Modified titanium-magnesium nanocatalysts in the polymerization of isoprene

The polymerization of isoprene on titanium-magnesium nanocatalysts modified with electron-donor compounds based on organic phosphines and sulfides has been studied. It was shown that the catalyst modification makes it possible to increase the content of trans-1,4 units in polyisoprene up to 97% (according to the data of ¹H NMR spectra). In the case of a catalyst modified with tributylphosphine, the effects of the phosphorus-to-titanium ratio on the polymerization kinetics, on the microstructure of trans-1,4-polyisoprene, and on the molecular mass of the polymer have been estimated.     

Kinetic behavior of ethylene polymerization in the presence of highly active titanium-magnesium catalysts

The influence of the composition of highly active titanium-magnesium catalysts (TiCl₄ supported on MgCl₂ and a TiCl₃·nMgCl₂ catalyst), the nature and concentration of organoaluminium cocatalyst, the concentration of catalyst and monomer on the activity and the shape of the kinetic curves during ethylene polymerization has been studied.

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(TiCl₄, MgCl₂ TiCl₃·nMgCl₂), , .

     

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.     

Influence of the substructure of supported titanium-magnesium catalysts on their activity in olefin polymerization

The influence of the substructure of magnesium chloride on the composition and activity of catalysts prepared by supporting TiCl₄ on MgCl₂ has been studied. Strong binding of TiCl₄ with the formation of highly active catalysts is shown to occur upon interaction with defects in the magnesium chloride structure.

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, TiCl₄ MgCl₂. , TiCl₄ .

     

Plasma polymerization of some organic compounds and properties of the polymers

Plasma polymerizations (under 13.5-MHz radiofrequency inductively coupled glow discharge) of some organic compounds are investigated by their properties (elemental analysis, surface energy, and infrared spectra) and their relations to the concentrations of free radicals in the polymers as detected by electron spin resonance (ESR) spectroscopy. Monomers that have been investigated are hexamethyldisiloxane, tetrafluoroethylene, acetylene, acetylene/N₂, acetylene/H₂O, acetylene/N₂/H₂O, allene, allene/N₂, allene/H₂O, allene/N₂/H₂O, ethylene, ethylene/N₂, ethylene oxide, propylamine, allylamine, propionitrile, and acrylonitrile. Plasma-polymerized polymers generally contain oxygen, even if the starting monomers do not contain oxygen. This oxygen incorporation is related to the free-radical concentration in the polymer. Molecular nitrogen copolymerizes with other organic monomers such as acetylene, allene, and ethylene, and their properties are very similar to those of plasma-polymerized polymers from nitrogen-containing compounds such as amines and nitriles. The addition of water to the monomer mixture reduces in a dramatic manner the concentration of free radicals in the polymer and consequently the oxygen-incorporation after the polymer is exposed to air. The concentrations of free radicals (by ESR) are directly correlated to the change of the properties of plasma-polymerized polymers with time of exposure to the atmosphere. These changes are primarily the introduction of carbonyl (and possibly hydroxyl) groups. The addition of water to the plasma introduces these groups during the polymerization.     

On the stability and properties of the polyacrylate/Na-MMT nanocomposite obtained by seeded emulsion polymerization

For high performance waterborne coatings usually polymer latexes with low emulsifier content are more preferred. Although polymer/clay nanocomposites offer improved properties, it is difficult to produce clay based nanocomposite latexes containing low emulsifier due to the stabilization problems especially caused by organoclays. Present study deals with the preparation of a tBA/BA/MAA ternary copolymer/clay nanocomposite containing 3 wt.% sodium montmorillonite (Na⁺-MMT) via seeded emulsion polymerization. Experimentally it was observed that even the usage of hydrophilic clay caused stabilization problem and a certain amount of emulsifier (>1 wt.%) was necessary to obtain stable latexes. In addition, the usage of a low molecular weight water soluble polymer as steric barrier was found to increase the stability of system. Obtained nanocomposite latex showed fine particle size diameter (127 nm) and very narrow size distribution (PDI = 0.06). The WAXD and TEM investigations indicated that a mostly exfoliated nanocomposite was obtained. Thermal analyses (DSC, DMTA and TGA) showed that there was no change at T_g of the copolymer while very high improvement was obtained for elastic modulus and a slight increase in thermal stability. According to the rheological measurements, the nanocomposite latex showed a higher low shear viscosity, a stronger shear thinning behavior and an improved physical stability in comparison to the reference latex.     

Synthesis and physicochemical properties of some spirochromenes obtained on the basis of 4-azaindoline

The condensation of N-methyl(ethyl)-3,3-dimethyl-2-methylene-4-azaindoline with salicylic acid derivatives was used to synthesize thermo- and photochromic spirochromenes. The kinetics of the spontaneous decolorization of these compounds in ethanol and toluene were studied. The photosensitivity to UV rays of the 4-azaindoline spirochromes is greater by a factor of 1.5 than that of the indoline analogs.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1367–1369, October, 1982.     

