Abstracts

№3, 2018

Comparative Evaluation of Characteristics of Commercial Polybutadienes Produced on Different Catalytic Systems

Galimova E.M. (Ph.D. [Techn.], Lead. Spec.), Sakhabutdinov A.G. (Ph.D. [Chem.], Chief Process Engineer), Korobeinikova O.A. (Process Engineer)

Dynamic properties of polybutadienes (PB) produced on neodymium (I), cobalt (II), nickel (III), and titanium (IV) catalytic systems have been studied. Mooney viscosity of all samples was ~ 45. «RPA 2000» («Alpha Technologies») was in use for measurements of complex shear modulus G", its real (G') and imaginary (G") parts, as well as tgδ and dynamic viscosity (η*) with its real part (η') at temperatures (T) 40–100 °С, frequency (ω) from 0,033 to 20 Hz and amplitudes (εа) from 10 to 1200 %. Results are compared with MMR, measured at T = 100 °С by liquid chromatography «Alliance GPCV-2000» («Waters») and viscosity (η1) and Mooney relaxation measured by viscometer «MV2000» («Alpha Technologies»). Invariant curves (dependencies of lgG', lgG" and lg(η'/η0) on (ωη0), η0 is initial dynamic viscosity) were obtained as the result of handling of dynamic properties data. The best coincidence of invariant curves founded for PB I and IV. PB II and III are of wider MMR and higher molecular branching (MB). Difference of tgδ (Δtgδ) at high and low ω (20 and 0,083Hz, measured at Т = 100 ºС, and εа = 20 %) are also good characteristics for MMR and MB. Dependencies of G" and tgδ on εа for all PB studied are presented. Under εа from 10 to 100 % this dependence is weak; under higher εа it is stronger. The possibility is open to use the obtained results as methods of express-control of the MMR and MB levels of PB and indirect evaluation of some processing properties of PB rubbers and PB based rubber compounds.

Key words: butadiene rubber, dynamic shear modulus, tgδ, amplitude deformation, dynamic viscosity, molecular weight, molecular-weight distribution, long-chain branching, processing properties

The Synthesis of Mixed Alcoholates of Alkali and Alkaline-Earth Metals

Glukhovskoy V.S. (Prof., D. Sc. [Techn.], Chief of Lab.), Blinov E.V. (Director), Berdnikov V.V. (Res.), Zemsky D.N. (Ph.D. [Chem.], Chief of Chair)

Methods of obtaining of alcoholate (A) of alkaline and alkaline-earth metals which are effective modifiers of lithium-organic initiator allowing to regulate structure and molecular characteristics of polymers at anionic polymerization were described. One of the fields of the use of A is modification of n-butyllithium at anyone polymerization of dienes, in particular, SBR (DSSK). Two methods of synthesis of alkaline and alkaline-earth metals mixed A well-soluble in hydrocarbon solvents, were under consideration. The first one is based on the direct interaction of alcohol of boiling-point higher than 150 0С with alkaline and alkaline-earth metals. This single-stage method is based on simultaneous charging of Na or Li and Mg or Ca; Mg and Ca are in use as a powder, Na and Li as a block. Reaction is in N and H environment. The first step is addition of toluene to metals and heating to 105–110 0С, the next step is addition of alcohols. Lapramol-294 and tetrahydrofurfuryl alcohols are in use. Exclusion of Na by Mg and Ca from A was detected. The second method is based on reaction of the metals hydroxides with alcohols and then interaction of alcohol-alcoholates mixture with calcium. The mixed A containing alcohol radicals with secondary and tertiary N were obtained.

