Isoprene polymerization on titanium-magnesium catalysts

Smetannikov, O. V.; Mushina, E. A.; Chinova, M. S.; Фролов, В. М.; Podol'skii, Yu. Ya.; Бондаренко, Г. Н.; Shklyaruk, B. F.; Антипов, Е. М.

doi:10.1134/s0965545x06080049

Cited by 9 publications

(5 citation statements)

References 3 publications

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“…The polymerization of isoprene initiated by these catalytic systems yields trans 1,4 polyisoprene or synthetic gutta percha [21]. The efficiency of polymerization increased owing to development of methods for the synthesis of TMCs with a particle size of 15-35 nm [19,20,22] or TMNCs (as opposed to conventional TMCs with a particle size of 120-1000 nm).…”

Section: Resultsmentioning

confidence: 99%

“…The advancement of studies in the field of design ing stereospecific and highly active TMCs enabled the authors of [16][17][18][19][20] to develop a new family of TMCs, titanium-magnesium nanocatalysts (TMNCs), which are suitable for the trans polymerization of con jugated dienes (butadiene, isoprene) [21][22][23][24], ethyl ene polymerization that yield ultrahigh molecular weight PE, and the polymerization of α olefins (pro pylene, 3 methyl 1 butene) [25][26][27].…”

Section: Introductionmentioning

confidence: 99%

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Polymerization of butadiene with titanium-magnesium nanocatalysts

et al. 2012

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As is known, the polymerization of 1,3 butadiene in the presence of Ziegler type titanium containing catalytic systems based on tetravalent titanium mostly yields cis 1,4 polybutadiene.The catalytic systems of tri and divalent titanium (α , γ , or δ ), TiCl 3 /R 3 Al possess the trans regulat ing ability in the polymerization of butadiene [2]. The polymerization of butadiene catalyzed by the system TiX 4 /organomagnesium compound/Al(i C 4 H 9 ) 3 (X = Cl, I) gives rise to polybutadiene containing 90-95% trans 1,4 units [3].For polymerization of conjugated dienes [4][5][6][7][8][9], the stereoregulation and activity of catalytic systems and the molecular mass distribution and microstructure of polydienes are substantially affected by such parame ters as the nature and valence state of a transition metal (titanium, vanadium), the catalyst concentra tion, the nature of an organoaluminum compound, the type of modifying additives, the polymerization temperature, the nature of the support (MgCl 2 , SiO 2 ) , and the homogenization or heterogenization of the catalytic system [4][5][6][7][8][9].On the basis of the published data, the authors of review [6] arrived at the conclusion that titanium con taining Ziegler systems cannot be regarded as promis ing for the trans polymerization of butadiene and 1 This work was supported by the Russian Foundation for BasicResearch, project no. 09 03 00231 a. † Deceased. other dienes in terms of their stereospecificity and activity. In summary, they mentioned that the situa tion changes when titanium containing catalysts sup ported on the surface of solid supports (MgCl 2 , SiO 2 ) are used.A series of studies was devoted to the polymeriza tion of 1,3 dienes and characterization of the resulting polymers [10][11][12][13][14][15]. It was shown that the polymeriza tion of both butadiene and isoprene occurs in the pres ence of silica gel supported titanium-magnesium catalysts (TMCs) combined with Al(i C 4 H 9 ) 3 and TMCs modified with organometallic compounds of Ni or Zr to produce polydienes containing 80-98% trans 1,4 units.The advancement of studies in the field of design ing stereospecific and highly active TMCs enabled the authors of [16-20] to develop a new family of TMCs, titanium-magnesium nanocatalysts (TMNCs), which are suitable for the trans polymerization of con jugated dienes (butadiene, isoprene) [21][22][23][24], ethyl ene polymerization that yield ultrahigh molecular weight PE, and the polymerization of α olefins (pro pylene, 3 methyl 1 butene) [25][26][27].The aim of this study is to investigate the polymer ization of 1,3 butadiene in the presence of TMNCs and to characterize the trans 1,4 polybutadiene (TPB) being synthesized.Abstract-The suspension polymerization of butadiene in the presence of titanium-magnesium nanocata lysts combined with triisobutylaluminum is studied. The resulting polybutadiene is shown to contain up to 99% trans 1,4 units. The dependences of polymer microstructure on temperature and the Al to Ti ratio are investigated. The kinetic parameters of...

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polymerization of butadiene with titanium-magnesium nanocatalysts

et al. 2012

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“…Plastic trans -1,4-polyisoprene mixed in less than 15 wt % percent with its cis-1,4-isomer or natural rubber constructs high-performance rubbers for preparation of the resulting green tires, which are anticipated to have properties superior to those of conventional butadiene–styrene copolymers. In addition, trans -1,4-polyisoprene has been employed as a material for medical purposes (orthopedics, reconstructive surgery) . Therefore, the exploration of highly efficient catalyst systems for trans -1,4-selective diene polymerizations has attracted increasing research interest.…”

