Abstracts

№1, 2017

Comparison of Laboratory and Industrial Data on Monomer Conversion at Isoprene Polymerization

Nasyrov I.Sh. (Ph. D. [Chem.], Deputy Gen. Director), Faizova V.Yu. (Ph. D. [Chem.], Chief of Lab), Zhavoronkov D.A. (Gen. Director), Zakharov V.P. (Prof., D. Sc. [Chem.]), Zakharova E.M. (Ph. D. [Chem.], Res.)

The results of comparative analysis of kinetic regularities of the polymerization of isoprene in the presence of titanium and neodymium catalysts prepared in the laboratory and industrial conditions are presented. Similarity of conversion curves of the isoprene polymerization in the presence of a neodymium catalyst is shown if monomer solution was obtained both in the laboratory and industrial conditions. In the case of titanium catalyst the industrial conditions of preparation of monomer solution results in the lower rate of polymerization. It may be due to the presence of isoamylene. Isoprene polymerization in a cascade of three polymerizers in the presence of a neodymium catalyst is characterized by a lower rate in comparison with the synthesis by a periodical process in laboratory dilatometer. Synthesis of polyisoprene in the presence of titanium catalyst in a cascade of two volume polymerizers occurs with higher rate in comparison with laboratory conditions. Comparison the rates of polymerization in this case is only qualitative because of the differences in polymerization temperatures. In the laboratory conditions it was 20 ºС, in industrial ones at adiabatic heating of reaction stock it increase in the interval 0–52 ºС for titanium catalyst and from –5 to 55 ºС for neodymium.

Key words: polyisoprene, polymerization, monomer solution, neodymium catalyst, titanium catalyst, industrial conditions, laboratory conditions

Effect of Nanocarbon on Structural and Thermophysical Parameters of Polymer Matrix

Voznyakovskii A.P. (D. Sc. [Chem.], Chief of Sector), Smirnov A.V. (Ph. D. [Phys.-Mat.], Assist. Prof.), Fedorov B.A. (Prof., D. Sc. [Phys.-Mat.]), Esina A.V. (Jun. Res.), Boreiko N.P. (D. Sc. [Techn.], Deputy director )

Effect of Nanocarbons (NC) of different origin: fullerene C60, single wall carbon nanotubes (SWCNT) and carbonized starch, as a model, on a structure and properties of filled and unfilled polyurethane matrix (PU) was studied. NC was incorporated into part of PU prepolymer and then was insonificated. Specific surface of fillers was recorded using the BET-method on Quantachrome NovaWin device (Quantachrome Instruments, USA). Aggregates of SWCNT, as revealed by the method of small angle scattering, SAXS, (diffractometer «AntonPaar», Austria), possess a high roughness of a surface (fractal dimension D = 2,9) while particles of C60 and PSC possess a smooth surface (D = 2,0). SAXS data also demonstrated an invariance of rigid block structural organization over a distance about 3 nm and less. Wide-angle X-ray scattering technique (Bruker «D2 Phaser») allows to draw a conclusion on preferred distribution of fine NC particles on elements of free polyurethane matrix fluctuation volume. As a result, these particles do not influence on morphology of matrix elements. Independence of glass transition temperature Tg from presence and nature of NC, as determined by differential scanning calorimetry (DSC 8000 of Perkin Elmer), testifies that mobility of polymer macromolecules don’t connect with presence of NC in PU matrix. Data of all these methods indicate that the NC particles are distributed in interdomain space, and mainly, in areas of peak local stresses in the polymer matrix. This conclusion is well confirmed by complex of strength parameters obtained (a tensile-testing machine («Tinius Olsen H10KT», England): stresses at elongation of 100 and 200 % increase by 20–50 % and tear resistance up to 80 %.

Keywords: polymer nanocomposites, nanocarbons, single wall carbon nanotubes, fullerenes, starch carbonized, polyurethane, reinforcement model, specific surface, SAXS, WAXS, DSC, Tg, heat capacity, deformation and strength properties

Effect of Functionalization of Low-Dispersion Carbon Black Series OMCARB by Hydrogen Peroxide

on the Properties of Filled Composites

Moiseevskaya G.V. (Head of Sector), Razdyakonova G.I. (Ph. D. [Chem.], Sen. Res., Assist. Prof.), A.A. Petin (Director)

