High pressure ethylene polymerization with a post‐metallocene bis‐phenyl phenoxy catalyst

The use of post‐metallocene bis‐phenylphenoxy catalysts to polymerize ethylene under high ethylene pressures (>25,000 psi) results in some remarkable catalytic properties. The high ethylene pressure produces molar ethylene concentrations in the reactor as much as 40 times higher than in typical low pressure ethylene polymerizations. This high ethylene concentration results in high catalyst efficiency at high temperatures and low reactor residence time, between 180 °C and 240 °C the catalyst efficiency surprisingly increases with increasing temperature, allowing for use of these catalysts at temperatures much higher than can be utilized in the low pressure processes. It has further been demonstrated that under these conditions increasing hydrogen levels up to 0.5 mol% does not significantly affect the polymer molecular weight; however, polymer molecular weight control can be realized with varying reactor temperature. The polymer produced is shown to be high density polyethylene made from a single site catalyst and not free radical initiated low density polymer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 861–866     

Properties of oriented film tapes prepared via solid-state processing of a nascent ultrahigh-molecular-weight polyethylene reactor powder synthesized with a postmetallocene catalyst

The correlation between the molecular mass of a nascent ultrahigh-molecular-weight polyethylene reactor powder synthesized with a postmetallocene catalyst and the specific features of plastic deformation during the orientational drawing of the material compacted and consolidated under laboratory conditions is studied. In the range 5 × 10⁶?7 × 10⁶, molecular mass is controlled via a change in the polymerization conditions. Under comparable conditions of orientational drawing, the highest values of strength (2.65 GPa) and the elastic modulus (100 GPa) are found for samples with M = 6.3 × 10⁶.     

Suzuki–Miyaura Cross‐Coupling Reaction of Naphthyl Triflate with Indole Boronic Acids Catalyzed by a Recyclable Polymer‐Supported N‐Heterocyclic Carbene–Palladium Complex Catalyst: Synthesis of Naphthalene‐Linked Bis‐Heterocycles

In this study, the Suzuki–Miyaura cross‐coupling reaction of naphthyl triflate with indole boronic acids catalyzed by a recyclable polymer‐supported Pd–NHC complex catalyst is presented. The polymer‐supported catalyst can be reused several times retaining high activity for the transformation. The structures of all the synthesized compounds were established by elemental analysis and from their mass, ¹H‐NMR, and ¹³C‐NMR spectra.     

Methyl branching in polyethylene from homopolymerization of ethylene with N‐arylcyano‐β‐diketiminate methallyl nickel‐B(C6F5)3

N‐Arylcyano‐β‐diketiminate methallyl nickel complexes activated with B(C₆F₅)₃ were used in the polymerization of ethylene. The microstructure analysis of obtained polyethylene (PE) was done by differential scanning calorimetry and ¹³C nuclear magnetic resonance (NMR). The branched polymer structures produced by these catalysts were attributed to one step isomerization mechanism of the catalyst along the polymer chain. The ortho or para position of the cyano group with co‐ordinated B(C₆F₅)₃ in both methallyl nickel catalysts influenced the polymer molecular weight, branching, and consequently melting and crystallization temperatures. NMR spectroscopic studies showed predominantly the formation of methyl branches in the obtained PE. Catalysts under study gave linear low‐density PEs with good crystallinities at temperatures of reaction between 50 °C and 70 °C at moderate pressures (12.3 atm). A propylene–ethylene copolymer produced by the metallocene catalyst had the same concentration of branches as the PE synthesized from methallyl nickel/B(C₆F₅)₃. Comparing the two polyolefins with the same degree of branching, it was observed that the polymer obtained with the nickel catalyst proved to be twice more crystalline and had greater T_m. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 452–458     

Synthesis and characterization of polymers based on the cyanate functional group

The chemistry and growth of polymer structures based on the cyanate linkage has been studied. The monofunctional model compound 2-(4-cyanatophenyl)-2-phenylpropane was used to study the reaction products. The synthesis was performed with four different transition metal catalysts and also without a catalyst. The quenched products were analyzed using Size Exclusion Chromatography(SEC) and ¹³C NMR. It was found that the reaction is relatively clean, with trimerization being the major product. A few side products were also detected, which included dimers and higher oligomeric species. Crosslinked polymers were synthesized without catalyst based on the bifunctional monomer 2, 2-bis(4-cyanatophenyl)propane. The structure was analyzed using ¹³C NMR. The conversion and number-average degree of polymerization based on ¹³C NMR is reported. Conversion at the gel point was found to be higher than 60%. On this basis it was concluded that polymerization based on cyanate linkages at the conditions studied is diffusion controlled and therefore not described by Flory's mean-field theory.     