Key words: SBR, n-butyllithium, alcoholates, alkaline and alkaline-earth metals, N,N,N’,N’-tetra(oxypropyl)ethylenediamine (Lapramol-294), tetrahydrofurfuryl alcohol, toluene

Search of Promising Chain Transfer Agents for Production of Butadiene-Styrene Rubbers by Continuous Polymerization

Rumyantseva A.L. (Sen. Res.), Polukhin E.L. (Ph.D. [Chem.], Sen. Res.), Popova S.B. (Sen. Res.), Tkachev A.V. (Ph.D. [Techn.], Head of Res. center) , Rakhmatullin A.I. (Ph.D. [Techn.], expert)

The influence of secondary aliphatic amines and substituted aromatic hydrocarbons was studied to reduce degree of gel formation on mixing device of reactor in the processes of continuous (co)polymerization of styrene with butadiene. For evaluation of efficiency of chain transfer reagents for reducing the probability of reactors clogging the indirect methods were used: kinetic measurements of polymerization process, changes in molecular-mass characteristics of polymer product with time of polymerization. The results demonstrated that aliphatic amines are not efficient agents of chain transfer. It was shown that the use of solvent which contains 10 % (wt) toluene leads to reduction of number-average molecular weight and Mooney viscosity of polymerzation products. This indicate that toluene potentially can be served as efficient agent of chain transfer and thus the probability of reactor surfaces clogging can be decreased in the presence of toluene.

Key words: styrene-butadiene copolymerization, anionic polymerization, continuous polymerization, jellying, high molecular weight fraction

Silanization of Tread Rubber Compound of Car Tires.

Part 1. Kinetics Features of the Silanization Process.

Dorozhkin V.P. (Prof., D.Sc. [Chem.]), Salaev M.V. (Postgrad. Stud.), Mokhnatkin A.M. (Ph.D. [Techn.], Head of Dep.), Mokhnatkina E.G. (Ph.D. [Techn.], Assist. Prof.), Makhotin A.A. (Director), Prinada A.L. (Director)

Dependence of dynamic shear modulus (storage G′ and loss G′′) of tread rubber compound (RC) of car tires on temperature (T) and silanization time (t) has been measured. RC based on blend of solution SBR and stereoregular butadiene rubber contains silica Zeosil 1165 МР and different amount (v) of silanization agent TESPT (from 4 to16 mass. part on 100 mass. part Zeosil 1165 МР). Silanization was conducted in rubber mixer (company «HP GROUP») at T from 115 to 165 ºС and t from 35 to 235s. G′ and G′‘ were measured by RPA-2000 (Alfa Technologes) at frequency ω =1Hz, temperature 100 ºС and amplitudes 0,7 и 279 %; dynamic viscosity was calculated as ηдин = G′′/ω. Payne effect was in use as a measure of silanization. Experimental design was applied for determining the silanization kinetics. The changes of kinetics under different conditions of Т, t and v are analyzed and some assumptions on mechanism of silanization are presented. Comparison of literature and obtained data is under discussion. The conclusion on the inadequacy of the first-order equation usually used for description of silanization kinetics is maid.

Key words: tread rubber compound, silica, silanization, kinetics, dynamic shear modulus, Payne effect

Silanization of Tread Rubber Compound of Car Tires.

Part 2. Description of Kinetics of the Silanization Process.

Dorozhkin V.P. (Prof., D.Sc. [Chem.]), Salaev M.V. (Postgrad. Stud.),

Mokhnatkin A.M. (Ph.D. [Techn.], Head of Dep.),

Mokhnatkina E.G. (Ph.D. [Techn.], Assist. Prof.),

Makhotin A.A. (Director), Prinada A.L. (Director)

Description of data on kinetics of the silanization process of Part 1 is presented. It opens the possibility to improve the insight into the mechanism of this process. The exponential equation of arbitrary order is suggested. Both positive and negative values for equation order n and effective activation energy Еeff are accepted. The dependence of n and Еeff obtained on condition of silanization is shown. The new method of calculation of kinetic data is proposed based on the calculation of the rate of change of storage module G' in a narrow range of shear strain and a short interval of time. Two separate processes of sharply different kinetic characteristics are possible to allocate in complex silanization process. The fraction of each process is dependent on silanization conditions. For example, the highest degree of silanization under small content of silanization agent is possible if the temperature is higher than 140 ºС. The validity of generally accepted model based on first-order equation is sown only in a narrow diapason of temperature, time and silanization agent. The best condition of silanization of tire tread rubbers containing silica is recommended.

