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¹6, 2017

Nizhnekamskneftekhim: Anniversary of the Industry's Flagship

Review fifty years of history, present day and development outlook of PJSC «Nizhnekamskneftekhim» – one of the flagships of the industry for the polymer and monomer production .

Êåó words: PJSC «Nizhnekamskneftekhim», history, polymer production, monomer production

The Main Steps Development of Production of Isoprene Rubber from Isobutylene and Formaldehyde

Dykman A.S. (D. Sc. [Techn.], General Director, Head of Lab.),

Sharifullin I.G. (Deputy General Director, Chief Engineer)

The main steps in the development of the method of production of isoprene and synthetic isoprene rubber (SKI) from isobutylene and formaldehyde are elucidated. The first time these raw materials were used for isoprene production in Soviet Union on Kuibyshev and Volzhsky Synthetic Rubber Plants (1964-65), and then on PJSC «Nizhnekamskneftekhim» (1981) and Chaikovsky Synthetic Rubber Plant (1984). Processing involves synthesis of 4,4-dimethyl-1,3-dioxane (DMD) by reaction of isobutylene with formaldehyde and following vapour-phase cleavage of DMD to isoprene («dioxane» process). A new liquid-phase processing method of isoprene production was developed in SPS «Eurochim» in 90s. This process includes three steps: synthesis of trimethyl alcohol (TMA) by hydration of isobutylene on cationites; synthesis of DMD followed by liquid-phase decomposition to isoprene in presence of TMA; decomposition of light fraction of high boiling by-products and pyrans. «Dioxane» process was stopped on PJSC «Nizhnekamskneftekhim» in 2006 and processing of isoprene production was changed to liquid-phase one. It permits to improve the production characteristics and increase SKI production. Present time production of isoprene on PJSC «Nizhnekamskneftekhim» using the new processing is 200 000 ton annually, its increase in 2018 is outlined to be 300 000 ton annually.

Key words: isoprene, monomer, isobutylene, formaldehyde, «dioxane method», isoprene rubber

Butyl Rubber: Development, Present, Future

Sofronova O.V. (Ph. D. [Chem.], Deputy Head of Lab. R&D Center), Markina E.A. (Ph. D. [Chem.], Lead ProcessEngineer R&D Center)

Fazilova D.R (Ph. D. [Chem.], Head of Lab. R&D Center), Sakhabutdinov A.G. (Ph. D. [Chem.], Chief Process Engineer)

Aglyamov I.A. (Director of Butyl Rubber Plant),

Khabibullin R.Kh. (Chief Engineer of Butyl Rubber Plant)

Review of the current state of butyl and halobutyl rubbers (IIR and HIIR) production in the world and in. The main ways of improvement of the processes of preparing IIR and HIIR (both in world companies ExxonMobil and Lanxess as well as in PJSC «Nizhnekamskneftekhim») are to increase the activity of catalytic systems used, lower their costs, decrease the consumption of energy resources, increase the efficiency of the facility while simultaneously improve the quality of the end product, and reduce the negative impact on environment. Specific features of production and quality of IIR and HIIR of PJSC «Nizhnekamskneftekhim» are under consideration. The role of raw products is shown; low polydispersity and gas permeability provided the quality of IIR and HIIR, resulting in the same level of quality, in some cases even higher, than that of their foreign analogs.

Key words: butyl rubber, halobutyl rubbers, cationic polymerization, polydispersity, gas permeability

Synthetic Rubbers of PJSC «Nizhnekamskneftekhim» for the Production of Styrene Plastics

Tkacheva E.N. (Lead. Process Engineer R&D Department),

Akhmetov I.G. (D. Sc. [Chem.], Head of Lab. R&D Department),

Trifonova O.M. (Ph. D.[Techn.], Deputy Director of R&D Department)

The data illustrated the experience of PJSC «Nizhnekamskneftekhim» in the development of the processing of butadiene and styrene-butadiene rubbers for the production of styrene plastics are presented. In addition to the classical parameters, a whole set of specific requirements the new rubbers have to meet is established. There are: low gel content, specified dynamic viscosity of rubber solution in toluene, low color and absence of oligomers. Processing developed by specialists of R&D Center of PJSC «Nizhnekamskneftekhim» jointly with scientists from Voronezh Branch of FSUE NIISK enable the successful establishment of the production of the required rubbers. Since 2008, imported elastomers were fully replaced by butadiene rubbers under the name SKD-L in the production of high-impact polystyrene; since 2013, styrene-butadiene block copolymers are used in the production of ABS plastics. The high quality of rubbers allows them to be exported to the leading manufacturers of styrene plastics.