A calorimetric investigation on high molecular weight polyethylene reactor powders

Reactor powders of high- and ultrahigh-molecular weight polyethylene have been investigated. Two different Ziegler-Natta synthesis processes were used: polymerization in a slurry and in the gas phase. Synthesis temperature range was 30–85°C. Monoclinic crystals were identified in samples synthesized at 30°C. Investigations of thermal parameters were carried out by differential scanning calorimetry. A range of heating rates (0.4–10.0°C/min) was used to obtain information on sample reorganization on heating. The corresponding melt-crystallized samples were scanned and their thermal parameters were compared with those obtained from the original nascent powders. Percent crystallinity and average lamellar thickness, computed by the Thompson-Gibbs equation, were found to be controlled by conditions of synthesis. For reactor powders, the fraction of crystallinity is found to be insensitive to synthesis temperature. Crystallinity is controlled mainly by the synthesis process type: slurry or gas phase. Lamellar thickness was found to decrease as synthesis temperature was increased. This trend is the opposite of what is obtained on melt crystallization and can be interpreted on the basis of Lauritzen and Hoffman's theory of crystal growth. Nascent reactor powders give experimental support for the dependence of lamellar thickness on crystallization temperature that follows the pattern described in the theory at high undercooling. The influence of molecular weight on crystallinity and lamellar thickness of both nascent powders and melt-crystallized samples was also studied. Catalyst and synthesis conditions were found to control crystallinity and crystallite dimensions of the reactor powders. Thus, polyethylenes suitable for a specific purpose can be obtained directly on synthesis.     

Structural analysis of polyethene prepared with rac‐dimethylsilylbis(indenyl)zirconium dichloride/methylaluminoxane in a high‐temperature,continuously stirred tank reactor

A study of ethene solution polymerization with the rac‐dimethylsilylbis(indenyl)‐zirconium dichloride/methylaluminoxane catalyst system in a high‐temperature (140 °C), continuously stirred tank reactor system was carried out. ¹³C NMR, gel permeation chromatography, Fourier transform infrared, and rheological measurements were used for polymer analyses. Polyethylenes with low molecular weights (weight‐average molecular weight ≈ 35–55 kg/mol) and small amounts of methyl, ethyl, and long‐chain branching were produced. ¹³C NMR measurements showed that the long‐chain and methyl branches increased and that the ethyl branch contents decreased with decreasing monomer concentrations. At high monomer concentrations, the chain transfer to the coordinated monomer was concluded to be the predominant chain termination mechanism, whereas the chain transfer to aluminum was dominant at low monomer concentrations, which was evidenced by the fact that the selectivity of end groups was reduced to about 50%. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3292–3301, 2002     

First example of latices synthesis via oligomerization of norbornene in aqueous emulsions,catalyzed by palladium chloride

Polymerization of norbornene using PdCl₂ as catalyst is generally carried out at high temperatures in the absence of solvent. Low yields of polymer with relatively undefined molecular weights are obtained under these conditions. We describe the first example of polymerization of norbornene in water dispersion or aqueous emulsions catalyzed by PdCl₂. Good yields of polymers and oligomers were obtained. Furthermore, in aqueous emulsions, novel microlatex which cannot be obtained by radical or ionic routes were synthesized, with particles sizes (10 nm.) generally only observed in microemulsion polymerizations.The stereochemistry of the polymers of low molecular weight was partially elucidated by¹³C NMR.     

