B. F. Shklyaruk

Effect of Electron Donors on Polymerization of Propylene in the Presence of Titanium—Magnesium Catalysts

The effect of internal and external electron donors on the polymerization of propylene in a liquid monomer or a hydrocarbon diluent (hexane) in the presence of a titanium-magnesium nanocatalyst activated with an organoaluminum compound (triethylaluminum, triisobutylaluminum) and the properties of the resulting PP are studied. The polymerization of propylene in the absence of internal and external donors yields atactic PP, whereas, in the presence of a catalyst containing an aryl internal donor, isotactic PP is formed. The activity and stereospecificity of the catalytic system substantially depends on the method of electron-donor introduction. The thermal treatment of the catalyst with an electron donor affects its activity and stereospecificity.

Copolymerization of propylene with 1-octene initiated by highly efficient isospecific metallocene catalytic systems

The copolymerization of propylene with 1-octene in liquid propylene is carried out in the presence of a highly active homogeneous ansa-m etallocene catalyst with the C2-symmetry rac-Me2Si(4-Ph-2- MeInd)2ZrCl2 activated by methyl aluminoxane and in the presence of ansa- metallocene C4H6Si(2-Et4- PhInd)2ZrCl2 (rac: meso = 2:1) supported on silica gel treated with methylaluminoxane. In the case of the heterogenized metallocene, (iso-C4H9 )3Al is used as a cocatalyst. The copolymers of propylene and 1-octene containing up to 24 and 9.3 mol% units of the second comonomer are prepared with the homogeneous and heterogenized systems, respectively. The copolymerization of propylene with 1-octene in liquid propylene shows the azeotropic (ideal) character, and the distribution of comonomer units in the copolymers is close to statistical. The modification of PP with even small amounts of 1-octene affects the regularity of polymer chains, molecular-mass characteristics of the copolymers, their melting temperature, and the degree of crystallinity and makes it possible to vary their rigidity and elasticity in a wide range. The character of changes in thermal and mechanical properties is almost the same for the copolymers synthesized with homogeneous and heterogenized catalysts.

Nanocomposites based on layered silicates and ultrahigh-molecular-mass polyethylene prepared via in situ polymerization

Nanocomposites based on ultrahigh-molecular-mass PE and layered silicates are prepared via in situ polymerization. The process is conducted in the suspension mode under mild conditions with the use of a conventional Ziegler-Natta catalyst and a bifunctional complex containing a nickel oligoallene component along with a titanium component. The fillers are four types of montmorillonite: nonmodified montmorillonite and three montmorillonites modified with various organic intercalants. In their presence, the activities of the catalysts appreciably increase (by a factor of 2–3). Composites containing 10–40 wt % aluminosilicates are prepared. The structures of the polymer matrix and composites are studied via X-ray diffraction. It is found that the degree of exfoliation of the filler depends not only on its amount but also on the type of modifier and the type of catalytic system. The PE matrix with a molecular mass of (1.5–1.6) × 106 has a melting point of T m = 141–143°C, a high enthalpy of melting, and a high degree of crystallinity. The IR-spectral studies of the polymers synthesized with the bifunctional complex reveal the presence of branches in a chain, thereby suggesting the formation of linear PE with a medium density (0.938–0.946 g/cm3). Nanocomposites containing 10% aluminosilicate possess the best complex of mechanical properties relative to that of unfilled polyethylene.

Isoprene polymerization on titanium-magnesium catalysts

The high activity of a titanium-magnesium catalyst in the polymerization of isoprene with formation of a unique thermoplastic material, synthetic gutta percha, was shown. It is established that a change in polymerization conditions over a wide range has no effect on the content of trans-1,4 units in the polymer. Unlike natural gutta percha with the crystalline phase containing a mixture of α-and β-crystalline modifications, the synthetic trans-1,4-polyisoprene crystallizes only in an α-monoclinic form, the melting temperature of which is close to 70°C. The melting followed by crystallization results in formation of a stable β-crystalline modification with a melting temperature approximating 50°C.

Nanocomposites and high-modulus fibers based on ultrahigh-molecular-weight polyethylene and silicates: Synthesis, structure, and properties

Nanocomposites based on ultrahigh-molecular-weight polyethylene and inorganic fillers—such as organomodified layered aluminosilicates, aerosil, and diatomite—are prepared via polymerization filling. The polymerization of ethylene was conducted in the suspension mode with the use of a conventional Ziegler-Natta catalyst, TiCl4 + Al(i-Bu)3, under mild conditions (a temperature of 30°C and a pressure of 0.1MPa). The structure and properties of the composites are studied via X-ray diffraction analysis and DSC. The polyethylene matrix features a high enthalpy, a high melting temperature (up to 143°C), a crystallinity of 70–80%, a content of the monoclinic phase of 12–15%, and a bulk density of 0.05–0.15 g/cm3; the molecular mass is (1.5–1.6) × 106. High-modulus, high-strength fibers with an elastic modulus of 25–28 GPa and a strength of 0.65–0.70 GPa are prepared via direct solvent-free molding of nascent reactor powders based on ultrahigh-molecular-weight polyethylene filled (7 wt %) with aerosol or montmorillonite modified with vinyltrimethoxysilane.

