Abstracts

№4, 2017

Study of Stabilizing Efficiency of Thermal Stabilizers Bisfenol-5 and Vulkanox BKF at Production of Butadiene Acrylonitrile Rubber

Akhmadullin R.M. (Ph. D. [Сhem.], Chief Eng.), Karimov I.A. (Assistant), Akhmedshin I.F. (Master), Kotyrev E.A. (Chief Eng.),

Alimanov D.V. (Chief of Production), Nadelyaev K.L. (Chief Process Eng.- Chief of Techn. Dep.)

Properties of thermostabilizers Bisphenol-5 (4,4'-bis(2,6-di-tert-butylphenol) and Vulkanox BKF 2,2-methylene-bis(4-methyl-6-tert-butylphenol) and their efficiency at stabilizing BNR (SKN-1865 and SKN -2665) were studied. Efficiency of stabilizers was evaluated measuring of thermo oxidation aging at 150 °С during 1 and 3 hours. Changes of Moony viscosity and solubility of rubbers with Bisphenol-5 is lower than that of rubbers with Vulkanox BKF. The high stability of dispersion of Bisphenol-5 after treatment in ball mill during 12 hours was shown. Stability was evaluated measuring the rate of sedimentation of Bisphenol-5 particles and the ratio of sediment to dispersion bulk. Comparison of vulcanization time and mechanical properties of vulcanizates based on rubbers contain of both antioxidants was presented. Recommended content of Bisphenol-5 in SKN-1865 is 0,23 phr and in SKN -2665 is 0,3 phr. It is possible to recommend Bisphenol-5 as alternative to imported Vulkanox BKF.

Key words: thermal stabilizer, antioxidant, Bisphenol-5, Vulkanox BKF, BNR, dispersion, thermo-oxidative aging, rheological and mechanical properties, importsubstitution

Поступила в редакцию 09.11.2016

«Emlants»—New Generation of Elastomeric Materials. Properties and Prospects

Part I. Lanthanide-Catalyzed Cis-Polyisoprenes

Tsypkina I.M. (Ph. D. [Тhech.], Lead. Res.)

Properties of new type of lanthanide-catalyzed elastomers («emlants»), as well as emlants (E) based rubber compounds and vulcanizates have been studied. E are general purpose rubbers prepared using different rare earth compounds as catalysts. Properties of isoprene E are compared with that of titanium-catalyzed SKI-3. Micro- and macro-structures have been examined by IR- and NMR-spectroscope. MMR was evaluated by gel-permeation chromatography (chromatograph Breese, company «Waters») with toluene at 35 °С as eluent. Features of processing were studied by plastycorder PLV-151 («Brabender»). Destruction of isoprene rubbers was made under air or argon. Rheological properties of rubber compounds were studied by Williams plastometer and viscometer MV2000 («Alfa Technologies»), vulcanizing properties by rheometer 100S («Monsanto») and MDR 2000 («Alfa Technologies»). «МОМ» and «Perkin Elmer» devices were in use for tests of thermo-changes. Metal content determined by mass spectroscopy (NexION 300D, «Perkin Elmer»). The effect of rare earth type on E structure is shown. In contrast with SKI-3 there are no trans-1,4 units in E, they contains 99–100 % cis-1,4 units, however the rate of low temperature crystallization is lower. There are nearly no gel-fraction in E. The high thermo-mechanical stability of E with gadolinium and terbium as catalysts is established. The systemization of common features and advantages of isoprene E is presented. The set of improved properties open the possibility to consider environmentally friendly isoprenes E as the basis for development of composition materials of a new generation.

