Search results for "Solution polymerization"

Surfactant Assisted Polymerization of Tetrafluoroethylene in Supercritical Carbon Dioxide with a Pilot Scale Batch Reactor.

2008

Chain-free radical polymerization of tetrafluoroethylene (TFE) was carried out in supercritical carbon dioxide (scCO2), at 50 °C and 121–133 bar, with tertiary-amyl-per-pivalate as a free radical initiator, using a 5-L pilot scale batch reactor. Experiments were carried out both in the absence and in the presence of perfluoropolyether (PFPE) carboxylate surfactants. Stabilizers were employed under the free acid form and as sodium and calcium salts. An expanded fibrillated poly(TFE) was obtained in all experiments. In the case of surfactant-free polymerizations, the product was mainly constituted by irregular shape macroparticles having size in the range 200–500 μm. Quite interestingly, when…

1977

The solution polymerization of styrene in methylene dichloride catalysed by trifluoromethanesulfonic acid takes place at a high rate even at low catalyst concentration. The S-shaped course of the conversion curves is explained by a reaction mechanism, in which the catalyst rapidly forms an inactive complex with one monomer molecule, and this monomer-acid complex is in equilibrium with the free catalyst molecule from which the propagating species are formed. Therefore, the formation of active initiating species becomes a slow process which depends also on the change of monomer concentration during polymerization. It is assumed that the active initiating species are formed from two or three m…

1988

The structure of 1-azabicyclo[4.2.0]octane (1) was evaluated by NMR spectroscopy. It was found that the six-membered ring has a chair conformation with the four membered ring in the N-axial and C-6-equatorial position, and as a consequence, the monomer allows neither a ring inversion nor a nitrogen inversion. It possesses two centers of chirality, one at the nitrogen atom and one at C-6. Homopolymerization was carried out in methanol at 60°C with N-alkyl ammonium salts of 1 affording the polymer in high yield within a few hours. Its NMR spectra reveal that the polymer chain is preferably arranged in the biequatorial position of the six-membered ring. As a polybase the polymer can be titrate…

1984

A dimeric biradical •M plays a central role in the initiation of the spontancous polymerization of methyl methacrylate (M1). Besides the initiation step by chain transfer reaction, a change of the multiplicity of ˙M seems to be of importance. Evidence is given by heavy atoms in the solvent or in an inert gas atmosphere, leading to an acceleration of the overall polymerization rate. The observed effect is related to the atomic number of the respective heavy atom. Measurements of the temperature dependence of the effect for carbon tetrachloride show that — as expected — no activation energy is needed for this reaction step. The results are summarized in a reaction scheme for the initiation me…

1990

The effect of lithium tert-butoxide (t-BuOLi) on rate constants and equilibrium constants of reactions involved in the initial stage of the anionic polymerization of methyl methacrylate (MMA) in tetrahydrofuran, initiated by methyl α-lithioisobutyrate (P) was investigated at 23 ± 3°C. Addition of t-BuOLi decreases the rate constants of initiation and propagation by one order of magnitude; the rate constants of termination by cyclization decrease by two orders of magnitude. This leads to an overall tenfold higher preference of propagation with respect to termination and explains the favourable effect of alkoxide in the polymerization reported earlier. Within experimental error, the equilibri…

Vanadium-based Ziegler-Natta catalyst supported on MgCl2(THF)2 for ethylene polymerization

1996

A supported magnesium‐vanadium‐aluminium catalyst was prepared by depositing –with the use of a milling technique–VOCl3 on the MgCl2(THF)2 support and subsequent activation with diethylaluminium chloride. Catalytic activity of the obtained system for ethylene polymerization was evaluated as a function of Mg/V and Al/V ratios as well as catalyst ageing time and polymerization temperature. High concentrations of THF in the catalytic system and considerable excess of an organoaluminium co‐catalyst were found to have no deactivating action on vanadium active sites. The catalyst obtained is stable and its activity for ethylene polymerization is high. It yields polyethylene with higher molecular …

Measurements on the temperature dependence of the cationic polymerization of styrene in CH2Cl2 with CF3SO3H as catalyst

1979

The cationic polymerization of styrene in CH2Cl2 with CF3SO3H as catalyst and at low monomer concentrations shows, at −15°C, −45°C and −60°C, the same formal dependence on monomer concentration. The dependence on the catalyst concentration is approximately but not exactly of a third order.

A supported titanium postmetallocene catalyst: Effect of selected conditions on ethylene polymerization

2011

Ethylene polymerization with a titanium complex [N,N-ethylenebis(3-methoxysalicylideneiminato)titanium dichloride] immobilized on the magnesium support with the formula MgCl2(THF)0.32(Et2AlCl)0.36 was studied. In particular, the effects of polymerization temperature, monomer pressure, and polymerization time on the activity of the catalyst and on the polyethylene properties (molecular weight and its distribution, melting point, crystallinity, and bulk density) were evaluated. The findings of investigations prove that the studied supported titanium catalyst is highly active in ethylene polymerization, and its activity increases with increasing temperature and monomer pressure. Moreover, stab…