Mechanistic Insights of Ethylene Polymerization on Phillips Chromium Catalysts.

Silica-supported chromium oxide catalysts, also named Phillips chromium catalysts (PCCs), provide more than half of the world's production of high- and medium-density polyethylenes. PCCs are usually prepared in the Cr(VI)/SiO2 form, which is subjected to reductive activation. It has been explicitly proven that CO reduces Cr(VI) to Cr(II) species that initiate ethylene polymerization; ethylene activates Cr(VI) sites as well, but the nature of the catalytic species is complicated by the presence of the ethylene oxidation products. It is widely accepted that the catalytic species are of a Cr(III)-alkyl nature, but this common assumption faces the challenge of "extra" hydrogen: the formation of similar species under the action of even-electron reducing agents requires an additional H atom. Relatively recently, it was found that saturated hydrocarbons can also activate CrOx/SiO2, and alkyl fragments turn out to be bonded with a polyethylene chain. In recent years, there have been numerous experimental and theoretical studies of the structure and chemistry of PCCs at the different stages of preparation and activation. The use of modern spectral methods (such as extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), and others); operando IR, UV-vis, EPR, and XAS spectroscopies; and theoretical approaches (DFT modeling, machine learning) clarified many essential aspects of the mechanisms of CrOx/SiO2 activation and catalytic behavior. Overall, the Cosse-Arlman mechanism of polymerization on Cr(III)-alkyl centers is confirmed in many works, but its theoretical support required the development of nontrivial and contentious mechanistic concepts of Cr(VI)/SiO2 or Cr(II)/SiO2 activation. On the other hand, conflicting experimental data continue to be obtained, and certain mechanistic concepts are being developed with the use of outdated models. Strictly speaking, the main question of what type of catalytic species, Cr(II), Cr(III), or Cr(IV), comes into polymerization still has not received an unambiguous answer. The role of the chemical nature of the support-through the prism of the nature, geometry, and distribution of the active sites-is also not clear in depth. In the present review, we endeavored to summarize and discuss the recent studies in the field of the preparation, activation, and action of PCCs, with a focus on existing contradictions in the interpretation of the experimental and theoretical results.

Tridentate Nitrogen Ligand as a Tool for the Construction of Well-Defined Rare Earth Trichloride Complexes.

LnCl3(THF)3 (Ln = Y, La ÷ Nd, Sm ÷ Lu) readily react with the tridentate 1,3,5-trimethyl-1,3,5-triazacyclohexane (Me3tach) ligand to form mono- or binuclear lanthanide trichloride complexes, depending on the stoichiometry of the reaction and the ionic radius of the metal: mononuclear pseudosandwich [LnCl3(Me3tach)2], (Ln = Y, La ÷ Ho) or binuclear complexes [Ln2Cl6(Me3tach)3], or [LnCl3(Me3tach)(THF)]2 (Ln = Sm, Tb). Detailed analysis of the NMR data of [LnCl3(Me3tach)2] complexes with paramagnetic lanthanide ions showed that their structures remained unchanged in the toluene solution. A series of isomorphous complexes [LnCl3(Me3tach)(Py)2] (Ln = La, Sm, Tb, Er, Lu; Py = pyridine) have been obtained by the recrystallization of either mononuclear or binuclear complexes from pyridine. Complexes of terbium and europium ions with the Me3tach ligand exhibit relatively high quantum yields of metal-centered luminescence (0.39 and 0.32, respectively).

Crystalline Micro-Sized Carbonated Apatites: Chemical Anisotropy of the Crystallite Surfaces, Biocompatibility, Osteoconductivity, and Osteoinductive Effect Enhanced by Poly(ethylene phosphoric acid).

