Abstracts

№6, 2018

Effect of the Temperature on the Kinetic Parameters of the (Co)Polymerization Process and the Characteristics of the Resulting Copolymer

Gasisov I.G. (Processing Engineer), Trifonova O.M. (Ph. D. [Techn.], Deputy Director), Khusainova G.R. (Chief of Lab.), Akhmeov I.G. (D. Sc. [Chem.], Chief of Lab.)

The process of styrene-butadiene diblock copolymer production in the presence of n-butyl lithium initiating system – a mixture of alkoxides of alkali and alkaline-earth metals – has been studied. The temperature effect on the kinetic parameters of the (co)polymerization process and the characteristics of the resulting copolymer has been examined. Molecular characteristics were determined by chromatograph Alliance GPCV 2000 (company Waters») of refractometer and viscometer detector, microstructure and combined styrene – by IR-spectrometer Perkin Elmer Spectrum GX 100 according ISO 21561/2. Increase of the rate of initial process of both butadiene and styrene polymerization with the temperature is shown.. However, in the case of styrene, the contribution of a change in the copolymerization initiation constant is more significant. The absence of the changes of microstructure of the butadiene part under the change of temperature of (co)polymerization process (in the studied interval) is determined. Decrease of the average molecular weights and increase of copolymer polydispersion under temperature increase are observed.

Key words: block copolymer, anionic polymerization, butadiene, styrene, solution viscosity, copolymerization

Thermo-oxidative Destruction as a Method of Obtaining of Low Molecular Weight Polydiene Polymers

Shehavtsova T.N. (postgraduate student), Shatalov G.V. (Prof., Dr. Sc. [Chem.]),

Shestakov A.S. ( Dr. Sc. [Chem.], Head of Dep.), Papkov V.N. ( Ph.D. [Techn.], Deputy Director)

Process of thermo-oxidative degradation of polybutadiene and polyisoprene (SKD-ND and SKI-3), as well as of SCID-L, SKDI-15 copolymers was studied. The process was carried out in toluene under the action of air oxygen in the presence of adduct of the radical initiator azodiisobutyronitrile (AIBN) with a heterocyclic carbonyl containing compound N-methylpyrrolidone (MPR). The influence of the amount and ratio AIBN/ MPR, temperature T, polymer concentration in solution, rates of moving air (V1) and styring (V2) on process of degradation was shown. There are decrease of Мw and intrinsic viscosity [ŋ] under constant T as a result of increase of AIBN content, as well as under increase of T (from 50 to 85 0С), V1 (from 130 cm3/min), and V2 (to 150–250 об/мин). Presence of peroxid (0,2–0,5 %), carboxil (0,5–1,0 %), and hydroxil (1,5–2,2 %) groups in products of thermo-oxidation was established by IR-spectroscopy. Industrially available method of obtaining of low molecular polymers of oxygen-containing functional groups is proposed. The possibility of reprocessing of substandard rubber and wastes of industrial synthesis is established.

Keywords: thermo-oxidative degradation, polybutadiene, polyisoprene, N-methylpyrrolidone, azoisibutyronitrile, industrial wastes

Low Molecular Weight Copolymers of Ethylene Chlorotrifluoroethylene, Vinylidene Fluoride, and Perfluoropropylvinylether

Rodin V.M. (Ph.D.[Chem.], Sen. Res.), Purtseladze V.I. (Sen. Res.), Emelianov G.A. (D.Sc.[Chem.], Chief of Lab), Lovchikov V.A. (Prof., D.Sc.[Chem.], Chief. Res.)

Low molecular weight copolymers of ethylene (E) and fluorine-containing compounds: chlorotrifluoroethylene (CTFE), vinylidene fluoride (VDF) and perfluoropropylvinylether (PFPVE) were obtained by the solution copolymerization method. 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and mixture of CFC-113 with 1,2-dibromotetrafluoroethane (R-114B2) were used as solvents. Bis(2-trifluoromethyl-3-oxaperfluorohexanoyl)peroxide or tert-butylperoxybenzoate were used as initiators. The molecular weight of the copolymers was determined on a Breeze liquid chromatography system with a Waters 2487 two-wavelength ultraviolet detector. The monomers ratio in the copolymers was determined by the Perkin Elmer Clarus 500 gas chromatograph, and the microstructure was defined by NMR-spectroscopy on a Bruker Spectrospin AM-500 spectrometer (500 MHz for 1H, 470 MHz for 19F). Models of the copolymers macro chain growth are proposed. Model parameters from the combined analysis of 1H and 19F NMR spectra were determined. It is shown that in the case of VDF, the result of copolymerization is low molecular weight products of the low content of fluoromonomer. For copolymers E–CTFE in medium CFC-113 without a chain growth regulator, the product is essentially insoluble high molecular weight polymer. To reduce the molecular weight R-114B2 was in use. The model of E–PFPVE copolymerization with the association of monomer on the active center is in good agreement with experimental data. A mechanism of the participation of the chain growth regulator and, in some cases, the solvent in the process of copolymers microstructure formation is proposed.