Synthesis of propylene-ethylene copolymers in liquid propylene using ansa-metallocenes of the C 1 symmetry

The copolymerization of ethylene with propylene in the liquid propylene initiated by ansa-metallocenes of the C 1 symmetry, rac-[1-(9-η5-fluorenyl)-2-(5,6-cyclopenta-2-methyl-1-η5-indenyl)ethane]zirconium dichloride and rac-[1-(9-η5-fluorenyl)-2-(5,6-cyclopenta-2-methyl-1-η5-indenyl)ethane]hafnium dichloride, activated by methylaluminoxane has been studied. Triisobutylaluminum has been used as a cocatalyst. The propylene-ethylene copolymers thus prepared contain 5–60 mol % ethylene units. The reactivity ratios have been measured. In the case of the zirconocene-based catalyst, the molecular mass of the copolymers decreases with an increase in the content of ethylene units. The reverse situation is observed in the case of the hafnocene-based catalytic system. The copolymers are characterized by the low T g values (down to −45°C). Incorporation of a small amount of ethylene units (5 mol %) results in a rise in the elastomeric behavior of the polymers.

Polymerization of butadiene with titanium-magnesium nanocatalysts

The suspension polymerization of butadiene in the presence of titanium-magnesium nanocatalysts 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 the process and the properties of trans-1,4-polybutadiene are examined.

Copolymerization of propylene with 1-butene and 1-pentene with the isospecific catalytic system rac-Me2Si(4-Ph-2-MeInd)2ZrCl2-MAO

The copolymerization of propylene with 1-butene and 1-pentene at 60°C in the propylene bulk in the presence of the homogeneous isospecific metallocene catalyst of the C2 symmetry rac-Me2Si(4-Ph-2-MeInd)2ZrCl2 activated by polymethylaluminoxane is studied. Copolymers containing up to 30 mol % 1-butene and up to 10 mol % 1-pentene are synthesized. For the copolymerization of the above monomers, reactivity ratios are estimated to be equal to unity, thereby indicating the azeotropic character of the process. It is found that the distribution of comonomer units in the copolymers is close to statistical. For both comonomers, the comonomer effect is observed: an increase in the rate of propylene polymerization after addition of a small amount of a less reactive comonomer. The addition of 1-butene and 1-pentene to polypropylene shows a weak effect on the stereoregularity of chains but causes a marked reduction in the molecular mass of the polymer and changes its thermophysical characteristics and mechanical properties. An X-ray diffraction study of the copolymers is performed.

Modification of polybutadiene with caprolacton during polymerization

Polybutadiene has been modified with ɛ-caprolacton during butadiene polymerization carried out in the presence of catalytic systems based on neodymium and organoaluminum compounds at a butadiene conversion of 90–96%. The structure, phase state, and temperature behavior of polybutadienes modified with ɛ-caprolacton have been studied by IR and 13C NMR spectroscopy, DSC, and X-ray diffraction analysis. The above approach shows promise for the synthesis of new-generation elastomers which do not rank below conventional rubbers in terms of their characteristics but possess biodegradability.

Starch–polyethylene polymer–polymer composites obtained by polymerization filling: Structure and oxidative degradability

The polymer–polymer composites bearing polyethylene and starch are obtained by polymerization filling. The polymerization of ethylene is carried out using catalyst system [TiCl4 + (С2H5)2AlCl] under mild conditions. It is found that the catalyst activity in the presence of a biopolymer is higher than that without the filler. The polyethylene matrix has a molecular mass of 1.26–1.40 M and features a melting point of 138–140°C, a high enthalpy, and a degree of crystallinity of 60–70%. Reduction in the decomposition temperature of the polymer–polymer composites and in the rate of mass loss compared to the unfilled polyethylene and biopolymers is detected. The stress-strain characteristics of the polymer matrix are improved; in particular, the elastic modulus and relative elongation at break are increased. The photooxidative degradation of the composites under the action of sunlight and UV radiation is studied. According to the data of IR spectroscopy, the polymer–polymer composites possess resistance to photooxidative aging 2–3 times lower than the unfilled polyethylene. The polymer–polymer composites subjected to UV radiation reveal a high intensity of growth of microorganisms: the degree of biofouling is up to four points.