Carbonated hydroxyapatites (CAp) are very close to natural bone apatite in chemical composition and are regarded as a prospective bone mineral substitute for bone surgery and orthopedics. However, until now, the studies and applications of CAp were limited because of the amorphous nature of the synthetic CAp. In the present work, microsized highly crystalline carbonated apatites with uniform hexagonal (hCAp) or platelike (pCAp) morphology have been studied for the first time in vitro and in vivo, comparing against commercial hydroxyapatite (HAp) and ß-tricalcuim phosphate (ßTCP). In vitro experiments on dissolution of those calcium phosphate ceramics (CPCs) in acetate (pH 5.5) and Tris (pH 7.3) buffer solutions showed the following rank order of the dissolution rates: ßTCP > hCAp > pCAp > HAp. The higher dissolution rate of hCAp in comparison with pCAp is explained by chemical anisotropy of the crystallite surfaces, which was proven by SEM studies of the changes in the morphology of hCAp and pCAp crystallites during hydrolysis. A 5-week experiment on subcutaneous implantation of CPC species showed the following rank order of bioresorption rates: ßTCP > pCAp > hCAp > HAp. pCAp matrixes exhibited the highest biocompatibility, confirmed by histomorphological analysis. Three-month bone regeneration experiments involving a rat tibial defect model were conducted with 250-500 µm granules of pCAp and pCAp-PEPA [pCAp, pretreated with 2 wt % poly(ethylene phosphoric acid)]. Notably, pCAp-PEPA implants were resorbed at higher rates and induced the formation of more mature osseous tissue, a compact bone with Haversian systems.

Polyisobutylenes with Controlled Molecular Weight and Chain-End Structure: Synthesis and Actual Applications.

The polymerization of isobutylene allows us to obtain a wide spectrum of polyisobutylenes (PIBs) which differ in their molecular weight characteristics and the chemical structure of chain-end groups. The bulk of the PIBs manufactured worldwide are highly reactive polyisobutylenes (HRPIBs) with -C(Me)=CH2 end-groups and low-molecular weights (Mn < 5 kDa). HRPIBs are feedstocks that are in high demand in the manufacturing of additives for fuels and oils, adhesives, detergents, and other fine chemicals. In addition, HRPIBs and CMe2Cl-terminated PIBs are intensively studied with the aim of finding biomedical applications and for the purpose of developing new materials. Both chain control (molecular weight and dispersity) and chemoselectivity (formation of exo-olefinic or -CMe2Cl groups) should be achieved during polymerization. This review highlights the fundamental issues in the mechanisms of isobutylene polymerization and PIB analysis, examines actual catalytic approaches to PIBs, and describes recent studies on the functionalization and applications of HRPIBs and halogen-terminated PIBs.

MAO- and Borate-Free Activating Supports for Group 4 Metallocene and Post-Metallocene Catalysts of α-Olefin Polymerization and Oligomerization.

Modern industry of advanced polyolefins extensively uses Group 4 metallocene and post-metallocene catalysts. High-throughput polyolefin technologies demand the use of heterogeneous catalysts with a given particle size and morphology, high thermal stability, and controlled productivity. Conventional Group 4 metal single-site heterogeneous catalysts require the use of high-cost methylalumoxane (MAO) or perfluoroaryl borate activators. However, a number of inorganic phases, containing highly acidic Lewis and Brønsted sites, are able to activate Group 4 metal pre-catalysts using low-cost and affordable alkylaluminums. In the present review, we gathered comprehensive information on MAO- and borate-free activating supports of different types and discussed the surface nature and chemistry of these phases, examples of their use in the polymerization of ethylene and α-olefins, and prospects of the further development for applications in the polyolefin industry.

Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral Composites.

Composites of synthetic bone mineral substitutes (BMS) and biodegradable polyesters are of particular interest for bone surgery and orthopedics. Manufacturing of composite scaffolds commonly uses mixing of the BMS with polymer melts. Melt processing requires a high homogeneity of the mixing, and is complicated by BMS-promoted thermal degradation of polymers. In our work, poly(L-lactide) (PLLA) and poly(ε-caprolactone) (PCL) composites reinforced by commercial ß-tricalcium phosphate (ßTCP) or synthesized carbonated hydroxyapatite with hexagonal and plate-like crystallite shapes (hCAp and pCAp, respectively) were fabricated using injection molding. pCAp-based composites showed advanced mechanical and thermal characteristics, and the best set of mechanical characteristics was observed for the PLLA-based composite containing 25 wt% of pCAp. To achieve compatibility of polyesters and pCAp, reactive block copolymers of PLLA or PCL with poly(tert-butyl ethylene phosphate) (C1 and C2, respectively) were introduced to the composite. The formation of a polyester-b-poly(ethylene phosphoric acid) (PEPA) compatibilizer during composite preparation, followed by chemical binding of PEPA with pCAp, have been proved experimentally. The presence of 5 wt% of the compatibilizer provided deeper homogenization of the composite, resulting in a marked increase in strength and moduli as well as a more pronounced nucleation effect during isothermal crystallization. The use of C1 increased the thermal stability of the PLLA-based composite, containing 25 wt% of pCAp. In view of positive impacts of polyester-b-PEPA on composite homogeneity, mechanical characteristics, and thermal stability, polyester-b-PEPA will find application in the further development of composite materials for bone surgery and orthopedics.

Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers.

Despite large-scale investigations of homogeneous single-site metallocene catalysts and systems based on them, there are still unsolved problems related to the control of their activity and chemo- and stereoselectivity. A solution to these problems is required to develop efficient methods for the synthesis of practically useful products of alkene transformations, such as dimers, oligomers, and polymers. Here we studied the catalytic activity of structurally diverse zirconocenes (L2ZrCl2, L = Cp, C5Me5, Ind, L2 = Me2CCp2, Me2SiCp2, Me2C2Cp2, rac-Me2CInd2, rac-H4C2Ind2, BIPh(Ind)2, H4C2[THInd]2), and co-catalysts activating the system, namely HAlBui2, MMAO-12, and (Ph3C)[B(C6F5)4], at low activator/Zr ratios in a 1-hexene oligomerization reaction. The influence of catalyst structure and system composition on the alkene conversion, the type of products, and the reaction stereoselectivity were investigated. The composition of hydride intermediates formed in the L2ZrCl2-HAlBui2-activator system (L2 = ansa-Me2CCp2, Ind) was studied by NMR spectroscopy. Participation of the bis-zirconium hydride complex as the precursor of catalytically active sites of the alkene dimerization reaction was shown.

Design, Synthesis and Actual Applications of the Polymers Containing Acidic P-OH Fragments: Part 2-Sidechain Phosphorus-Containing Polyacids.

Macromolecules containing acidic fragments in side-groups­polyacids­occupy a special place among synthetic polymers. Properties and applications of polyacids are directly related to the chemical structure of macromolecules: the nature of the acidic groups, polymer backbone, and spacers between the main chain and acidic groups. The chemical nature of the phosphorus results in the diversity of acidic >P(O)OH fragments in sidechain phosphorus-containing polyacids (PCPAs) that can be derivatives of phosphoric or phosphinic acids. Sidechain PCPAs have many similarities with other polyacids. However, due to the relatively high acidity of −P(O)(OH)2 fragment, bone and mineral affinity, and biocompatibility, sidechain PCPAs have immense potential for diverse applications. Synthetic approaches to sidechain PCPAs also have their own specifics. All these issues are discussed in the present review.

Design, Synthesis and Actual Applications of the Polymers Containing Acidic P-OH Fragments: Part 1. Polyphosphodiesters.

Among natural and synthetic polymers, main-chain phosphorus-containing polyacids (PCPAs) (polyphosphodiesters), stand in a unique position at the intersection of chemistry, physics, biology and medicine. The structural similarity of polyphosphodiesters PCPAs to natural nucleic and teichoic acids, their biocompatibility, mimicking to biomolecules providing the 'stealth effect', high bone mineral affinity of polyphosphodiesters resulting in biomineralization at physiological conditions, and adjustable hydrolytic stability of polyphosphodiesters are the basis for various biomedical, industrial and household applications of this type of polymers. In the present review, we discuss the synthesis, properties and actual applications of polyphosphodiesters.

Coordination Polymers of Polyphenyl-Substituted Potassium Cyclopentadienides.

A series of potassium salts of di- and tri-arylsubstituted cyclopentadienes has been obtained by the metalation of the corresponding cyclopentadienes with benzylpotassium in THF media. Crystals of all compounds, afforded by recrystallization from THF/hexane, diglyme-THF/hexane and toluene/hexane mixtures, have been studied by X-ray diffraction. All studied potassium cyclopentadienides exhibit the luminescence at room temperature and overall quantum yield of photoluminescence for potassium salt of diarylsubstituted cyclopentadiene is 18%.