Key words: low molecular weight copolymers, ethylene, fluoropolymer, copolymerization, microstructure, NMR spectrum, Markov model of macrochain growth

Morphologies of Two- and Three-Component Compositions on the Base of Polypropylene, Petrolatum and Styrene/Ethylene/Butylene/Styrene Сopolymer

Kilin S.A. (Res., Postgrad. Stud.), Onofriychuk E.D. (Jun. Res., Student), Sirotinkin N.V. (Prof., D.Sc.[Chem.], Dean, Head of Chair),

Baranets I.V. (Ph. D. [Chem.], Lead. Res.), Nadervel T.A. (Ph. D. [Chem.], Sen. Res.), Kurland S.K. (Prof., D. Sc. [Techn.], Consultnt)

The structures of two- and three-component blends based on polypropylene (PP), petrolatum (PL) and styrene/ethylene/butylenes/styrene copolymer (SEBS) have been studied by light microscopy with digital image recording (microscope LEICA DM-2500 from Leica, with Peltier-cooled LEICA DFC 420С and a specialized computer station) and differential scanning calorimetry (DSC 8500 firm Perkin Elmer, heating rate of 10 °C/min in the range from –80 to +200 °C). The influence of PL and PP contents on morphology, processing and mechanical behavior was investigated. The competing interaction of the components has been found resulted, depending on their ratio, in the set of phase structures. Joint analysis of morphology features with processing and mechanical behavior of SEBS has evidenced that high values of stress-strain characteristics are achieved with the formation of single-phase, uniform in volume, composition of network matrix with bead-fibrillar supramolecular structure. The optimal properties of compositions are achieved at a SEBS-PP-PL ratio of 2:1:3. In this case the significant increase of frost resistance (glass transition temperature Тg = –77,0 °С) and the improved processing properties (melting temperature Тm = 144,9 °С) are provided at one-phase structure formation.

Keywords: thermoplastic elastomers, styrene-containing thermoplastic elastomers, styrene/ethylene/butylene/styrene, polypropylene, petrolatum, light microscopy, morphology, differential scanning calorimetry, physical and mechanical properties

Vulcanized Rubber of Improved Low-Temperature Resistance Based on Acrylic Rubber

Perminova N.A. (Chief Process Engineer), Gainullin N.T. (Gen. Director)

Influence of proportion of ethylene-acrylic rubbers Vamac Ultra IP and Vamac Ultra LT of different methacrylate content, organic and mineral fillers, curing agents, as well as plasticizer ester on properties of rubber compounds and vulcanized rubber has been studied. Curing, plasto-elastic, low-temperature, physical and mechanical properties (FMP) as well as aggressive media resistance were tested. FMP, swelling, compression set (CS) and low-temperature brittleness Тb of vulcanizates were measured according to standard testing methods. Vulcanization kinetics was tested by rotorless rheometer MD-3000А (Gotech), rubber mpounds Mooney viscosity at 100 0С by viscometer GT-7080S2 (Gotech). There are Vamac Ultra IP and Vamac Ultra LT in proportion 10/90 phr, carbon black N-550 (75 phr) as reinforcing filler, curing agent Diak №1 (1,5 phr), accelerator DOTG (4 phr), and plasticizer ester (2 phr) in developed receipt. Test results show high level of FMP, Shore A hardness no less then 75, reasonable low-temperature behavior (Тb = –49 °С), and low level of CS without deterioration of the processing properties.

Key words: ethylene acrylic rubbers, rubber compound, reinforcing filler, physical and mechanical properties, hardness Shore A, low temperature resistance, swelling, vulcanization kinetics, viscosity

Silanization of Tread Rubber Compounds of Passenger Tires.

P.7. The Search of Optimal Silanization Conditions

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)

The possibility to find the conditions of silanization corresponding to the optimal complex of properties of the tread rubber compounds and the tread rubbers is studied. Based on the data on the individual desirability indices of each of the properties studied in the previous papers, equations for the dependence of the generalized desirability index D on х1, х2, х3, represented the conditions of silanization, i.e. temperature, silanization time and the dosage of the silanizing agent TESPT, respectively, are obtained. D was determined stepwise, the first step was to find D values for the properties of similar D dependence on the conditions of silanization. Thus, the best complex of mechanical properties is achieved at a minimum temperature (115°C), the lowest silanization time (35 s) and low dosage of TESPT. Under these conditions, D =D1= 0,807. The value of D1= 0,757 has a tread rubber from a rubber compound obtained at a very high temperature (165°C), the maximum silanization time (235 s) and a large dosage of TESPT (16.0 mass phr). To characterize the processes of silanization, the parameter β (the portion of silanization processes resulting in decrease of the storage module G') and the exponent n of the equation describing the kinetic processes of silanization, were in use. The changes in the conditions of silanization provided the optimal characteristics of production of passenger «green» tires are recommended.

Key words: silanization conditions, properties of tread rubbers, desirability indices, optimization

Determination of Glass Transition Temperature of Polydiene Rubbers by DSC: Influence of Calibration.