Key words: polybutadiene, styrene-butadiene block copolymer, molecular weight characteristics, impact-resistant polystyrene, ABS plastic, physical and mechanical properties, chemical resistance, importsubstitution

The Influence of Temperature on 1,3-Butadiene and Styrene Copolymerization Induced by Multicomponent Initiation System

Vagizov A.M. (Ph. D. [Chem.], Head of Lab. R&D Department), Khusainova G.R. (Process Engineer R&D Department),

Akhmetov I.G. (D. Sc. [Chem.], Head of Lab. R&D Department), Sakhabutdinov A.G. ( Ph. D. [Chem.], Chief Process Engineer)

The influence of temperature from 30 to 70 oC on the 1,3-butadiene and styrene copolymerization process in hexane solvent was studied. n-butyllithium, mixture of amine-containing alkali with alkaline-earth metal alcoholates, and 2,2’-ditetrahydrofurylpropane as initiation system were in use. Characteristics of SSBR synthesized samples were also determined. Introducing of amine-containing alkali and alkaline-earth metal alcoholates and 2,2’-ditetrahydrofurylpropane increases the activity of initiation system and the initial rate of copolymerization process. The rise in the copolymerization temperature from 30 to 70° C is accompanied by a multiple increase in the values of the kinetic constants. The decrease of the process temperature is followed by the growth of 1,2- units content in the butadiene part of the copolymer.

Key words: anionic polymerization, solution SBR, random copolymer, vinyl units, process temperature, process rate

The Properties of TDAE and MES Type Oil-Extended Solution Styrene-Butadiene Rubber

Plekhanova I.S. (Lead. Process Engineer, R&D Center), Borisenko V.N. (Head of Lab., R&D Center),

Akhmetov I.G. (D. Sc. [Chem.], Head of Lab., R&D Center)

The effect of the type and dosage of plasticizing oils with low polycyclic aromatic hydrocarbon (PAH) content on the properties of solution styrene-butadiene rubber (SSBR), rubber compounds and vulcanizates was investigated. Oil-extended SSBR with oil samples of TDAE and MES types of trade marks «Norman-346» and «Norman-132» respectively, in the dosage range from 12,0 to 25,0 % by weight were studied. Microstructure of SSBR was studied by IR-Spectrometer «Spectrum 100» («Perkin Elmer»), glass transition temperature (Òg) – by DSC «204 F 1 – Phoenix» («Netzsch») at heating rate, 5 °Ñ/min, vulcanizing characteristics – by MDR 2000, tgδ at 60 °Ñ (tgδ60) – by RPA 2000 («Alfa Technologies»). The use of tested oils results in reducing of power consumption at preparing of rubber compositions as well as change of rheometric parameters in comparison with the control samples without oil. Advantages of oil-extended rubbers include reduction of hysteresis losses, hardness, and rolling resistance (determining according tgδ60 value). As the oil content increases, the elastic properties are improved and heat formation of rubber under dynamic compression decreases. The higher plasticizing ability of oil «Norman-132», lower Òg of SSBR was established, however at dosage higher than 15 % by weight his compatibility with SSBR became lower. Better compatibility with rubber at the content of more than 15 % by weight, and smaller migration of oil from vulcanizates as an advantage of «Norman-346» are shown.

Key words Solution styrene-butadiene rubber, plastisizing oils, MES, TDAE, microstructure, Òñ, tgδ at 60 °Ñ, physical-mechanical properties of rubbers, hardness, rebound elasticity, Goodrich heat build-up, rolling resistance, migration activity

Polymers Based on Anionic Macroinitiators of Anion Nature and Isocyanates

Sharifullin R.R. (Ph. D. [Techn.], Head of Lab. R&D Center),

Davletbaev R.S. (Prof., D. Sc. [Chem.]),

Atlaskin A.A. (Postgrad. Student),

Dzhabbarov I.M. (Postgrad. Student),

Gumerov A.M.(Prof., D. Sc. [Chem.]),

Davletbaeva I.M. (Prof., D. Sc. [Chem.])