Transition Metal-(µ-Cl)-Aluminum Bonding in α-Olefin and Diene Chemistry.

Olefin and diene transformations, catalyzed by organoaluminum-activated metal complexes, are widely used in synthetic organic chemistry and form the basis of major petrochemical processes. However, the role of M−(µ-Cl)−Al bonding, being proven for certain >C=C< functionalization reactions, remains unclear and debated for essentially more important industrial processes such as oligomerization and polymerization of α-olefins and conjugated dienes. Numerous publications indirectly point at the significance of M−(µ-Cl)−Al bonding in Ziegler−Natta and related transformations, but only a few studies contain experimental or at least theoretical evidence of the involvement of M−(µ-Cl)−Al species into catalytic cycles. In the present review, we have compiled data on the formation of M−(µ-Cl)−Al complexes (M = Ti, Zr, V, Cr, Ni), their molecular structure, and reactivity towards olefins and dienes. The possible role of similar complexes in the functionalization, oligomerization and polymerization of α-olefins and dienes is discussed in the present review through the prism of the further development of Ziegler−Natta processes and beyond.

Chain-End Functionalization of Poly(ε-caprolactone) for Chemical Binding with Gelatin: Binary Electrospun Scaffolds with Improved Physico-Mechanical Characteristics and Cell Adhesive Properties.

Composite biocompatible scaffolds, obtained using the electrospinning (ES) technique, are highly promising for biomedical application thanks to their high surface area, porosity, adjustable fiber diameter, and permeability. However, the combination of synthetic biodegradable (such as poly(ε-caprolactone) PCL) and natural (such as gelatin Gt) polymers is complicated by the problem of low compatibility of the components. Previously, this problem was solved by PCL grafting and/or Gt cross-linking after ES molding. In the present study, composite fibrous scaffolds consisting of PCL and Gt were fabricated by the electrospinning (ES) method using non-functionalized PCL1 or NHS-functionalized PCL2 and hexafluoroisopropanol as a solvent. To provide covalent binding between PCL2 and Gt macromolecules, NHS-functionalized methyl glutarate was synthesized and studied in model reactions with components of spinning solution. It was found that selective formation of amide bonds, which provide complete covalent bonding of Gt in PCL/Gt composite, requires the presence of weak acid. With the use of the optimized ES method, fibrous mats with different PCL/Gt ratios were prepared. The sample morphology (SEM), hydrolytic resistance (FT-IR), cell adhesion and viability (MTT assay), cell penetration (fluorescent microscopy), and mechanical characteristics of the samples were studied. PCL2-based films with a Gt content of 20 wt% have demonstrated the best set of properties.

The Use of Branching Agents in the Synthesis of PBAT.

Biodegradable polyesters represent an advanced alternative to polyolefin plastics in various applications. Polybutylene adipate terephthalate (PBAT) can compete with polyolefins in terms of their mechanical characteristics and melt processing conditions. The properties of PBAT depend on the molecular weight, dispersity, and architecture of the copolymer. Long-chain branching (LCB) of the PBAT backbone is an efficient method for the improvement of the copolymer characteristics. In the present work, we studied branching agents (BAs) 1-7 of different structures in the two-stage polycondensation of 1,4-butanediol, dimethyl terephthalate, and adipic acid and investigated the composition and melt rheology of the copolymers. According to the results of the research, 1,1,1-tris(hydroxymethyl)ethane 2 and 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid 5 outperformed glycerol 1 as BAs in terms of shear thinning behavior and viscoelasticity.

Bis(η5-cyclo-penta-dien-yl)(2-{[(2-meth-oxy-phen-yl)imino]-meth-yl}phenolato-κ3 O,N,O')terbium.

The air- and moisture-sensitive title compound, [Tb(C5H5)2(C14H12NO2)], was synthesized from tris-(cyclo-penta-dien-yl)(tetra-hydro-furan)-terbium and 2-{[(2-meth-oxy-phen-yl)imino]-meth-yl}phenol. Each Tb atom is coordinated by two cyclo-penta-dienyl ligands in an η5-coordination mode and by one N and two O atoms of the organic ligand in a tridentate κ3 O,N,O'-mode.

Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation.

Ultra-high molecular weight poly-α-olefins are widely used as drag reducing agents (DRAs) for pipeline transportation of oil and refined petroleum products. The synthesis of polyolefin DRAs is based on low-temperature Ziegler-Natta (ZN) polymerization of higher α-olefins. 1-Hexene based DRAs, the most effective at room temperature, typically lose DR activity at low temperatures. The use of 1-hexene copolymers with C8-C12 linear α-olefins appears to offer a solution to the problem of low-temperature drag reducing. The present work aims to develop two-stage synthesis of polyolefin DRAs that is based on selective oligomerization of ethylene in the presence of efficient chromium/aminodiphosphine catalysts (Cr-PNP), followed by polymerization of the olefin mixtures, formed at oligomerization stage, using efficient titanium-magnesium ZN catalyst. We have shown that oligomerization of ethylene in α-olefin reaction media proceeds faster than in saturated hydrocarbons, providing the formation of 1-hexene, 1-octene, and branched C10 and C12 olefins; the composition and the ratio of the reaction products depended on the nature of PNP ligand. Oligomerizates were used in ZN polymerization 'as is', without additional treatment. Due to branched character of C10+ hydrocarbons, formed during oligomerization of ethylene, resulting polyolefins demonstrate higher low-temperature DR efficiency at low polymer concentrations (~1 ppm) in comparison with benchmark polymers prepared from the mixtures of linear α-olefins and from pure 1-hexene. We assume that faster solubility and more efficient solvation of the polyolefins, prepared using 'tandem' ethylene-based process, represent an advantage of these type polymers over conventional poly(1-hexene) and linear α-olefin-based polymers when used as 'winter' DRAs.

Zirconocene dichlorides as catalysts in alkene carbo- and cyclometalation by AlEt3: intermediate structures and dynamics.

A series of zirconocenes L2ZrCl2 (23 examples) were studied as catalysts in the reaction of alkenes with AlEt3. The catalyst activity and reaction chemoselectivity were found to depend on the ligand structure in the complex and the nature of the solvent. The alkyl exchange in the triethylaluminum dimer was studied by NMR spectroscopy; a solvent effect on the alkyl exchange parameters was established. In the reaction between L2ZrCl2 and AlEt3, the formation of intermediates L2ZrEtCl, L2Zr(µ-Cl)CH2CH2AlEt2, L2Zr(µ-H)CH2CH2AlEt2, and L2Zr(µ-Cl)CH2CH(AlEt2)2 was shown; the ratio of the intermediates depends on the ligand structure in the initial complex and the solvent. The exchange in the ethanediyl bridge ZrCH2CH2Al, proceeding via zirconocenecyclopropane structures, was demonstrated for the first time for five-membered bimetallic complexes L2Zr(µ-Cl)CH2CH2AlEt2 with ansa-ligands (L2 = Me2SiCp2, H2CInd2, Me2CInd2, Me2SiInd2, and C2H4Ind2). Five-membered bimetallic complexes were shown to participate in the formation of cyclic organoaluminum products - 3-substituted alumolanes.

Antibacterial Poly(ε-CL)/Hydroxyapatite Electrospun Fibers Reinforced by Poly(ε-CL)-b-poly(ethylene phosphoric acid).

In bone surgery and orthopedics, bioresorbable materials can be helpful in bone repair and countering post-op infections. Explicit antibacterial activity, osteoinductive and osteoconductive effects are essential to achieving this objective. Nonwoven electrospun (ES) fibers are receiving the close attention of physicians as promising materials for wound dressing and tissue engineering; potentially, in high contrast with dense materials, ES mats hamper regeneration of the bone extracellular matrix to a lesser extent. The use of the compositions of inherently biodegradable polyesters (poly(ε-caprolactone) PCL, poly(lactoglycolide), etc.), calcium phosphates and antibiotics is highly prospective, but the task of forming ES fibers from such compositions is complicated by the incompatibility of the main organic and inorganic ingredients, polyesters and calcium phosphates. In the present research we report the synthesis of hydroxyapatite (HAp) nanoparticles with uniform morphology, and demonstrate high efficiency of the block copolymer of PCL and poly(ethylene phosphoric acid) (PEPA) as an efficient compatibilizer for PCL/HAp mixtures that are able to form ES fibers with improved mechanical characteristics. The materials obtained in the presence of vancomycin exhibited incremental drug release against Staphylococcus aureus (St. aureus).