Makhiyanov N. (Ph.D.[Phys.-Mat.], Deputy Chief of Lab), Temnikova E.V. (Ph. D. [Chem.], Eng.), Khasanov M.N. (Eng.)

Influence of calibration method for determination of glass transition temperature Тg of polydiene rubbers (polyisoprene and polybutadiene) by differential scanning calorimetry (DSC) has been studied. The measurements were carried out by «Netzsch-DSC-204F1-Phoenix» DSC instrument. Isomeric composition of samples determined by high resolution NMR spectroscopy (spectrometer Bruker-Avance-III-HD-700, the Larmor’s frequency for the resonance on the protons was 700 MHz). Comparison of values Тg, received by temperature calibration of DSC instrument with the use of two standard calibration material sets was performed. One of them includes metals of known melting temperatures and another consists of organic materials of low reference temperatures. Advantages and disadvantages of both variants are under discussion. Practical recommendations on the use of calibration methods at the study of isoprene and butadiene industrial rubbers are presented.

Key words: differential scanning calorimetry (DSC), polyisoprene, polybutadiene, temperature calibration of DSC, glass transition temperature

Influence of Composition Factors on the Bound Strength in Elastomeric Systems of Different Polarity

Tret’yakova N.A. (Ph. D. [Techn.], Head of Dep.), Khodakova S.Ya. (Ph. D. [Techn.], Assist. Prof., Chief of Lab.), Abol’skaya I.I. (Process. Eng.), Khorova E.A. (Lead. Process. Eng.)

The results of studying the influence of the type of rubber and the modifying composition on the adhesive strength fa between the components of the rubber-cord composite (RСC) are presented. The RСС consisted of: rubber based on hydrogenated NBR Therban C-3446 (RHNBR) or NBR BNKS-40AMN (RNBR) and cord Arom 75 coated with rubber compositions based on polar and non-polar rubbers. Bonding was carried out using hot-setting glues based on chloroprene rubber capable of interacting with substrates of different polarities. The higher values of fa of RHNBR in comparison with RNBR are shown. This difference is not directly connected with the difference in the nonsaturation of rubbers. Optimization of the dosage of the RU modifier and the polyisocyanate blocked by caprolactam in the formulation of rubbers as well as in composition of the adhesive included in the RCC, allows to receive bipolar connecting of maximum fa values. Receipt formulations providing maximal diffusion of macromolecules or their segments and synchronization of vulcanization rates of rubbers in RCC are shown to contribute to an increase in fa under the use of adhesion modifiers.

Key words: BNR, HBNR, rubber-cord composites, bond strength, adhesion modifiers

On Base of Data «Moulds» (Short Communication)

Drabkin S.S.

Information on base of data «Moulds» developed by author is presented. There are main and auxiliary tables in the base. The brief content of both types of tables is described. Advantages of Microsoft Access 2010 at development of bases of data are under consideration.

Key words: base of data, moulds, standards, Microsoft Access 2010

Elastomeric Sealing Materials for Use in Cold Climates of Russia

Sokolova M.D. (D.Sc.[Chem.], Acting Director), Shadrinov N.V. (Ph. D. [Techn.], Sen. Res.), Davydova M.L. (Ph. D. [Techn.], Sen. Res.), Khaldeeva A.R. (Postgrad. Stud.), Pavlova V.V. (Postgrad. Stud.)

Review devoted to consideration of data, including patent information, on composition of elastomeric sealing materials of improved low temperature resistance.

Key words: low temperature resistance, rubber technical products, seals, safety and durability, cost, rubbers, modification, nanofillers, glass transition temperature, brittleness, compression set

Scientific-Practice Conference «Petrochemical Industry in Tatarstan:

Science, Innovations, Production», Devoted to 60th Anniversary of PJSC «Kazanorgsynthesis»

Akhsanova O.L. (Ph. D. [Chem.], Lead. Processing Engineer), Trifonova O.M. (Ph. D. [Techn.], Deputy Director)

Review of papers presented at Conference «Petrochemical Industry in Tatarstan: Science, Innovations, Production» devoted to 60th anniversary of PJSC «Kazanorgsynthesis», organized by PJSC «Nizhnekamskneftekhim», and PJSC «Kazanorgsynthesis» (Kazan, 05.09.18).

Key words: conference, petrochemistry, innovation, rubber, butyl rubber, Nd-PBR, Li-PBR, BSR (DSSK), PI (SKI-3), modification, polyethylene, polypropylene

Summary of International Exhibition «Chemistry-2018»

Post-Release on 21 International Exhibition «Chemistry-2018». 250 companies from 19 countries and more than 9000 specialists tacked part in the work of Exhibition. VI Moscow International Chemical Forum was the center of the busy business program of Exhibition. (29.10–01.11.18, Expocenter, Moscow).

Key words: exhibition, row materials, chemical machine building, innovations, small business, low-tonnage chemistry, safety of chemical products, «Industry 4.0», digital technologies, Startup Chemzone