Polymer‐supported half‐titanocene catalysts for the syndiospecific polymerization of styrene

Monocyclopendienyltitanium trichloride (CpTiCl₃) was supported on polymer carriers with different hydroxyl contents, and the supported catalysts were used for styrene polymerization. The supported catalysts exhibited high activity even at low Al/Ti ratios and increased the molecular weight of the products, indicating that polymer carriers could stabilize the active sites. The polymers prepared with unsupported and supported catalysts were extracted with boiling n‐butanone and characterized by carbon nuclear magnetic resonance (¹³C NMR) and differential scanning calorimetry. The polymers obtained by supported catalysts had a high fraction of boiling n‐butanone‐insoluble part and high melting temperatures, but ¹³C NMR results showed that syndiotacticity decreased compared with that of polymers prepared with an unsupported catalyst. ESR study on the supported catalysts confirmed that the active sites supported on the carrier dropped into the solution and formed active sites the same as those in the unsupported system when they reacted with methylaluminoxane. ¹³C NMR analysis showed that the polymerization mechanism of the supported active sites was an active‐site controlled mechanism instead of a chain‐end controlled mechanism of the unsupported active sites. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 127–135, 2000     

Solid‐State NMR investigations of anhydrous proton‐conducting acid–base poly(acrylic acid)– poly(4‐vinyl pyridine) polymer blend system: A study of hydrogen bonding and proton conduction

NMR studies of the structure and dynamics of a system composed of the acidic polymer poly(acrylic acid) (PAA) and the basic polymer poly(4‐vinyl pyridine) (P4VP) are presented. This system aims at the application of anhydrous proton‐conducting membranes that can be used at elevated temperatures at which the proton conduction of hydrated membranes breaks down. The ¹H NMR measurements have been preformed under fast magic angle spinning (MAS) conditions to achieve sufficient resolution and the applied ¹H NMR methods vary from simple ¹H MAS to double‐quantum filtered methods and two‐dimensional ¹H double‐quantum spectroscopy. The dynamic behavior of the systems has been investigated via variable temperature ¹H MAS NMR. ¹³C cross‐polarization MAS NMR provides additional aspects of dynamic and structural features to complete the picture. Different types of acidic protons have been identified in the studied PAA‐P4VP systems that are nonhydrogen‐bonded free acidic protons, hydrogen‐bonded dicarboxylic dimers, and protons forming hydrogen bonds between carboxylic protons and ring nitrogens. The conversion of dimer structures in dried PAA to free carboxylic acid groups is accomplished at temperatures above 380 K. However, the stability of hydrogen‐bonding strongly depends on the hydration level of the polymer systems. The effect of hydration becomes less apparent in the complexes. An inverse proportionality between hydrogen‐bonding strength and proton conduction in the PAA‐P4VP acid–base polymer blend systems was established. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 138–155, 2009     

Copolymerization of 1‐hexene and ethylene catalyzed by the Ziegler catalyst Cp*TiMe3/B(C6F5)3

The Ziegler–Natta system Cp*TiMe₃/B(C₆F₅)₃ catalyzed the copolymerization of ethylene and 1‐hexene in toluene into materials that were characterized by ¹H and ¹³C{¹H} NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. The effects of temperature and ethylene/1‐hexene and olefin/catalyst ratios on catalyst activities and copolymer molecular weights and molecular weight distributions were studied; the ethylene proportions varied from less than 5% to 85% or more. In addition, significant amounts of 1‐hexene were incorporated into the growing polymer chain in a 2,1‐fashion; consequently, conventional ¹³C NMR analytical methodologies for deducing monomer proportions and dispersions and polymer microstructures, based on a low 1,2‐incorporation of α‐olefin, did not work very well. A soluble (in toluene at ambient temperature) but very high molecular weight (weight‐average molecular weight ∼ 8 × 10⁵, weight‐average molecular weight/number‐average molecular weight = 1.8) rubbery copolymer that formed at −78 °C exhibited a predominantly alternating microstructure. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3966–3976, 2000     

Investigation of Catalyst Fragmentation in Gas‐Phase Olefin Polymerisation: A Novel Short Stop Reactor