Polymer Cold-Flow Improvers for Biodiesel.

In recent decades, biodiesel has been explored as a prospective comparable fuel to petroleum diesel for compression ignition engines. However, several drawbacks have limited the wide application of biodiesel as motor fuel, and the poor cold-flow property is one of the major problems. This problem is compounded by the diversity of the biodiesel characteristics arising from a variety of chemical compositions of biodiesel from different sources. Among the methods investigated to improve the cold-flow properties of biodiesel, the use of additives seems highly promising. Despite the significant number of publications, the potential of this method is still far from having been completely discovered or exploited. In the present review, we briefly describe the sources, chemical composition, and physico-chemical characteristics of the main types of biodiesel. Next, we discuss the examples of the use of different polymer additives for the improvement of the cold-flow characteristics of biodiesel and biodiesel/petroleum diesel blends. Additionally, we tried to assess the prospects of the polymer additives to enhance biodiesel performance. The main conclusion of this survey is that innovative and high-efficiency cold-flow improvers for biodiesel should be further developed.

Low-Temperature Mechanical Properties of High-Density and Low-Density Polyethylene and Their Blends.

Low-temperature properties of high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and their blends were studied. The analyzed low-temperature mechanical properties involve the deformation resistance and impact strength characteristics. HDPE is a bimodal ethylene/1-hexene copolymer; LDPE is a branched ethylene homopolymer containing short-chain branches of different length; LLDPE is a binary ethylene/1-butene copolymer and an ethylene/1-butene/1-hexene terpolymer. The samples of copolymers and their blends were studied by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), 13С NMR spectroscopy, and dynamic mechanical analysis (DMA) using testing machines equipped with a cryochamber. It is proposed that such parameters as "relative elongation at break at -45 °C" and "Izod impact strength at -40 °C" are used instead of the ductile-to-brittle transition temperature to assess frost resistance properties because these parameters are more sensitive to deformation and impact at subzero temperatures for HDPE. LLDPE is shown to exhibit higher relative elongation at break at -45 °C and Izod impact strength at -20 ÷ 60 °C compared to those of LDPE. LLDPE terpolymer added to HDPE (at a content ≥ 25 wt.%) simultaneously increases flow properties and improves tensile properties of the blend at -45 °C. Changes in low-temperature properties as a function of molecular weight, MWD, crystallinity, and branch content were determined for HDPE, LLDPE, and their blends. The DMA data prove the resulting dependences. The reported findings allow one to understand and predict mechanical properties in the HDPE-LLDPE systems at subzero temperatures.

Phase Equilibria and Interdiffusion in Bimodal High-Density Polyethylene (HDPE) and Linear Low-Density Polyethylene (LLDPE) Based Compositions.

The compositions based on bimodal high-density polyethylene (HDPE, copolymer of ethylene with hexene-1) and in mixture with monomodal tercopolymer of ethylene with butene-1/hexene-1 (LLDPE, low-density polyethylene) have been studied. Phase equilibrium, thermodynamic parameters of interdiffusion in a wide range of temperatures and ratios of co-components were identified by refractometry, differential scanning calorimetry, optical laser interferometry, X-ray phase analysis. The phase state diagrams of the HDPE-LLDPE systems were constructed. It has been established that they belong to the class of state diagrams of "solid crystal solutions with unrestricted mixing of components". The paired parameters of the components interaction and their temperature dependences were calculated. Thermodynamic compatibility of α-olefins in the region of melts and crystallization of one of the components has been shown. The kinetics of formation of interphase boundaries during crystallization of α-olefins has been analyzed. The morphology of crystallized gradient diffusion zones has been analyzed by optical polarization microscopy. The sizes of spherulites in different areas of concentration profiles and values of interdiffusion coefficients were determined.