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Propagation Reaction (propagation + reaction)
Selected AbstractsFluorenyl based syndiotactic specific metallocene catalysts structural features, origin of syndiospecificityMACROMOLECULAR SYMPOSIA, Issue 1 2004Abbas Razavi Abstract The stereochemistry of propylene insertion/propagation reactions with a variety of Cs symmetric fluorenyl- containing single site catalysts is discussed. Our recent results indicate that independent of the chemical composition of the ancillary ligand fragments, or nature of the transition metal, active sites with local Cs symmetry and enantiotopic coordination positions behave syndioselectively in the general context of chain migratory insertion mechanism. Perfect bilateral symmetry neither exists nor is required in these processes. In this context the mechanism of syndiospecific polymerization is revisited by taking into account the structural characteristics and catalytic behavior of the original metallocene based (,5 -C5H4 -CMe2 -,5 -C13H8) MCl2/ MAO; M = Zr (1), Hf (2) catalyst systems and new syndiotactic specific systems including (,5 -C5H4 -CPh2-,5-3,6-di-tBut-C13H6)ZrCl2 (3), ,1,,5 -(,Me2Si)(3,6-di-tBut-Flu)(t-ButN)MCl2/ MAO; M =Ti (4), Zr (5) and ,1,,5 -(,Me2Si)(2,7-di-tBut-Flu)(t-ButN)MCl2/ MAO; M = Ti (6), Zr (7). [source] Hydrogen-bond-assisted stereocontrol in the radical polymerization of N -isopropylacrylamide with primary alkyl phosphate: The effect of the chain length of the straight ester groupJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2005Tomohiro Hirano Abstract The radical polymerizations of N -isopropylacrylamide (NIPAAm) were carried out in toluene at low temperatures in the presence of phosphoric acid esters such as trimethyl phosphate, triethyl phosphate (TEP), tri- n -propyl phosphate, and tri- n -butyl phosphate (TBP). Syndiotactically rich poly(NIPAAm)s were obtained from ,60 to 0 °C, and TEP provided the highest syndiotacticity (racemo dyad = 65%) at ,40 °C. On the other hand, lowering the temperature reversed the stereoselectivity of the propagation reaction so that isotactically rich poly(NIPAAm)s were obtained at ,80 °C. In particular, TBP exhibited the most isotactic specificity (meso dyad = 57%). Job's plots for NIPAAm,TBP mixtures revealed that NIPAAm and TBP formed a 1:1 complex at 0 °C and a predominantly 1:2 complex at ,80 °C through a hydrogen-bonding interaction. Therefore, the stereospecificity of NIPAAm polymerization should depend on the stoichiometry of the hydrogen-bond-assisted complex. Thus, the mechanism for this polymerization system was discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 50,62, 2005 [source] A New View of the Anionic Diene Polymerization MechanismMACROMOLECULAR SYMPOSIA, Issue 1 2004A.Z. Niu Abstract We investigated the anionic polymerization of butadiene in d-heptane solvent using tert -butyl lithium as initiator. Two complementary techniques were used to follow the polymerization processes: 1H NMR and small angle neutron scattering (SANS). The time resolved 1H NMR measurements allowed us to evaluate quantitatively the kinetics of the processes involved. The initiation event commences slowly and then progressively accelerates. This indicates an autocatalytic mechanism. The microstructure of the first monomer units attached is to a high extent 1,2. The disappearance of initiator --- at about 10% monomer conversion --- signals the onset of the normal ,6% vinyl content of the chain. Small angle neutron scattering was used to study the aggregation behavior of the carbon lithium head groups. It is well known that the polar head groups aggregate and form micellar structures. For dienes in non-polar solvents the textbook mechanism assumes the formation of only tetramers during the propagation reaction. By combining 1H NMR and SANS results we were able to determine quantitatively the aggregation number during all stages of the polymerization. Our measurements show the existence of large-scale structures during the initiation period. The initial degree of aggregation of more than 100 living polymer chains diminished as the polymerization progressed. In addition, even larger, giant structures with Nagg >>1000 and Rg , 1000Å were found. [source] Aluminate and Magnesiate Complexes as Propagating Species in the Anionic Polymerization of Styrene and DienesMACROMOLECULAR SYMPOSIA, Issue 1 2004Alain Deffieux Abstract The influence of MgR2 and AlR3 additives on alkyllithium initiators in the anionic polymerization of butadiene has been investigated in non polar solvents. A strong decrease of the diene polymerization rate in the presence of the two Lewis acids was observed, similarly to that observed in the retarded anionic polymerisation of styrene. With n,s-Bu2Mg, the percentage of 1,2 vinyl units increases with the [Mg]/[Li] ratio. This behavior is specific to magnesium derivatives bearing secondary alkyl groups and likely results from the additional complexation of lithium species by free dialkylmagnesium and/or a 1,4- to 1,2- chain end isomerization process during chain exchanges between polybutadienyl active chains and dormant ones attached to magnesium species. These reversible exchanges also lead to the formation of one supplementary chain by initial dialkyl magnesium which acts as reversible chain transfer agent. On the contrary with the R3Al/RLi systems the number of chains is only determined by the concentration of initial alkyllithium and no modification of the polybutadiene microstructure compared to lithium initiators (1,4 units = 80%) is noticed. Dialkyl magnesiate complexes with alkali metal derivatives (i.e. alkoxide) are also able to influence the stereochemistry of the styrene insertion during