Summary: A short stop reactor (SSR) was developed to study nascent particle morphology and reaction kinetics in the gas‐phase polymerisation of olefins on supported catalysts. It is shown that the SSR provides a useful means to look into important phenomena such as catalyst fragmentation and catalyst site activation and deactivation that take place during the very early stages of the heterogeneous polymerisation of olefins. New experimental results obtained from gas‐phase polymerisation of ethylene show that, depending on the type of catalyst system and on the reaction conditions, different kinds of morphologies can be obtained for the nascent polymer (e.g., cracks and folded chain). Experimental data also indicate that the growth of the polymer chains occur at a non‐steady state during the very early stages of the polymerisation.

SEM image showing the morphology of a polymer/catalyst particle after 2 seconds of polymerisation at 8 bars of ethylene on an MgCl₂‐supported Ziegler‐Natta catalyst.     

Synthesis,structures, and thermal properties of terpolymers of propylene oxide,carbon dioxide,and cyclohexene oxide

High molecular weight block terpolymers with different contents of polypropylene carbonate and cyclohexene carbonate units in the polymer chain were synthesized by the copolymerization of carbon dioxide, propylene oxide, and cyclohexene oxide. Zinc adipate was used as a catalyst. The terpolymerization products were characterized by ¹H and ¹³C NMR spectroscopy, IR spectroscopy, GPC, DSC, and DMA methods. The influence of the reaction conditions on the composition, microstructure, and molecular-weight and thermal characteristics was studied.

     

Effect of valence state of vanadium on stereoblock polymerization of methyl methacrylate with VOCl3–AlEt2Br catalyst system

The polymerization of methyl methacrylate with the VOCL₃–ALEt₂Br catalyst system in n-hexane has been studied. The first-order dependence of rate of polymerization on catalyst and monomer concentrations, activation energy of 6.67 kcal/mole, and NMR spectra of polymer lend support to a coordinate anionic mechanism of polymerization. It has been shown that the vanadium in V⁺² oxidation state is less active than V⁺³ oxidation state of active complex.     

Carbothermal synthesis of ultra-fine zirconium carbide powders using inorganic precursors via sol–gel method

Ultra-fine zirconium carbide (ZrC) powders have been synthesized by carbothermal reduction reactions using inorganic precursors zirconium oxychloride (ZrOCl₂ · 8H₂O) as sources of zirconium and phenolic resin as the carbon source. The reactions were substantially completed at relatively lower temperatures (∼1400 °C/1 h) and the synthesized powders had a small average crystallite size (<200 nm) and a large specific area (54 m²/g). The oxygen content of the powder synthesized at 1400 °C/1 h was less than 1.0 wt%. The thermodynamic change process in the ZrO₂–C system and the synthesis mechanism were studied.     

Proline‐based polymeric monoliths: Synthesis,characterization, and applications as organocatalysts in aldol reaction

Proline‐based polymer monoliths were synthesized via green protocol using lipase‐catalyzed esterification of methacrylic acid and 4‐hydroxyproline. Prolinyl methacrylate thus prepared was polymerized in situ as crosslinked monolith. The monolith was characterized by various techniques such as Fourier transform infrared, ¹H‐NMR, ¹³C‐NMR, scanning electron microscopy (SEM), X‐ray diffraction (XRD), and nitrogen analysis and used as catalyst in aldol reactions. The swelling behavior of the monolith was also studied as function of various external parameters like pH and temperature. The monoliths synthesized with 1% crosslinker was selected as candidate monolith for use as catalyst in aldol reaction, which was studied as a function of time, temperature, substrate structure, and amount of water:EtOH. The catalysts exhibited high efficiency in the cross aldol reaction, especially with the aromatic substrates having electron withdrawing substituent, and also good activity retention was observed when recycleability was studied up to five cycles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1007–1015, 2010     