Section: Introductionmentioning

confidence: 99%

Rare-Earth-Metal Complexes Bearing Phosphazene Ancillary Ligands: Structures and Catalysis toward Highly Trans-1,4-Selective (Co)Polymerizations of Conjugated Dienes

et al. 2012

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The bis-arylated phosphazene compounds [HN(PPh2NAr)2] (Ar = phenyl (HL1), 2,6-dimethylphenyl (HL2), 2,6-diisopropylphenyl (HL3)) and the imidodiphosphinate compound HN(PPh2O)2 (HL4) have been prepared via the Staudinger reaction. Treatment of the neutral compounds HL1, HL2, and HL3 with Ln(CH2SiMe3)3(THF)2 (Ln = Sc, Y, Lu) generated the solvent-free bis(alkyl) complexes L1Ln(CH2SiMe3)2 (Ln = Sc (1a), Y (1b), Lu (1c)), L2Sc(CH2SiMe3)2 (2a), L3Y(CH2SiMe3)2 (3b), and L3Lu(CH2SiMe3)2 (3c), respectively. The reaction between HL4 and Y(CH2SiMe3)3(THF)2 gave the rare zwitterionic complex 4b. Lithiation of the ligand HL1 by nBuLi followed by a metathesis reaction with Nd(BH4)3(THF)3 afforded the corresponding complex L1Nd(BH4)2(THF)2 (5). Complexes 1 upon incorporation of [Ph3C][B(C6F5)4] and AliBu3 led to ternary systems that initiated isoprene polymerization with high activities, among which complex 1a was the first example of a scandium catalytic precursor providing trans-1,4-selectivity (90.0%), while the lutetium analogue 1c had medium trans-1,4-selectivity (54.3%) and the yttrium complex 1b exhibited high cis-1,4-selectivity (76.3%). The ternary system based on the zwitterion 4b displayed the highest activity for the isoprene polymerization among these complexes and gave cis-1,4-regularity-enriched polyisoprene (70.6%). Highly stereospecific homopolymerizations of isoprene (trans-1,4-content: 97.0%) and butadiene (trans-1,4-content: 94.0%) were achieved by using the borohydrido complex 5 upon the activation of dibutylmagnesium. The copolymerization of isoprene and butadiene with 1a/[Ph3C][B(C6F5)4/AliBu3] gave randomly arranged trans-1,4-regulated polybutadiene and polyisoprene sequences. The kinetics study displayed competitive polymerization rates of r BD = 2.89 and r IP = 0.41. The thermal behaviors of the (co)polymers were investigated.

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“…The polymerization of isoprene on titanium-magnesium nanocatalysts (TMNCs) modified with electron donor (ED) compounds based on organic phosphine and sulphide have been studied [75,76]. The isoprene polymerization on TMC com-bined with TIBA was carried out at 30-50 °C, the titanium concentration in the reaction zone ranged from 10 -4 to 10 -3 mol/L and molar ratio Al:Ti = (20-100):1; the concentration of isoprene in the reaction medium was 1-2 mol/L.…”

Section: Isoprene Polymerizationmentioning

confidence: 99%

“…Melting and the subsequent crystallization results in the formation of the β-crystalline modification (second heating) with a melting temperature of about 50°C [76]. The study of isoprene polymerization on TMNCs/Bu3P showed that the presence of the electron donor leads to a reduced initial rate of polymerization, which becomes more pronounced with an increase in the content of the modifier in the TMNCs relative to the content of Ti (up to 50 mol/mol).…”

Section: Isoprene Polymerizationmentioning

confidence: 99%

Nanocatalysts in Olefins and Dienes Polymerization Processes

Nasirov¹

2021

J Mater Sci Manufac Res

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Sustainable development, the design of green and economically feasible processes to produce synthetic polymers is one of the major needs and biggest challenges. Catalysis of polymerization processes is among the most important applications within the field of nanoscience. Intensive research is being conducted and considerable success has been achieved in the heterogenization of various homogeneous catalysts on nano supports for polymerization of olefins and dienes. The large surface area of various nanomaterials qualifies them quite naturally to act either as a heterogeneous promoter for catalytic reactions or as a support for the heterogenization of homogeneous catalysts. To the polymerization of olefins and dienes by using nanocatalysts are devoted significant numbers of published papers, but to elucidate the possible effect of both the type and properties of nano supports and their sizes and amounts on the activity and stereoselectivity of heterogenized catalysts and the properties of the obtained polymers are needed more detailed studies. This review attempted to collect some published research materials in the field of the nanocatalysis of olefins and dienes polymerization processes and our main aim is to assess the critical points and to indicate the future perspectives and possible strategies in this area of research. We are confident that this review will be a helpful companion and deliver key hints to those, in academia and in the industry, who decide to move their research interest in this direction

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Isoprene polymerization on titanium-magnesium catalysts

Cited by 9 publications

References 3 publications

Polymerization of butadiene with titanium-magnesium nanocatalysts

Polymerization of butadiene with titanium-magnesium nanocatalysts

Rare-Earth-Metal Complexes Bearing Phosphazene Ancillary Ligands: Structures and Catalysis toward Highly Trans-1,4-Selective (Co)Polymerizations of Conjugated Dienes

Nanocatalysts in Olefins and Dienes Polymerization Processes

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