The goal of this work is obtaining the polymer filler of low surface activity combined with the high structure and surface functionalization. The use of the filler of this combination of properties open the possibility to obtain the rubber compounds of characteristics similar to those of rubber compounds filled with channel carbon black. Low dispersion high-structure OMCARB S820 was oxidized by water solution of hydrogen peroxide of different concentration. The types and amount of oxygen containing groups (carboxylic, phenol, lactone) on oxidized S820 particles comparative to channel carbon black was evaluated. The physical and chemical properties of fillers were also compared by means of different methods, in particular X-ray (D8 Advance, «Bruker») and TEM (JEM 2100, «JEOL»). NR rubber compounds containing different fillers were tested for rheological (MDR3000 and MV3000, «MonTech»), physical and mechanical (DМА 242D, «Netsch») properties. Comparison of temperature dependence of tgδ in the interval -60 – +60ºС for rubbers of different fillers is presented. The main difference in the tgδ for rubber with channel carbon black К354 both at –60 and +60ºС is shown, the data in the intermediate temperatures are nearly similar. It was found that new carbon black provided improved strength and dynamic characteristics of rubbers together with unique properties obtainable for rubber compounds filled with channel carbon black.

Key words: carbon black, functionalization, hydrogen peroxide, water suspension pH, X-ray, TEM, NR rubber compounds, rheological properties, physical properties, mechanical properties, tgδ

The Use of Master Batches of Shungite in the Tread and Carcass Tire Rubber Compounds

Potapov E.E. (Prof., D. Sc.[Chem.]), Miroshnikov Yu.P. (Prof., D. Sc. [Chem.]), Bobrov A.P. (Ph. D. [Techn.], Head of Sci. Dep.), Smal V.A. (Chairman of Board)

Processing and mechanical properties of master batches (MB) of shungite (Karelit, K) have been studied, as well as properties of tire rubbers based on BSR. Content (c) of K in MB was up to 100 phr and more, in tire rubbers it was 15–20 phr. Dependence of tgδ on deformation amplitude (Payne Effect) of MB is the same for с ≤ 10 phr and at с > 10 phr is increased with c. On the basis of data obtained the mechanisms of interaction of K particles with elastomer matrix and between one another are under discussion. The improvement of processing properties of MB at introduction of benzoic acid was shown. The level of the main mechanical properties of tire rubbers is the same or higher under the use of MBK of с = 20 phr. Experimental batches of three types of truck tires with the use of MBK in tread and carcass were tested.

Key words: shungite, Karelit, master batch, Payne Effect, tire rubbers on basis of BSR, truck tires

Investigation of the Effect of Filling by Taurit of Rubber Compound for Rubber Covering of Breaker of Radial Tires for Trucks

Mindubaev R.R. (Deputy Executive Director), Moknatkin A.M. (Ph. D. [Techn.], Chief of Department), Dorozhkin V.P. (Prof., D. Sc. [Chem.]), Moknatkina E.G. (Ph. D. [Techn.], Chief of Chair)

The results of study of influence of analog of shungite, Taurit (T), brand TSD, on properties of rubber compound (RC) and tire rubber (R) based on synthetic rubber SKI-3 (measured by RPA2000) are presented. Different ways of T introduction: 10 phr in the SKI-3 at production; 10 phr in breaker RC at the first stage of compounding; 10 phr in SKI-3, previously plasticized at 100 °С are tested. Introduction of lower amount of T for the lowering of the portion of SKI-3 in RC are also tested. The results are compared with that of usual breaker RC. Introduction of T in SKI-3 at production results in the increase of green strength and vulcanization rate. Components of dynamic modulus G’ and G” are also increased as at introduction of T in plasticized SKI-3. This way results in the increase of plasticity and decrease of the Defo-elasticity of RC. Breaker rubber of this RC shows the best adhesion to cord and the higher fatigue life. Data of the Payne Effect show on the best particles distribution of carbon black in the case of introduction of T in SKI-3 at production. However the decrease of the lowering of the portion of SKI-3 in RC results in the worse particles distribution.

Key words: shungite, Taurit, rubber compounds and rubber for breaker truck tires, processing and mechanical properties, Payne

Effect, particles distribution, adhesion The Influence of Composition of Rubber Compounds on Aging Resistance of Vulcanizates Based on Butadiene Acrylonitrile Rubbers of Different Polarity

Yulovskaya V.D. ( Ph. D. [Chem.], Assist. Prof.), Monakhova T.V. ( Ph. D. [Chem.], Sen. Res.), Petrova V.S. (Undergrad. Stud.), Karpova S.G. (Ph. D. [Phys.-Mat.], Sen. Res.)