Key words: tire tread rubber compound, silica, silanization, silanization agent, silanization kinetics, equation order, activation energy

The Influence of Oxygen-Containing Groups on Nanostructure of Carbon Black and the Reduction of Rubber Gas Permeability

Nagornaya M.N. (Eng.-Techn.), Razdjakonova G.I. (Ph.D.[Chem.], Sen. Res., Assist. Prof.),

Khodakova S.J. (Ph.D. [Techn.], Head of Lab.), Rumyantsev P.A. (MS Student)

The influence of oxygen-containing groups of carbon black (CB) on the nanostructure of carbon layer and CB nanostructure on the rate of permeability to gas (GTR) throw the filled rubber based on butyl rubber have been studied. Two samples of furnace CB: N326 and N121 of different porosity were in use. Both original and oxidized by active oxygen CB were under investigation. Physical and mechanical properties of filled rubber were determined. Increase of time of scorching beginning from 13,8 min to 17,3 min and from 10,82 min to 11,17 min, respectively as a result of the change of original N326 and N121 CB on oxidized ones in rubber compounds was revealed. GTR was measured by manometric method (apparatus VAC-V2, «Labchink Instruments», Китай) under room temperature and atmosphere pressure difference to 0,1 MPa according standard China GB 1038. GTR, connected both with gas solution on one side of the sealed medium and diffusion with next evaporation on the other, reduced under the use of oxidized CB’s. The values of energy Ese, calculated by simulation with the use of program Cambridgesoft Chem3D Ultra 14, was adopted as generalized parameter of nanostructure of carbon layers. The reverse linear dependence of GTR on Ese was obtained for rubbers filled with ТУ N326.

Key words: carbon black, functionalization, functional groups, nanostructure butyl rubber, filling, physical and mechanical properties, speed of nitrogen permeability, simulation

Influence of Dithiophosphate Accelerators on Vulcanization and the Properties of Elastomer Materials Based on Butadiene Acrylonitrile Rubbers

Shemyakina L.S .(Lead. Eng.), Shakirzyanova R.R. (MS Student), Kanauzova A.A. (Ph.D. [Chem.], Lead. Res.),

Yulovskaya V.D. (Ph.D. [Chem.], Sen. Res., Assist. Prof., Chief of NICH), Rakhmatulin T.T. (Res.), Reznichenko D.S. (Ph.D. [Techn.], Deputy Director)

The influence of dialkyl dithiophosphate (DTP) accelerators Rhenogran TP-50 (I) and Kvalaks A (II) on the vulcanization process and the properties of vulcanizates based on BNR has been studied and prospect of their application in the development of oil and cold-resistant elastomeric composite materials (EKM) for hoses, seals and other industrial rubber goods determined. It was established that I provides a longer induction period and a lower plateau torque in comparison with II, the vulcanization rate of EKM with different grades of DTP is practically the same and there is no reversion of vulcanization in the case of both DTP. The scorching time of rubber compounds with I is longer than with the Sulphenamide C (SC), and the vulcanization optimum time and the vulcanization rate correspond to those of the SC. However, the value of the maximum torque in EKM with DTP is lower than that with the SC. A synergism in the change of the main vulcanization characteristics of rubber compounds under the coaction of I and SC was established. The maximum deviation from additivity is reached at the same content (0,5 phr) of both I and SC in EKM. The use of I and SC mixture makes it possible to regulate the vulcanization mode (increase the speed and shorten the time for achieving the vulcanization optimum) of the rubber compounds studied without significantly affecting the vulcanizate properties. It has been established that the additional introduction of I as a secondary accelerator into a chamber rubber compound for the inner layer of hoses provides an increase in the relative elongation at break and the oil and petrol resistance of vulcanizates while maintaining their tensile strength. The results obtained show that DTP can be used as a secondary accelerator to intensify the vulcanization process and enhance the properties of EKM based on BNR.