Study of the formation and electrochemical properties of nickel oxide-carbon fiber composites obtained in the presence of surfactants

The electrochemical properties of nickel oxide-carbon fiber composites obtained in the presence of SDS and PEG surfactants and chitosan biopolymer by means of cyclic voltammetry have been investigated. The material’s capacity parameters have been determined and the charging times and electrolyte resistance in pores have been calculated. The interrelation between the electrochemical and structural composite parameters are demonstrated.     

Physicomechanical properties of grafted polymers obtained by radiation-induced polymerization by radical and ionic mechanisms

The radiation-induced grafting of acrylonitrile, 4-vinylpyridine, and styrene was carried out by both radical and ionic mechanisms. Grafted polymers with equal percentages of graft were obtained by the radical and ionic propagation of the grafted chains. The molecular weight of homopolymers has been determined. The thermomechanical properties of the graft polymers were investigated. The yield temperatures for the graft polymers obtained by ionic propagation of the grafted chains is higher than that of graft polymers obtained by a radical mechanism. This is attributed to the higher molecular weight of the grafted chains obtained by the radiation-induced grafting by the ionic mechanism. The radiation-induced grafting of polyacrylonitrile increases significantly the thermal stability of polyethylene. The differential thermal analysis shows no marked differences in properties of the polymers.     

The cohydrolysis of γ-trifluoropropenylmethyldichlorosilane with dimethyldichlorosilane and the polymerization of the products obtained

The cohydrolysis of -trifluoropropenylmethyldichlorosilane and dimethyldichlorosilane at 70°–75° C leads to the formation of -trifluoropropenylnonamethylcyclopentasiloxane, -trifluoropropenyl-pentamethylcyclotrisiloxane, and bis(-trifluoropropenyl)hexamethylcyclotetrasiloxane. These oligomers were polymerized in the presence of a Ziegler-Natta catalyst, forming low-molecular-weight oily polymers with M = 1000–3000.     

The cohydrolysis of γ-trifluoropropenylmethyldichlorosilane with dimethyldichlorosilane and the polymerization of the products obtained

The cohydrolysis of γ-trifluoropropenylmethyldichlorosilane and dimethyldichlorosilane at 70°–75° C leads to the formation of γ-trifluoropropenylnonamethylcyclopentasiloxane, γ-trifluoropropenyl-pentamethylcyclotrisiloxane, and bis(γ-trifluoropropenyl)hexamethylcyclotetrasiloxane. These oligomers were polymerized in the presence of a Ziegler-Natta catalyst, forming low-molecular-weight oily polymers with M = 1000–3000.     

A study on the plasma polymerization of some cyano-containing compounds and their electrical properties

Plasma polymerization of some cyano-containing organic compounds was carried out at 13.56 MHz from the gas phase. The resulting polymer films were smooth and pinhole free. The electrical conductivities of the polymer films varied from 10^?12 to 10^?7 S cm^?1 depending upon which cyano-containing monomer was used. The Al/polymer film/ITO (indium-tin oxide) sandwich cells made from the films demonstrated a photovoltaic effect, and some of them showed good rectifying behavior. Infrared spectroscopy (IR) and ultraviolet spectroscopy (UV) were utilized to characterize the structure of the product polymers. The effects of the original structure in the starting monomers on the structure of the resulting polymers are investigated. The influence of incident light intensity on the photovoltaic characteristics was also investigated.     

Synthesis and properties of the polythiourethanes obtained by the cationic ring‐opening polymerization of cyclic thiourethanes

The cationic ring‐opening polymerization of a five‐membered thiourethane [3‐benzyl‐1,3‐oxazolidine‐2‐thione (BOT)] with boron trifluoride etherate afforded the corresponding polythiourethane with a narrow molecular weight distribution in an excellent yield. The molecular weight of the polymers could be controlled by the feed ratio of the monomer to the initiator. A kinetic study of the polymerization revealed that the polymerization rate of BOT (1.3 × 10^?2 L mol^?1 min^?1) was two times larger than that of the six‐membered thiourethane [3‐benzyltetrahydro‐1,3‐oxazolidine‐2‐thione (BTOT); 6.8 × 10^?3 L mol^?1 min^?1], and the monomer conversion obeyed the first‐order kinetic equation. These observations, along with the successful results in the two‐stage polymerization, supported the idea that this polymerization proceeded in a controlled manner. Block copolymerizations of BOT with BTOT were also carried out to afford the corresponding di‐ and triblock copolymers with narrow molecular weight distributions. The order of the 5% weight loss temperatures was as follows: poly(3‐benzyltetrahydro‐1,3‐oxazolidine‐2‐thione) [poly(BTOT)] > poly(BTOT₅₄‐b‐BOT₄₆) > poly(3‐benzyl‐1,3‐oxazolidine‐2‐thione) [poly(BOT)]. This indicated that an increase in the BTOT unit content raised the decomposition temperature. The order of the refractive indices was poly(BOT) > poly(BTOT₅₄‐b‐BOT₄₆) > poly(BTOT₅₄‐b‐BOT₄₆‐b‐BTOT₅₀) > poly(BTOT); this was in accord with the order of the sulfur content in the polymer chain. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4795–4803, 2006     