The influence of composition of rubber compounds based on butadiene acrylonitrile rubbers of different polarity (BNRS-18, BNRS-28 and BNRS-40) on mechanical properties of vulcanizates before and after thermooxidation aging has been studied. Sulfuric and peroxide cure systems were used for vulcanization. EPR-spectroscopy was in use and its results show the similarity of correlation time before and after thermooxidation aging. This is indirect evidence of absence of destruction. Introduction of curing systems and vulcanization itself activate the oxidation process of the samples, increase the speed of oxidation and the amount of bound oxygen. The substitution of sulfur-containing curing system with a peroxide one results in 6-7 times increase of the induction period of oxidation. Introduction of nanosized titanium dioxide Degussa (NDT) results in some decrease of strength and elongation at rupture. The addition of 1% of NDT in the pure rubber has little effect on oxidation kinetics. The addition of 3% of NDT results in decrease of correlation time after oxidation (from 19∙10 -10 to 16∙10-10 s).

Key words: BNR, nanosized titanium dioxide, oxidation resistance, rubber composition, vulcanizates, EPR, Instron-1122

New Antiozonants for Rubber Compounds, Based on the Oxyalkylated Derivatives of 4-Aminedipphenylamine

Ushmarin N.F. (Ph. D. [Techn.], Deputy Chief of Prod., Chief of Techn. Dep.), Kavun S.M. (Ph. D. [Chem.], kavun05@mail.ru), Vinokurov Yu.V. (Ph. D. [Tech.])

Properties and results of testing of the new antioxydants (NAO) 2PPD and 3PPD for rubber compounds are presented. NAO are recommended instead of imported 6PPD and IPPD usually used in all types of technical rubber goods, as wall as sidewall and tread compounds of tires. The structure and the manufacturing way of NAO are declared as the invention. The offered way allows organizing industrial production of NAO with the low processing cost, unlike processing of 6PPD and IPPD. The raw materials are ethylene - and propylene glycoles, available in the Russian Federation, and 4-aminodiphenilamine (4-ADPA). 4-ADPA is imported for manufacture in Russian Federation of С789, antioxidant for synthetic rubbers, mainly for stabilization of large volume of synthetic polyisoprene SKI-3, 70 % and more of this rubber is exported. Some advantages of 3PPD in comparison with imported ones are established, including higher efficiency at protection of rubber compounds against thermooxidation and ozone cracking. Some disadvantages of NAO are under consideration (the final form, the influence on vulcanization kinetics), and approved versions of their overcoming are also presented.

Key words: antioxydants, chemical structure, raw materials

Influence of Molecular Complex of Lactam Containing and Proton-donor Substances on Adhesive Properties of Adhesive Composition

Puchkov A.F. (Ph. D. [Techn.], Assist. Prof.), Tretyakova N.A. (Ph. D. [Techn.], Chief of Department), Khodakova S.Ya. (Ph. D. [Techn.], Chief of Lab.), Abolskaya I.I. (Eng.-Techn.), Bobrov S.P. (Ph. D. [Techn.], Deputy Gen. Director)

Results of the investigation of the influence of molecular complex (MC) based on a lactam and a hydroxyl compound, on the adhesive properties of elastomer adhesive are presented. MK are binary melts based on trihydric alcohol (TA) and ε-caprolactam. MK were introduced into a adhesive based on chloroprene rubber in the different proportions together with an isocyanate of 4,4'-methylene diphenyl diisocyanate (MDI). The MC adhesion activity was evaluated by the bond strength between the elements of the rubber-cord composites «rubber-based on BNKS 40AMN + cord, coated by the rubber compound based on the general purpose rubbers» according to GOST 6768-75. Comparison of IR spectra (IR-Fourier spectrometer FSM 1201) of MC and their individual components open the possibility to assume the presence of some hydrogen bonds. The analysis of the NMR spectrum (NMR-spectrometer Bruker Avance-400) of MC showed a lack of the new chemical bonds between its components. Theoretically, a binary MK introduced into the adhesive composition in conjunction with an isocyanate, should favor the increase of the bond strength between the substrates due to the formation of the urethane groups. The results of the test of the MC in the adhesive compound show the higher bond strength of the rubber/cord samples if the ratio of TC and ε-caprolactam was 2:1. The admission of MC in conjunction with MDI results in increase of the adhesion strength by 25 %.