Key words: vulcanization accelerators, BNR, vulcanization characteristics, physical and mechanical properties, oil and petrol resistance

Study on Heterogeneous Structure of Sulfur-Vulcanized Rubbers by AFM

Glebova Yu.A. (Assistant., Ph.D. [Chem.]), Shershnev V.A. (Prof., D.Sc. [Chem.]), Reznichenko S.V. (D.Sc. [Techn.], Head of Chair), Severin N. (Ass. prof., Ph.D.[Phys.-Math.]), Rabe Jü.P.(Prof., Dr.Sc. [Phys.-Math], Head of Department)

The nano- structure of sulfur-vulcanized rubber based on solution SBR (DSSK-2560) have been studied by AFM – Bruker Multimode 8 PeakForce (QNM) и JPK Nanowizard III in Quantitative Imaging (QI). Composition of rubber (phr): SBR–100, sulfenamide-T–1,5, sulfur –1,8, and activator ZnO –3,0 or Schungite – 10. Mathematical data treatment exclude effect of scanning parameters.A higher Young's modulus and lower adhesion of rubber matrix around particles of activator was shown. We attribute this to a higher cross-link density in rubber surrounding the activator particles and connected with adsorption properties of surface of ZnO and Schungite. This data confirm the early proposed theory. The transition regions were revealed of Young's modulus higher then that of matrix on 30–40 %, and lower than that of regions near activator particles on 70 %. Rheological and mechanical properties of rubbers studied were also measured.

Key words: scanning AFM, Nano-mechanical imaging, SBR, sulfur vulcanization, activator, Zinc oxide, Schungite, cross-link distribution, mechanical properties

Silicone Rubbers of Enhanced Thermal and Fire Resistance

Gadelshin R.N. (Ph.D. [Techn.], Res.), Kurbangaleeva A.R. (Ph.D. [Techn.], Assoc. Prof.), Taiorova V.I. (MS Student), Sabirov R.K. (Ph.D. [Chem], Assoc. Prof.), Volfson Sv.I. (Prof., D. Sc. [Techn.], Head of Chair),

Khakimullin Yu.N. (Prof., D. Sc. [Techn.]), Nefedyev E.S. (Prof., D. Sc. [Chem.], Head of Chair)

The possibility to increase the fire resistance of silicone rubbers (by the example of filled rubber based on rubber SKTV-1) through the application with aluminum hydroxide of the better fireproof compounds: organic bentonite (OB) and decabromodiphenyloxide (DBDPO) has been studied. In this case the content of aluminum hydroxide (AH) can be decreased. Thermo resistance was examined by synchronous thermoanalyser STA 409 PC Luxx from Netzsch, Germany (heating rate 10 оС/min, temperature range 25–600 °С, air medium) and by TGA SDT Q 600 from TA Instruments, USA (heating rate 10 оС/min, temperature range 22–650 °С, air medium, rate of air flow 100 ml/min). Mass loss of initial filled rubber at 260–350 °С was 12 %. Increase of OB content from 2,5 to 5,0 phr results in increase of destruction temperature from 440 to 500 ºС. Specimens in form similar to tension specimens of (1±0,2) mm in thickness were in use for estimation of fire resistance. Flame acted on their narrow part at a right angle in 5–15 s; jet of «MEGA 1» type of piezoignition Kovica KS-1005 (Korea) was exploited. The possibility to decrease the AH content to 50 phr at the same level of thermo- and fire resistance and improvement of standard strength properties under the use of 15 phr DBDPO was established. Improvement of both thermo- and fire resistance of silicone rubbers by addition of OB was shown. They surpasses the initial ones, containing 120 phr of AH (TREFIL744-300VST) in fire resistance. Rubbers containing both AH and OB are of selfdumping after long action of open flame. This opens the possibility to receive silicone rubbers of the lower combustibility and the same level of strength properties; oxygen index may be as much as 60.

Key words: silicone rubbers, thermoresistance, fire resistance, flame-retardant, aluminum hydroxide, organic bentonite, decabromodiphenyloxide, selfdumping, standard strength properties

Application of Secondary Polymer Materials as Interfacial Combination Agents in Rubber/Fibrous Composites

Pugacheva I.N. (D. Sc. [Techn.], Assist. Prof., Dean), Sedykh V.A. (Ph.D. [Techn.], Assist. Prof.), Nikulin S.S. (Prof., D.Sc. [Techn.])