The methods of controlling the initiating ability of terminal potassium alcoholate groups of macroinitiators (MI) which are oligomeric polyoxyethylene glycols and block copolymers of propylene oxide and ethylene oxide are under considation. Physical-chemical as well as physical and mechanical properties of polymer film materials prepared based on MI and aromatic isocyanate are investigated. It is shown that the effect of transition metal ions on anion-active potassium alcoholate groups leads to the significant changes in kinetic parameters, mechanism of MI interaction with isocyanates, and, accordingly, mechanical properties of coatings produced. The production of multiblock copolymers of the properties of highly selective gas separation membranes appeared to be possible with the use of potassium-substituted block copolymers of propylene oxide and ethylene oxide as macroinitiators.

Key words: macroinitiators, oligomeric polyoxyethylene glycols, block copolymers of propylene oxide and ethylene oxide, aromatic isocyanates, modification, polymer coatings, gas separation, membranes

Precision of Determination of Glass-Transition Temperature of Polydiene Rubbers by DSC

Makhiyanov N. ( Ph. D. [Phys.-Mat.], Deputy Head of Lab.),

Temnikova E.V. ( Ph. D. [Chem.], Eng.), Khasanov M.N. (Eng.)

Precision of determination of glass transition temperature (Tg) by differential scanning calorimetry (DSC) for industrial polydiene rubbers was studied under conditions of repeatability and intralaboratory reproducibility. Effect of ways of preliminary specimen treatment as well as thermogram treatment on precision of analysis is established. Possible causes of scatter of Tg data taking into account potentials of modern DSC were under discussion. Possible random errors of Tg under heating rate of 5˚Ñ/min at the level of 0,1˚Ñ for polyisoprene and of 0,2˚Ñ for cis-polybutadiene were shown.

Key words: polybutadiene, polyisoprene, glass transition temperature, differential scanning calorimetry, precision

Cis-1,4-Polybutadiene Modification by Maleic Anhydride and α-Olefin Copolymer

Kubanov K.M. (Deputy Head of Division),

Fazilova D.R. (Ph. D. [Chem.], Head of Lab. R&D Center),

Akhmetov I.G. (D. Sc. [Chem.], Head of Lab. R&D Center),

Nifant'ev I.E. (D. Sc. [Chem.], Head of Lab. RAN),

Tavtorkin A.N. (Ph. D. [Chem.], Sen. Res. RAN)

Process principles of modification of cis-1,4-Polybutadiene (PB) by copolymer of maleic anhydride and α-olefins were studied. PB was synthesized in laboratory reactor, molecular parameters PB were measured by liquid chromatograph Waters Alliance GPCV-2000. Efficiency of the use of hexadecane-1 in copolymer is shown. Kinetic parameters of polymerization and properties of PB in dependence of composition of catalytic system and temperature were measured. MM PB increase exponentially in temperature range from 50 to 75 îÑ, at Ò < 30 îÑ the data of dMM/dt are lower than expected; possible, it is the result of the lowering of diffusion rate, connected with the increase of the viscosity of the system. Mechanism of modification reaction was proposed. Optimum conditions of modification process were determined. Industrial tests conducted and full-scale trial results were under discussion. Dynamic properties of tire rubbers and tires containing synthesized PB are on the level of that of better foreign examples.

Key words: cis-1,4-polybutadiene, modification, maleic anhydrite, α-olefins, catalytic system, dynamic properties

Modification of Filled HDPE with Synthetic Elastomers.

Influence on Cold-Resistance

Shaidullin N.M. (Processing Engineer R&D Center), Yakovlev V.B. (Ph. D. [Chem.], Techn. Director),

Salakhov I.I. (Ph. D. [Techn.], Head of Lab. R&D Center)

The influence of modifiers (M) based on elastomers (E) on cold-resistance and other properties of filled by carbon black high-density polyethylene (PE) was investigated. In compositions E were introduced in form of concentrates based on low-density PE. E in the use are: EPDM, IIR, SBR, copolymer of ethylene with propylene (SPE) and butene (SEB). E viscosity was measured by «MV 2000» ALFA TECHNOLOGEST, heat properties of E and concentrates by DSC «DSC-204F1 Phoenix» Netzsch under heat rate 20 °Ñ/min. Thermo-oxidative stability of compositions was determined by STA 409 PS Netzsch at 200 °Ñ and oxygen flow of 100 ml/min. MM characteristics were studied by Gel-Permitted Chromatograph «Viskotec HT GPC 350» Malvern. Manifold increase of elongation at break (εb) at 45 °Ñ. Ì based on SEB is the most effective, its use provide the highest results of εð at negative temperatures, and also the better thermal oxidative stability as compared with the other M based on IIR-1675, EPDM-50, SSBR-2012, and ÑÐE. According the data of εð at minus 45 oC, studied E can be aligned in the row: EPDM-50>IIR-1675>SSBR-2012. The high resistance of modified compositions to thermal oxidative breakdown and improved resistance to thermal aging was established. The aging under 120 °Ñ for 500 h in air and under 95–100 oC for 30 days in water withstand the specified conditions. The best resistance to thermal aging was shown by compositions with M containing SEB and ÑÐE. This is appeared to be connected with unsaturation of other studied E.