Combination of olefin insertion polymerization and olefin metathesis to extend the topology and composition of polyolefins

正Since Ziegler, Hogan and Banks’ seminal discoveries for the catalytic polymerization of olefins, many generations of catalysts have been reported [1–5]. These include the transition from the original heterogeneous catalysts (Ziegler and Phillips) to homogeneous catalysts combining metallocene,post-metallocene and late transition metal-based catalysts.The development of new catalysts has enabled a higher     

The role of monomer geometry on the properties of polyolefins: A numerical study

We explore the role of monomer geometry on the structural, dynamic, and thermodynamic properties of polyolefis by employing all-atom molecular dynamic simulations. Specifically, we compare properties of atactic polyolefins in the molten state including polypropylene (aPP), a short-chain branched polymer: poy(1-hexene) (aPH), and a polymer having cyclic olefins: poly(vinyl cyclobutane) (aPVCB). We find polymers having the same chain mass and atom composition (hydrocarbon-based molecules), but having different monomer architecture differ strongly in material properties. In particular, the polymer glass transition ( $T_{\mathrm{g}}$) and bulk modulus ( $B$) show higher values for aPVCB in comparison to aPP and aPH. This increase is caused by having the carbon atoms in a cyclic structure, making aPVCB achieve higher mass and energy densities. By contrast, adding linear short side chains to polymer backbones causes a reduction in $T_{\mathrm{g}}$ and $B$, since side chains make backbones displace each other reducing their packing and thus their mass and energy densities. More broadly, our numerical results suggest that the incorporation of VCB monomers to linear polyolefins will enhance their properties, opening the possibility for designing a new set of materials.     

The relationship between gas-phase processes and the structure of polyaniline obtained by plasma polymerization

The composition of the gas phase during plasma polymerization of aniline was studied with the use of mass spectrometry; it was shown that at least 20% of aniline is consumed for the formation of secondary products (C₂H₂ and HCN). According to solid-state NMR data, the macromolecular chain of polyaniline obtained by plasma polymerization includes both aniline and aliphatic units. The latter units appear as a result of polymerization of the secondary product acetylene.     

The role of the liquid interface agent in mechanical properties improvement of modified chalk filled polyolefins

On the basis of the experimental results described in detail in the following sections an explanation of the mechanism of liquid modifier in chalk filled PP action was proposed. After concluding that liquid modifier does not change the sample morphology and crystallinity it was stated that it facilitates filler particles translocation in polymer matrix during deformation. Such translocations are the necessary condition for saturation of volume increase of the sample due to void formation in the process of polymer filler separation preserving the sample from its premature fracture. The most important physicochemical parameter of liquid modifier seems to be its molecular weight. This parameter determines liquids ability to migrate in micropore structure arising under stress and thus to act as a cracking agent. The possibility of the importance of more efficient heat dissipation in the sample was shown indicating the role of better thermal contacts in the sample in the case of modified chalk used as a filler. Such picture of mechanism of liquid modifier action leads also to two important conclusions:

Due to polymer filler separation by means of liquid layer no further filler particles surface processing, as in some cases, is needed.

The method of modification can be easily generalized for other polymers especially other polyolefins [19], [20] as physicochemical requirements for liquid are known.

     

Cationic polymerization of a novel oxetane‐bearing ionic liquid structure and properties of the obtained poly(ionic liquid)

An ionic liquid, 1‐ethyl‐3‐(3‐ethyl‐3‐oxetanylmethyl)imidazolium bis(trifluoromethanesulfonyl)imide (OXImTFSI), was synthesized, and its cationic polymerization was examined. The heating of a mixture of 1‐ethylimidazole and 3‐chloromethyl‐3‐ethyloxetane at 90 °C for 48 h yielded 1‐ethyl‐3‐(3‐ethyl‐3‐oxetanylmethyl)imidazolium chloride, which was transformed to a room‐temperature ionic liquid, OXImTFSI, by ion exchange with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). This ionic liquid was polymerized using boron trifluoride ethyl ether complex as a catalyst to give polyOXImTFSI. Five percent weight loss temperature (T_d5) of polyOXImTFSI evaluated by thermal gravimetric analysis was 409 °C, indicating the high thermal stability. Glass transition temperature (T_g) of the polymer evaluated by differential scanning calorimetry was ?19 °C, indicating the high flexibility of the material. Ionic conductivity of polyOXImTFSI was determined to be 1.86 × 10^?8 S/cm at 23 °C, which was far lower than that of the OXImTFSI monomer (5.05 × 10^?4 S/cm). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2986–2990