The possibility of complex processing of secondary polymer materials formed as wastes and by-products at the enterprises of petrochemical and textile industries is under consideration. Additives based on fibrous wastes and oligomers synthesized from the by-products of polybutadiene production, modified with maleic anhydride and the pinane hydroperoxide (Ad) were in use. Aqueous dispersion of Ad were introduced in latexes of emulsion BSR (SKS-30 ARK and SKMS-30 ARK) on the stage of their coagulation The use of 30–70 kg of Ad on the ton of rubber results in increase of yield of rubber crumbs because of decrease of rubber losses in form of fine-dispersed crumbs as well as introduction of Ad components in crumbs composition. It has been shown that the modified oligomers additives are perspective as the agents of interfacial combination (AC) between the rubber matrix and fibrous material; as a result thermo-oxidative aging, as well as tear and repeated stretching resistance increases. Increase of swelling Q of vulcanizates, based on rubbers, containing Ad, has been discovered. Q depends on type of both solvent and fiber in Ad, and decreases if AC is in use.

Key words: wastes, by-products, oligomers, fibers, additives, filling interfacial combination agents, mechanical properties, swelling

VMI EDGIQ

Davidse T. (Sales Manager for VMI Cutter Platform, the Netherlands)

VMI steel belt cutter EDGIQ with MAXX technology is presented. The original EDGIQ launched in 2010 has been transformed at every stage – loading, cutting, splicing, gum strip application and wind-up. Its advantages are shown. VMI vision system and CORTEXX technology provide greater accuracy, more sensitive controls and improves auditability.

Key words: EDGIQ, ergonomics, MAXX technology, higher productivity, disc and bar cutter

Kinetic Parameters of Chlorination of Butyl Rubber by Water Solution of Chlorine

Orlov Yu.N. (Ph.D. [Chem.], Assist. Prof.)

Kinetics of chlorination of butyl rubber in a hydrocarbon medium by an aqueous solution of chlorine has been determined experimentally in a laboratory scale. Chlorination by an aqueous solution of chlorine is a base of process of chlorobutyl rubber production developed by the specialists of Togliattikauchuk LLC. As a result of mathematical processing of the kinetic curves, the form of the kinetic equation and the value of the effective reaction rate constant are presented. The results obtained correlate with the literature data on the chlorination of unsaturated compounds in nonpolar solvents.

Key words: clorination of butyl rubber, chlorobutyl rubber, aqueous chlorine solution, chlorination reaction rate

Reserve but Right

Post-release on the Conference «PVC. Results of the year»

Post-release on the Conference «PVC. Results of the year», organized by INVENTRA (in the CREON group) (01.12.17, Moscow).

Key words: PVC, export, import, import substitution, building, windows profiles, markets, net cost, production quality, stabilizers

The News in the Field of Science, Technology and Production of Rubber and Rubber Materials and Goods 8th RUSSIAN RUBBER CONFERENCE Rubber’2018: Traditions and Innovations. Part I

Reznichenko S.V. (D. Sc. [Techn.], Chief of Chair, Editor in Chief), Morozov Yu.L. (Prof., D. Sc. [Techn.], Deputy Editor, Consultant of Gen. Director), Konikova T.B. ( Executive Director, Project Director–Executive Secretary), Yurchenko A.Yu. (Res.),

Report on 21th International Exhibition «Tire & Rubber-2018» (Moscow, Expocenter, 24 – 27.04.18) and Part I of detail review of papers presented on 8th Russian Rubber Conference «Rubber’2018: Traditions and Innovations» (Moscow, Expocenter, 25 – 26.04.18)

Key words: exhibition, conference, elastomer industry, equipment, processing, tires, technical rubber goods, science, innovations, rubbers, nontraditional sources of raw materials, tire retreading, rubber blends, fillers, adhesives, processing oils, oil resistance, low temperature resistance, modification