Polymerization of methyl methacrylate by 2‐pyrrolidinone and n‐dodecyl mercaptan

The bulk polymerization of methyl methacrylate initiated with 2‐pyrrolidinone and n‐dodecyl mercaptan (R‐SH) has been explored. This polymerization system showed “living” characteristics; for example, the molecular weight of the resulting polymers increased with reaction time by gel permeation chromatographic analysis. Also, the polymer was characterized by Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR techniques. The polymer end with the iniferter structures was found. By the initial‐rate method, the polymerization rate depended on [2‐pyrrolidinone]^1.0 and [R‐SH]⁰. Combining the structure analysis and the polymerization‐rate expression, a possible mechanism was proposed. n‐Dodecyl mercaptan served dual roles—as a catalyst at low conversion and as a chain‐transfer agent at high conversion. Finally, the thermal properties were studied, and the glass‐transition temperature and thermal‐degradation temperature were, respectively, 25 and 80–100 °C higher than that of the azobisisobutyronitrile system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3692–3702, 2002     

s‐Triazine‐based hyperbranched polyethers: Synthesis,characterization, and properties

A series of s‐triazine‐based hyperbranched polyethers (HBPE) have been synthesized to obtain thermostability but flexible polymers by an interfacial polycondensation of different diols as A₂ and cyanuric chloride as B₃ monomers using A₂ + B₃ approach in the presence of a phase transfer catalyst. The polymerization reaction parameters are optimized, and the results indicate that the optimum conditions for the interfacial polycondensation are a 2:3 mole ratio of cyanuric chloride to diol using butanediol, benzyldimethylhexadecyl ammonium chloride as the catalyst, dichloromethane as the organic solvent, and a three‐step procedure with keeping the reaction mixture at different low temperatures for 2h/2h/5h. Other techniques such as high‐temperature solution, one‐step polycondensation, and transesterification were also carried out to synthesize the HBPE but proved to be not suitable due to large number of side reactions. The synthesized polymers were characterized by FTIR, ¹H NMR, and ¹³C NMR spectroscopy, hydroxyl number determination, solution viscosity measurements, and GPC analysis. The thermal behavior of the hyperbranched polymer was investigated by thermogravimetric analysis and differential scanning calorimetry. All the results were compared with those from an analogous linear polyether, obtained from 2‐methoxy‐4,6‐dichloro‐s‐triazine and butanediol by using the same polymerization technique. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3994–4004, 2010     

SYNTHESIS AND POLYMERIZATION OF BISPHENYLENE ORTHOCARBONATE

Bisphenylene orthocarbonate (Ⅱ) was synthesized by the reaction of dicopper catecholate with carbon tetrachloride, and underwent cationic ring-opening polymerization with the introduction of phenyl group into the main chain. The obtained polymer with ester and ether group was verified by IR and ~1H NMR spectra. Based on the analysis of the polymer structures, the polymerization mechanism was proposed. Its T_m and T_(?) are 254℃and 160℃respectively. No decomposition of the polymer was observed below 320℃. The volume expansion property of the monomer during polymerization was studied by measuring the density difference between Ⅰand its polymer at various temperatures.     

NMR and FT-IR Investigation of Spinel LiMn2O4 Cathode Prepared by the Tartaric Acid Gel Process

The structure of the lithium manganese tartrate precursor and the synthesis mechanism of LiMn₂O₄ were investigated by FT-IR, NMR, TG/DSC, and XRD in this study. The results of FT-IR and ⁷Li and ¹³C NMR measurements revealed that lithium ions bond with carboxylic acid ligands and the O–H stretching modes of tartaric acid. Manganese ion bonds only with carboxylic acid. Lithium and manganese ions were trapped homogeneously on an atomic scale throughout the precursor. Such a structure eliminates the need for long-range diffusion during the formation of lithium manganese oxides. Therefore, spinel LiMn₂O₄ was synthesized at temperatures as low as 300°C. In this work, the electrochemical properties of Li/Li_xMn₂O₄ were studied. It is clear that the discharge curves exhibit two pseudo plateaus as the LiMn₂O₄ is fired to higher temperatures. The discharge capacity of LiMn₂O₄ increases from 84 to 117 mAh/g as the calcination temperature increases from 300 to 500°C. The LiMn₂O₄ powders calcined at low temperatures with a high specific surface area and an average valence of manganese exhibit a better cycle life.