Key words: adhesive composition, triatomic alcohol/triol, ε-caprolactam, isocyanate, IR-Fourier spectroscopy, NMR, adhesion strength, rubber/cord samples

Influence of Рigments on Сharacteristics of Сombustibility of Technical Rubber Based on Methylvinylsilicone Rubber

Barbot’ko S.L. (Ph. D. [Techn.], Chief of Lab.), Naumov I.S. (Ph. D. [Techn.], Eng.-Techn.), Volnyj O.S. (Lead. Eng.), Alifanov E.V.(Ph. D. [Chem.], Act. Sen. Res.)

At the application of the articles of polymeric materials in different industrial fields the wide color gamma can be demanded. The change of characteristics of fire danger can arise as a result of the use of pigments of various chemical natures, often of some catalytic activity. Combustibility of silicone technical rubber (VR-42 brand) containing several inorganic pigments was studied. Essential effect of pigment composition (on the base of carbon black or metals compounds) was determined under comparison with standard rubber, containing magnesium hydroxide. Essential effect

of carbon pigment of nanoparticles on characteristic of duration of residual burning is shown. No statistically significant changes of this characteristic at the introduction of mineral pigments of different color gamma based on metals compounds is established.

Key words: fire safety, combustibility, silicone technical rubber, pigment, color, carbon black, nanoparticles, metals compounds

Quality Control over Joints of Rubber-Textile Conveyer Belts by the Use of Thermovisor

Golikov G.F. (Ph. D.[Techn.], Chief of Sector), Ryabov D.V. (Gen. Director), Galashin S.N. (Consultant), Kondrashin Yu.A. (Ph. D.[Techn.], Gen. Director)

The method of the direct control over joints of rubber-textile conveyer belts by the use of thermovisor TESTO 875-1 (Germany) of high resolution was aprobated. The method is based on the difference between the heat conductivity of the materials in the region of defects and in the other areas. This difference results in temperature differences of defect and the other areas of conveyer belts under heating or cooling and measured by temperature detectors or strikingly illustrated by Thermovisor. Conveyer belts 500mm wide (from fabric ТК-200) with widespread artificial defects were tested. The belts with defects were heated in vulcanizing press from +10 to +70ºС or cooled from +90 to +70ºС. The belts with defects in greasing were heated from –10 to +70 ºС. The temperature differences between defect and the other places was from 15 to 4ºС. Later on the control over joints in the service of rubber-textile conveyer belts, especially in the most demanded conveyers, is supposed.

Key words: rubber-textile conveyer belts, joints defects, quality control, heat conductivity, temperature differences, Thermovisor

Evaluation of Mechanical Properties of Hyperelastic Composite Materials with Small Additions of Disperse Mineral Fillers

Part 2. Realization of the Task in the Cell by Finite Element MethodVlasov A.N. (D. Sc.[Techn.], Director), Volkov-Bogorodsky D.B. (Ph. D. [Phys.-Mat.], Sen. Res.), Karnet Yu.N.(Ph. D. [Phys.-Mat.], Sen. Res.), Gamlitsky Yu.A.(Assist. Prof., Ph. D. [Phys.-Mat.], Ch. Res.,),Mudruk V.A. (Assist. Prof., Ph. D. [Phys.-Mat.])

Numerical method of determining the effective mechanical properties of hyperelastic composites filled by particles of spherical form, based on the solution of periodic tasks in the cell to include simulating the conditions of uniaxial tension and pure shear is presented. On the basis of this technique and the experimental data on the properties of micro- and nano-scale filler (shungite) as well as elastomer (SBR) the increase of stiffness (both effective elongation and shear modulus) of the composite material was shown. The increase of stiffness of elastomer matrix in comparison with unfilled elastomer is also shown. The data obtained are illustrated the difference between the mechanical properties of composite materials of micro- and nano-scale filler.

Key words: elastomer composite materials, elastomer matrix, SBR, dispersed filler, shungite, interphase layer, aggregates of particles, elongation modulus, shear modulus, FEM, periodical cell, hyperelasticity

«Interplastic 2017» – the Key to World Markets

Post-release on two International Trade Fairs «Interplastica» and «Upakovka» organized by «Messe Düsseldorf» and «Messe Düsseldorf Moscow» (Moscow, Expocenter, 24–27.01.17).

Key words: trade fairs, polymers, machine building, 3D technology, raw materials, innovations