Key words: emlants, rare earth-catalyzed polyisoprenes, titanium-catalyzed polyisoprene, micro-structure, macro-structure, gel content, crystallization, thermo-mechanical stability, processing properties, physical and mechanical properties

Compatibilizing Agents for Enhance the Interaction on the Phase Boundary of TPV Based on Rubbers of Different Polarity

Panfilova O.A. (Postgrad. St.), Volfson S.I. (Prof., D. Sc. [Techn.], Chief of Chair), Okhotina N.A. (Prof., Ph. D.[Techn.]), Sabirov R.K. (Assist. Prof. Ph. D.[Chem.]),

Baranets I.V. (Ph. D. [Tecn.], Lead. Res.), Karimova A.R. (Undergraduate Student), Shishkina A.A. (Undergraduate Student)

The opportunities of enhance interaction between components of early-developed TPV based on polypropylene (PP), isoprene (IR) and nitrile-butadiene rubber (NBR) combination were studied. The optic microscopy (optic microscope Leica DM-2500, high resolution color digital camera Leica DFC-420C and specialized computer station) was used to fix the composition morphology. The PP crystallization parameters were measured using the method of differential scanning calorimetry (DSC 204F1 Phoenix, (NETZSCH). The physical and mechanical properties of vulcanizates were also determined. As a compatibilizing agents the maleinized polypropylene (MAPP), the polyethylene-co-vinyl acetate and combination of thereof were used. MAPP (1–10 weight parts) introduced with PP. Usage more than 4 weight parts didn’t affect on the properties. Polyethylene-co-vinyl acetate (1–10 weight parts) introduced with rubbers and was used to increase interaction between rubbers. MAPP introduction resulted in technological and stress-strain properties (such as elastic modulus and hardness) growth. The growth of distribution uniformity at TPV bulk, high dispersing of rubbers at PP matrix, the decrease of pores amount and increase the PP degree of crystallinity were shown. The use of combination of polyethylene-co-vinyl acetate and maleinized polypropylene results in increase of tensile strength at 34 %, elongation at break – at 15 %. The compatibility of polymer components increases, the interphases become more diffusive, rubber-reached zones optical density decreases, the PP fibrils penetrate rubber-reached zones.

Keywords: TPV, PP, IR, NBR, components interaction, components compatibility, interphases, optical density, maleinized polypropylene, polyethylene-co-vinyl acetate, morphology, optic microscopy, DSC, physical and mechanical properties, crystallization

Structure and Properties of the Oligodienurethanes Modified by Fluorine Containing Chain Branching Agents

Novakov I.A. (Academician, Prof., D. Sc. [Chem.], President, Chief of Chair),

Medvedev V.P. (Ph. D. [Techn.], Assist. Prof.), Vantsev M.A. (D. Sc. [Techn.], Chief of Chair),

Gugina S. Yu. (Postgrad. Stud.), Frolova B.I. (Ph. D. [Techn.], Lead. Eng.)

With the aim of compatibility improving of urethane-forming components the possibility of using fluorine containing modifying components was investigated. There were two types of fluorine containing glycerol esters of trihydroperfluoroheptanol (FOM-1 and FOM-2), that were using as chain branching agents because of presence of two and three reactive hydroxyl groups. As urethane-forming components were used low-molecular butadiene rubber Krasol LBH-3000, polymethylenepolyphenylisocyanate, glycerol and dibutyldilaurynate tin. Structure parameters of polymer network were studied by method of the Sol-gel analysis, which means 24 hours extraction of soluble part of material in Soxhlet’s apparatus. The compatibility of components was assessed by difference of solubility parameters δ. The dependence between the effective viscosity and the rate of deformation was investigated for systems containing and non-containing FOM. Physical and mechanical properties of elastomers (tensile strength, relative elongation, tear resistance) were measured by tensile-testing machines Zwick and RMI-60. The resistance to thermal-oxidative (72h at T = 70 ºC) and hydrolytic (72h at T = 80 ºC) aging was evaluated by the change of these parameters. The surface morphology of elastomers was studied by atomic force scanning microscope SolverPRO and by scanning electron microscope Versa 3D DualBeam. Improvement of the compatibility of urethane-forming components under addition of FOM-1 and FOM-2 to the blend of diene oligomer with glycerol was shown. It allows to increase the degree of cross-linking and improves the complex of mechanical properties of oligourethanes. The introduction of polyfluoromethylene pendants into the structure of dienurethane elastomer increases the interaction intensity between macromolecules due to additional associative interactions with fluoromethylene fragments. As a result both heat and hydrolytic aging resistance are enhanced.

