Search results for "Chain propagation"

Current views on the mechanism of catalytic cracking

2000

Abstract The cracking mechanisms of hydrocarbons have been reviewed and the kinetic and thermodynamic implications of the different steps, i.e. initiation, chain propagation, and termination, have been discussed. Although the cracking mechanism of olefins and alkylaromatics is well established, the initiation step for the cracking of paraffins is still under debate. The role of Bronsted-type active sites and also the possible influence of extra-framework Al species in the case of zeolite catalysts, especially when commercial feeds and industrial conditions are employed, are presented. The product distribution is determined by the number of propagation events occurring per initiation step, a…

Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains

2012

The reaction in water of cobalt(II), nickel(II) or manganese(II) chloride with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na 4 P 2 O 7 ) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H 2 O)(H 2 P 2 O 7 )]·H 2 O} n with M = Co( 1 ), Ni( 2 ) and Mn( 3 ). The di-hydrogen-pyrophosphate anion featured in these complexes adopts a rare bidentate/monodentate bridging mode leading to chain propagation. This unusual bridging pathway produces a metal–metal intra-chain separation of about 6.6–6.7 A for 1 – 3 , values much larger than the metal–metal distance across the classic bis-bidentate PPi in the parent…

Diene-Containing Half-Sandwich MoIII Complexes as Ethylene Polymerization Catalysts: Experimental and Theoretical Studies

2001

International audience; Seventeen-electron compounds of Mo III having the general formula [(h 5-C 5 R 5)Mo(h 4-diene)X 2 ] (R H, Me; diene butadiene, iso-prene, or 2,3-dimethylbutadiene; X Cl, CH 3) are a new class of ethylene polymerization catalysts. The polyethy-lene obtained shows a bimodal distribution , the major weight fraction being characterized by very long (M around 10 6) and highly linear polymer chains. The newly prepared pentamethylcyclo-pentadienyl (Cp*) derivatives are more active than the cyclopentadienyl (Cp) derivatives, but much less active than previously investigated niobium III compounds having the same stoichiometry. On the other hand, the turnover frequency of the a…

Two-step polymerization of propylene over MgCl2-supported titanium catalyst

1998

The prepolymerization effect on propylene polymerization in the presence of a MgCl 2 -supported titanium catalyst was studied. The catalyst was pre-activated by polymerizing a small amount of propylene in the presence of Et 3 Al and cyclohexylmethyldimethoxysilane under mild conditions, and then it was used in a second step of propylene polymerization. Comparative studies of the polymerization process involving the investigated catalyst and its unmodified counterpart showed the rate-enhancement effect of prepolymerization and the same molecular weights, MWD's and isotacticities of the polymers obtained. Concentrations of active sites and propagation rate as well as transfer rate constants w…

1972

The determination of reactivity ratios is simplified by using an excess of one monomer (M1) at a time large enough that the copolymers will have a very small content of the other monomer (M2). In this case chain propagation takes place almost exclusively by addition to polymer radicals with a terminal M1-unit (P) and monomer consumption by propagation of P may be neglected. One reactivity ratio (r1) is obtained from monomer conversions by means of a simple integrated equation which is valid up to high conversions. A calculation is proposed in order to account for the neglected propagation via P. The other reactivity ratio (r2) is obtained from copolymerizations with excess M2. As the new me…

1973

The mechanism of radiation-induced polymerizations in the solid state has been a subject mostly open to speculation. As radiation usually generates several kinds of active species (radicals and ions) it is difficult to find out, which of these actually causes polymerization. We have developped a method distinguishing between cationic and anionic active centers. Cationic polymerizations are terminated by addition of a base such as sodium alkoxide in a suitable solvent. The alkoxide is incorporated into the polymer as an endgroup. This endgroup is determined analytically after isolation and purification of the polymer. The incorporation of alkoxy endgroups into the polymer is a proof of the o…