the propagation reaction. Polystyrenes with different tacticities ranging from predominantly isotactic (85% triad iso) to syndiotactic (80% triad syndio) can be obtained with these initiators. [source] Modeling of Slurry Polymerization of Ethylene Using a Soluble Cp2ZrCl2/MAO Catalytic SystemMACROMOLECULAR THEORY AND SIMULATIONS, Issue 5 2007Mostafa Ahmadi Abstract The slurry homopolymerization of ethylene catalyzed by a Cp2ZrCl2/MAO catalytic system was studied. A simple kinetic model including initiation, propagation, transfer to monomer and cocatalyst, spontaneous transfer and spontaneous deactivation was developed to predict dynamic yield of polymerization and molecular weight of final products. Kinetic constants were estimated by numerical solution of polymerization kinetic model, combined with Nelder-Mead simplex method. The model predicts that the propagation reaction has the lower activation energy in relation to chain transfer reactions which leads to decrease of molecular weight at elevated temperatures. The initiation reaction has however, the highest activation energy that results in raising the peak of reaction rate at higher temperatures. [source] Anionic ring-opening polymerization of small phosphorus heterocycles and their borane adducts: An ab initio investigationHETEROATOM CHEMISTRY, Issue 2 2007Michelle L. Coote The kinetics and thermodynamics of anionic ring-opening reactions of phosphiranes, phosphetanes, and phospholanes and their borane adducts have been studied by high-level ab initio procedures. For the free heterocycles, model propagation reactions involving nucleophilic attack by Me2P, at the ring ,-carbon were found to be feasible for the three- and four-membered rings, but not for the five-membered ring. For the borane adducts, nucleophilic attack by Me2(BH3)P, was only facile for the three-membered ring, despite an increased thermodynamic tendency toward ring opening for the borane adducts of both the three- and four-membered rings. The formation constants of the borane adducts of methylphosphirane and methylphosphetane were K = 2.6 × 1013 L mol,1 and K = 1.2 × 1020 L mol,1, respectively. A Marcus analysis of the ring-opening reactions of methylphosphirane, methylphosphetane, and their borane adducts showed that the release of ring strain and an "additional factor" contribute to rate enhancement compared with their strain-free analogues. The additional factor was larger for the three-membered rings than for the four-membered rings and was larger in the free heterocycles than in their borane adducts. The additional factor is complex in origin and appears to reflect an increase in the separation between the bonding and antibonding orbitals of the breaking bond on going from the three-membered rings to the four-membered rings, and on going from the free heterocycles to the borane adducts. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:118,128, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20323 [source] Comparative study of kinetics and reactivity indices of free radical polymerization reactions,INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2005K. Van Cauter Abstract Density functional theory calculations are used to determine the kinetics and reactivity indices of the first propagation steps of the polyethylene and poly(vinyl chloride) polymerization. Transition state theory is applied to evaluate the rate coefficient from the microscopically determined energies and partition functions. A comparison with the experimental Arrhenius plots validates the level of theory. The ability of reactivity indices to predict certain aspects of the studied propagation reactions is tested. Global softnesses of the reactants give an indication of the relative energy barriers of subsequent monomer additions. The correlation between energy and hardness profiles along the reaction path confirm the principle of maximum hardness. Local indices predict the regioselectivity of the attack of the growing radical to vinyl chloride. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Synthesis and Characterization of Poly(N -vinylimidazole- co -acrylonitrile) and Determination of Monomer Reactivity RatiosMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 8 2004Nursel Pekel Abstract Summary: Radical-initiated solution copolymerization of N -vinylimidazole (VIM) and acrylonitrile (AN) was carried out with 2,2, -azobisisobutyronitrile (AIBN) as an initiator in benzene at 70,°C in nitrogen atmosphere. The structure and composition of synthesized copolymers for a wide range of monomer feeds were determined by FTIR, 1H and 13C NMR spectroscopy with the aid of recorded analytical absorption bands for VIM (667 cm,1, CN of imidazole ring) and AN (2,242 cm,1, CN group), as well as by using the areas of proton and carbon atom signals from corresponding functional groups of monomer units. Monomer reactivity ratios for VIM (M1)-AN (M2) pair were determined by nonlinear regression (NLR), Kelen,Tüdös (KT) and Fineman,Ross (FR) methods. They were found to be r1,=,0.24 and r2,=,0.15 for the NLR method, r1,=,0.22 and r2,=,0.094 for the KT method, and r1,=,0.24 and r2,=,0.12 for the FR method, respectively. The relatively high activity observed of VIM growing macroradical and the results of FTIR and 1H NMR structural analysis of copolymers suggest the formation of complexed linkages between monomers and growing radicals in chain propagation reactions. Similar complexation between monomer,comonomer units in the structure of formed macromolecules showed an increase in isotactic triad fractions in the copolymer. Complex formation between the imidazole ring and nitrile group in both the monomer mixture and chain growing reactions. [source] | |||||||||||||