Keywords: oligodienurethane compositions; Krasol LBH-3000, glycerol, fluorine containing chain branching agents, compatibility of urethane-forming components, solubility parameters, Sol-gel analysis, surface morphology, viscosity, physical and mechanical properties, resistance to thermal-oxidative and hydrolytic aging

Investigation of the Influence of Methyl Cellulose and Sodium Polyacrylate on Hydrosorption Properties

of Polychloroprene Based Technical Rubbers

Ivanova A.V. (Postgrad. Stud.), Ushmarin N.F. (Ph. D. [Techn.], Deputy Chief of Production), Egorov E.N. (Ph. D. [Chem.], Senior Lecturer),

Sandalov S.I. (Ph. D. [Techn.], Chief of Production), Kol’tsov N.I. (Prof., D. Sc. [Chem.], Chief of chair)

The influence of hydrophilic additives methylcellulose MS-2000 and sodium polyacrylate on the properties of the rubber based on neoprene W has been studied. Two studies were used for preparation of rubber mixtures: at the first one hydrophilic additives introduced in rubber, at the second one the other ingredients added. Vulcanization at 150 °C during 30 min was in use. Viscosity (M) was measured by viscometer MVR 3000 Basic («Mon Tech»), vulcanization parameters (including vulcanization rate υ) were measured by reometer MDR 3000 Basic («Mon Tech») at 170 °С according to ASTM D2084-79. The data obtained show that the combined use of sodium polyacrylate and methylcellulose results in the synergistic decrease of both M and rate of vulcanization of rubber mixtures. Vulcanizate, containing both hydrophilic additives, has the best hydro-sorption properties and has satisfactory physico-mechanical properties (conditional strength at tensile, elongation at break, hardness and tear resistance). The values of these properties and their changes under the influence of distilled water (70 ° C, 24 h) satisfy the requirements for water-swelling rubber sealing elements.

Key words: rubber, neoprene W, methylcellulose, sodium polyacrylate, plasto-elastic and rheometric properties, physical and mechanical properties, hydrosorption, synergism, water-swellable sealing elements

Morphology Development in Unfilled BNR Vulcanizates during Mechanical «Plasticzisation»

Baranets I.V. (Ph. D [Tecn.], Lead. Res.),

Kurland S.K. (Prof., D. Sc. [Tech.], Scientific Consultant),

Suzdaltseva E.S. (Postgrad. St., Res.)

Peculiarities of morphology transformation in unfilled BNR-based vulcanizates under their treatment at a thin nip of the mills, followed by thermal re-curing with no more components added have been studied. Analytical complex of optical microscope Leica DM-2500, high resolution camera Leica DFC-420C and special computer was in use. Effect of the milling time within 0–40 min on morphology parameters and thin structure of plasticized pieces was determined. Mechanisms of structure formation and degradation of elastomeric networks in the course of plasticizing have been analyzed. The formation of addition 3d network in «secondary» vulcanizates and increase of the intensity of this process in the course of plasticizing have been found. As a result the level of mechanical properties might become higher than that of initial vulcanizates. However increase of composition nonhomogeneity might result in decrease of oil-resistance.

Key words: BNR, unfilled vulcanizates, degradation, structure formation, morphology, thin structure, mechanical properties

Elastomer Thermal Protective Materials Containing Microspheres Modified by Elementоorganic Modifier

Kablov V.F. (Prof., D. Sc. [Techn.]), Novopoltseva O.M. (Prof., D. Sc. [Techn.], Deputy Chief of Chair),

Keybal N.A. (Prof., D. Sc. [Techn.], Chief of Chair), Kochetkov V.G. (Assistant), Pudovkin V.V. (Eng.)

