participation of bound nitrogen in the amine form in the formation of the vulcanization network of rubbers;

- the possibility of reducing tire rolling loss and fuel consumption, since there is a linear relationship between rolling resistance and the tangent of the angle of mechanical losses at a shear amplitude of 6% (Kraus G. "Journal of Applied Polymer Science: Applied Polymer Symposium", 1984, Bd. 23, s . 75-92);

- the possibility of replacing expensive and difficult to disperse soot with increased dispersion and structure to obtain high modulus rubbers with easily processed modified soot with less dispersion and structure to achieve an economic effect.

Claims (3)

1. A method of producing granular modified carbon black, comprising mixing carbon black powder with an aqueous solution of a primary aromatic amine, granulating carbon black and subsequent drying of the granules at elevated temperature and air access, characterized in that metaphenylenediamine or metatoluene diamine is used as the primary aromatic amine, and concentrated it is preliminarily prepared a solution in chemically purified water, acidified to a pH of 3 to 6.5, before being introduced into the granulator, dilute with chemically purified water to a working concentration radios from 0.5 to 2.0, preferably from 0.5 to 1.2 phr based on 100 parts by weight soot, and introduced through the nozzles of the granulator into the flow of dusty soot at a ratio of soot: solution "= 1: 1, after which the drying of wet granules is carried out at a temperature of 220-260 ° C. 2. Granular modified carbon black obtained by the method according to claim 1, containing from 0.15 to 0.40% bound nitrogen, including from 36 to 58% in amine form, with an oxygen content of at least 0.6%. 3. A polymer composition comprising synthetic or natural rubber, granular modified carbon black, target additives and processing aids, characterized in that as carbon black it contains carbon black according to claim 2 in the following ratio of components (% weight):
- rubber - 40-65;
- granular modified carbon black - 25-40;
- target additives - 1-10;
- technological additives - the rest.