Key words: high-density polyethylene, modification, elastomers, low-density polyethylene, cold-resistance, strength properties, heat aging, oxidative breakdown, glass transition temperature, crystallization

Development of Raw Materials Base for Catalytic Processes of Production of Synthetic Oils Based on Higher ɑ-Olefins

Zaripov I.R. (Processing Engineer R&D Center),

Shepelin V.A. (Ph. D. [Chem.], Deputy Director R&D Center),

Sayahov M.D (Ph. D. [Chem.], Head of Lab. R&D Center),

Kharlampidi H.E. (Prof., D. Sc. [Chem.])

The influence of a catalytic complex of cationic type on oligomerization reaction of octene-1, dodecene-1 and tetradetcene-1 has been investigated. Composition of reaction mass was studied by chromatograph «Fisons – GC 8000». As a result of the experiments by the use of catalytic complex ethylaluminium dichloride and chlorocyclohexane, the possibility to use the oils based on polyalphaolefins (PAO) as alternative to obtaining synthetic oils of high viscosity was shown. Traditional raw materials for production of synthetic oils is decene-1. The closest molecular weight analogous to decene-1 confirmed by physico-chemical parameters of obtained PAO is a mixture of α-olefins of octane-1: dodecene-1 ratio 50:50. According the results of olygomerization of α-olefins the temperature of pour point is –50 oC, i.e. 5–19 oC lower than that for PAO based on decene-1; index of the viscosity is 159, i.e. higher than that for PAOO based on decene-1. The increase of temperature of reaction from 40 up to 120 oC results in the increase of the proportion of oligomers of boiling temperature lower than 390 oC. Optimum conditions and ratios of α-olefins for obtaining high-viscosity oils based on PAO are found.

Key words: octene-1, decene-1, dodecene-1, tetadecene-1, oligomer C8-C14, ethylaluminium dichloride, chlorocyclohexane, oligomerization, polyalphaolefin oils, viscosity

The Treatment of Wastewater of Synthetic Rubber Production from Anionic Surfactants

Gilaeva G.V. (Ph.D. [Techn.], Head of Lab. R&D Center),

Nikonorova V.N. (Lead Processing Engineer R&D Center), Burganov R.T. (Ph.D. [Techn.], Head of Lab. R&D Center)

The possibility of wastewater (WW) purification of BR production from antiagglomerator (AA) by treating them by WW of SKI production. AA – surfactants based on the mixtures of polycarboxylates (isobutylene- maleic anhydride copolymer salts of sodium, potassium, calcium) and characterized by poor biodegradability. AA action is directed to prevent the adhesion of rubber crumb during its degassing and separation. WW of SKI production based on titanium tetrachloride and trialkylaluminium are formed at the stage of polymerization and washing of product from catalyst; the possibility to use WW of SKI containing aluminum and titanium ions as a mixed coagulant is shown. The value of chemical oxygen demand (COD) was used for evaluation of AA content. COD was used also for evaluation of removing of AA from the mixture of WW of both BR and SKI after centrifuging. The results of the modeling of the coprecipitation of aluminum, titanium and AA compounds are presented. Mechanism of precipitation of AA based on formation of hydrogels of aluminum and titanium salts in water is suggested.

Key words: waste water, BR, SKI, anionic surfactants, antiaglomerate, coagulation, chemical oxygen demand, sludge volume, aluminum salts, titanium salts, hydrogels

Scientific-Practice Conference «Polymers of the Republic Tatarstan: Science, Innovations, Production», Devoted to

50 Anniversary of Formation of PJSC «Nizhnekamskneftekhim»

Akhsanova O.L. (Ph. D. [Chem.], Lead. Process Engineer),

Shalfeev A.Yu. (Deputy Chief Process Engineer)

Review of papers presented at the Conference «Polymers of the Republic of Tatarstan: Science, Innovations, Production» (Kazan, 07.09.17)

Key words: conference, review, petrochemistry, innovation, rubber, butyl rubber, Nd-PBR, Li-PBR, BSR, polyisoprene, microstructure of rubber, physical and mechanical tests of polymers, modification, tires

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