The effect of the introduction of aluminosilicate microspheres (MSF) on thermal and fireproof properties of elastomer materials based on ethylene-propylene rubber was studied. MSF was treated with an elementоorganic modifier – phosphor- bore- nitrogen-containing olygomer (PO), known as combustion inhibitor. The value of the Payne effect and physical and mechanical properties were also measured. There are 30 phr of filler (BS-120), sulfur vulcanizing system and 1 phr of MSF in composition of rubber studied. The best ratio MSF:PO is 1:3. The treatment by UHF was also in use. The increase of diameter MSF and the change of atomic composition of MSF surface as a result of treatment by modifier were studied by electron microscope «Versa 3D». Some increase of Payne effect and rubber-filler interaction, decrease of density, and increase of green strength as a result of MSF modification were shown. The rate of linear combustion (according wit GOST 28157– 89) is 10 % less in comparison with specimen without MSF; modification of MSF result in addition 5 % decrease. The time of heating to 100 оС of unheated surface under heating of the other surface to 2000 оС, increases on 50–60 % and 11–19 % correspondingly. The strength of formed coke increases on 4–7 %. The use of PO provides the possibility to increase the adhesion of coating to the substrate. Scheme of interaction between MSF and PO is presented.

Key words: elastomer material based on ethylene-propylene rubber, thermal and fireproof properties, coatings, filler, microspheres, modifier, Payne effect, mechanical properties, green strength, adhesion

Rubberized Fabric for Soft Tanks of Fuel Storage

Rybakov Yu.N. (Assist. Prof., Ph. D. [Techn.], Head of Dep.),

Dedov A.V. (D. Sc. [Techn.]), Plokhoy D.S. (Jun. Res.), Kolotilin D.V. (Res.)

Extraction kinetics of dibutyl sebacate by different brands of automobile fuel from a rubberized fabric based on the blend of two types of BNR (SKN-26M and SKN-40M) was studied. Kinetics was determined in accordance with GOST 9.030-74 by the change of weight of a sample after endurance in fuel at 50 °C and drying. The change of fuel quality after contact with fabric was registered on the change of content of the pitches actually existing in fuel in accordance with GOST 1567-97 (ISO 6246-95) and its acidities in accordance with GOST 5985-79 before and after the contact with a rubberized cloth. Two stages of extraction process were shown. The time of the first one doesn't depend on a fuel type in experimental conditions; its speed is much higher, than that of the second one. The ratio of speeds and a share of the extracted fuel at the first and second stages depend on a fuel type. It is possible to conclude that the excess amounts of the extracted substances are impurities including the residual monomer or its derivatives and substances used at rubber synthesis. The mechanism of a counter flow of extragent in rubber and its dependence on gasoline brand is presented. It is based on taking into account diffusion processes in system.

Key words: rubberized fabric, BNR, DBC, automobile fuel, diffusion processes

The Principles of Parametric Definition of Rubber Taking in the Account its Functional Possibilities

Kablov V.F. (Prof., D. Sc. [Techn.]),

Gamlitskiy Yu.A.( Assist. Prof., Ph. D. [Phys.-Mat.], Chief Res.)

Review devoted to description of existing ways of parametric definition of rubber as composite material, including author’s ones. The main features of nonlinear mechanical behavior of elastomer composites are presented.

Key words: rubber, high elasticity, classification, mechanical properties, composite material, system approach

The Hostage of the Demand

Post-release on 9th International Conference «Polymers in automobile manufacturing 2017», organized by INVENTRA (19.05.17, St. Petersburg).

Key words: automobile manufacturing, profitableness, automobile components, net cost, quality level, international standard, certification, omologation, supplier chains, composition materials, innovations, glass microspheres, hermetic mastics, fluorine-elastomers

ROSMOLD/ROSPLAST 2017

Post-Release

Post-Release on two united Exhibitions: 12-th International Exhibition «ROSMOLD: Moulds, Compression Moulds, Stamps» and 8-th International Exhibition «ROSPLAST: Plastics, Equipment, Goods» as well as International Conference «Ideas, Design, Goods» (20–22.06.17, Crocus Expo, Moscow)

Key words: moulds, compression moulds, 3D-Equipment, 3D-Print, design, plastic processing, goods

VMI Opens New Manufacturing Facility in Poland

Press-Release

Press-Release of VMI on opening 05.09.17 a new manufacturing facility in Lezno (Poland). On 8 hectare of land is plotted 13,500 m2 of manufacturing floor space, warehousing and offices.

Keywords: manufacturing floor space, warehousing, offices, delivery time, competition, innovative solutions, Lean principles