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Comonomer Incorporation (comonomer + incorporation)
Selected AbstractsEthylene/,-olefin copolymerization using diphenylcyclopentadienyl-phenoxytitanium dichloride/Al(iBu)3/[Ph3C][B(C6F5)4] catalyst systemsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008Hongchun Li Abstract Copolymerization of ethylene with 1-octene and 1-octadecene using constrained geometry catalysts 2-(3,4-diphenylcyclopentadienyl)-4,6-di- tert -butylphenoxytitanium dichloride (1), 2-(3,4-diphenylcyclopentadienyl)-6- tert -butylphenoxytitanium dichloride (2), 2-(3,4-diphenylcyclopentadienyl)-6-methylphenoxytitanium dichloride (3), and 2-(3,4-diphenylcyclopentadienyl)-6-phenylphenoxytitanium dichloride (4) was studied in the presence of Al(iBu)3 and [Ph3C][B(C6F5)4](TIBA/B). The effect of the catalyst structure, comonomer, and reaction conditions on the catalytic activity, comonomer incorporation, and molecular weight of the produced copolymers was also examined. The 1/TIBA/B catalyst system exhibits high catalytic activity and produces high molecular weight copolymers. The melting temperature and the degree of crystallinity of the copolymers show a decrease with the increase in the comonomer incorporation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Ethylene polymerization and ethylene/hexene copolymerization with vanadium(III) catalysts bearing heteroatom-containing salicylaldiminato ligandsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2009Ji-Qian Wu Abstract A series of novel vanadium(III) complexes bearing heteroatom-containing group-substituted salicylaldiminato ligands [RNCH(ArO)]VCl2(THF)2 (Ar = C6H4, R = C3H2NS, 2a; C7H4NS, 2c; C7H5N2, 2d; Ar = C6H2tBu2 (2,4), R = C3H2NS, 2b) have been synthesized and characterized. Structure of complex 2c was further confirmed by X-ray crystallographic analysis. The complexes were investigated as the catalysts for ethylene polymerization in the presence of Et2AlCl. Complexes 2a,d exhibited high catalytic activities (up to 22.8 kg polyethylene/mmolV h bar), and affording polymer with unimodal molecular weight distributions at 25,70 °C in the first 5-min polymerization, whereas produced bimodal molecular weight distribution polymers at 70 °C when polymerization time prolonged to 30 min. The catalyst structure plays an important role in controlling the molecular weight and molecular weight distribution of the resultant polymers produced in 30 min polymerization. In addition, ethylene/hexene copolymerizations with catalysts 2a,d were also explored in the presence of Et2AlCl, which leads to the high molecular weight and unimodal distributions copolymers with high comonomer incorporation. Catalytic activity, comonomer incorporation, and polymer molecular weight can be controlled over a wide range by the variation of catalyst structure and the reaction parameters, such as comonomer feed concentration, polymerization time, and polymerization reaction temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3573,3582, 2009 [source] Ethylene/,-olefin copolymerization with bis(,-enaminoketonato) titanium complexes activated with modified methylaluminoxaneJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2005Li-Ming Tang Abstract Copolymerizations of ethylene with ,-olefins (i.e., 1-hexene, 1-octene, allylbenzene, and 4-phenyl-1-butene) using the bis(,-enaminoketonato) titanium complexes [(Ph)NC(R2)CHC(R1)O]2TiCl2 (1a: R1 = CF3, R2 = CH3; 1b: R1 = Ph, R2 = CF3; and 1c: R1 = t -Bu, R2 = CF3), activated with modified methylaluminoxane as a cocatalyst, have been investigated. The catalyst activity, comonomer incorporation, and molecular weight, and molecular weight distribution of the polymers produced can be controlled over a wide range by the variation of the catalyst structure, ,-olefin, and reaction parameters such as the comonomer feed concentration. The substituents R1 and R2 of the ligands affect considerably both the catalyst activity and comonomer incorporation. Precatalyst 1a exhibits high catalytic activity and produces high-molecular-weight copolymers with high ,-olefin insertion. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6323,6330, 2005 [source] Structure,property transition-state model for the copolymerization of ethene and 1-hexene with experimental and theoretical applications to novel disilylene-bridged zirconocenesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2003Hanne Wigum Abstract Ethene homopolymerization and copolymerization with 1-hexene were performed with three new tetramethyldisilylene-bridged zirconocene catalysts with 2-indenyl ligand (A), 2-tetrahydroindenyl ligand (B), and tetramethyl-cyclopentadienyl ligand (C) and with methylaluminoxane as a cocatalyst. Catalysts A and B showed substantial comonomer incorporation, resulting in a copolymer melting temperature more than 20° lower than that of the corresponding homopolymer. In contrast, catalyst C produced a copolymer with a low 1-hexene content and a high melting temperature. The reduction in the molecular weight with 1-hexene addition also correlated well with the comonomer incorporation. For all three catalysts, the homopolymer and copolymer unsaturations indicated frequent chain termination after 1-hexene insertion and a high degree of chain-end isomerization during the homopolymerization of ethene. The chain transfer to Al in the cocatalyst also appeared to be important. The comonomer response could be correlated with the structural properties of the catalyst, as derived from quantum chemical calculations. A linear model, calibrated against recent experiments with unbridged (MenC5H5,n)2ZrCl2 catalysts, suggested that the low comonomer incorporation obtained with catalyst C was caused partly by a narrow opening angle between the aromatic ligands and partly by steric hindrance in the transition state of comonomer insertion. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1622,1631, 2003 [source] Characterization of Ethylene-1-Hexene Copolymers Made with Supported Metallocene Catalysts: Influence of Support TypeMACROMOLECULAR SYMPOSIA, Issue 1 2007Beatriz Paredes Abstract Summary: It is known that the nature of the support, as well as the technique used to anchor the metallocene onto it, play important roles on catalytic activity and on the properties of the polymers produced with supported metallocenes. In the present work, the effect of different support types on the microstructure of ethylene/1-hexene copolymers made with supported metallocene catalysts has been investigated through the analysis of molecular weight and chemical composition distributions using high temperature gel permeation chromatography (GPC) and crystallization analysis fractionation (Crystaf). The copolymer samples obtained using commercial carriers (silica and silica-alumina) had unimodal chemical composition distributions and were used to create a linear calibration curve relating the peak crystallization temperature from Crystaf and the comonomer content as determined by 13C NMR. This calibration curve is useful to determine the 1-hexene fractions for each peak in the resins showing bimodal chemical composition distributions, such as those obtained with catalysts supported on MCM-41 and SBA-15 materials. The structure and chemistry of the support used had a large influence on comonomer incorporation and the shape of the chemical composition distribution of the polymer, which suggests that the supporting process creates different types of active sites. [source] Synthesis and Characterization of Ethylene/Propylene Copolymers in the Whole Composition RangeMACROMOLECULAR SYMPOSIA, Issue 1 2007Ma. Joaquina Caballero Abstract Summary: The incorporation of comonomer molecules in the backbone of a homopolymer can influence the final properties of the material, decreasing its crystallinity and the melting and glass transition temperatures, and increasing its impact resistance and transparency. In the present work, ten ethylene/propylene copolymers have been synthesized using a supported metallocene catalytic system covering the whole composition range. Any desired composition was obtained by controlling the feed composition during the reaction. These synthesized copolymers have been characterized by different techniques in order to study the effect of the comonomer incorporation onto their final properties. When the comonomer content is low, the behaviour of the copolymer is similar to that of the corresponding homopolymer. Nevertheless, if the comonomer content increases, the copolymer becomes more amorphous (low crystallization temperature and soft XRD signals) and easily deformable, reaching a behaviour close to that corresponding to an elastomeric material. In order to corroborate these results the samples have been characterized by TREF and GPC-MALS. TREF analysis showed that copolymers containing less than 10% and more than 80% of ethylene are semicrystalline, with elution temperatures typical of this kind of polymers. Molecular weights are higher for homopolymers and they decrease as the comonomer concentration increases, whereas the polydispersity index keeps almost constant at the expected value for this kind of samples. [source] On-line monitoring and fingerprint technology: new tools for the development of new catalysts and polyolefin materialsMACROMOLECULAR SYMPOSIA, Issue 1 2004Arno Tuchbreiter Abstract The High-Output Polymer Screening (HOPS) combines process-relevant automated reactor systems and rapid polymer characterization with on-line polymerization monitoring and automated data acquisition ("electronic notebook") in order to make effective use of advanced data mining tools. This has led to the development of fingerprint technology based upon correlations between spectroscopic data and polymerization process conditions, catalyst compositions, as well as polymer end-use properties. Infrared spectroscopic fingerprints proved to be very useful for accelerating polymer analyses including characterization of polymer molecular architectures as well as non-destructive testing of the mechanical, thermal and other end-use polymer properties. Such spectroscopic fingerprints represent important components of effective on-line quality control systems. With ATR-FT-IR probes on-line monitoring of catalytic olefin copolymerization was performed in solution to measure in real time copolymerization kinetics, catalyst productivities, catalyst deactivation as well as copolymerization parameters and copolymer sequence distributions. Monomer consumption and comonomer incorporation were monitored simultaneously. Advanced fingerprint technology can reduce significantly the need for time- and money consuming polymer testing and can also stimulate the search for new catalyst systems and polymeric materials. [source] | ||||||||||