Search results for "Solution polymerization"

1987

ESR spectroscopic analyses of the deep-green solutions of living poly(2-isopropenylnaphthalene) [poly(2-IPN)] in THF at −80°C provided no evidence of the presence of radical anions as long as butyllithium (BuLi) was used as initiator. In contrast to this finding, radicals could indeed be detected if the polymerization was performed with metallic potassium in THF. These radicals were found to be only stable at low temperatures. UV/VIS spectra of solutions of 2-IPN in THF or toluene and of catalytic quantities of BuLi were recorded at temperatures between −45 and +20°C. On heating to >0°C, the colour of the deep-green solution changes irreversibly to reddish-brown, and this colour change is a…

1990

The anionic polymerization of tert-butyl acylate (tBuA) initiated by tert-butyl α-lithioisobutyrate was investigated in THF at 25°C. The individual oligomers were isolated and characterized by UV, IR and NMR spectroscopy. The distribution of products was determined in the range of reaction times 0,02 s ≤ t ≤ 1800 s. The oligomerization is extremely fast. Even after 0,02 s at -30°C, no residual monomer could be detected. After short reaction times the reaction mixture almost exclusively consists of linear oligomers of tBuA. This indicates that there is no termination reaction by Claisen condensation during polymerization. Nevertheless, the molecular weight distribution is rather broad (Mw/Mn…

1987

1987

Dichlorovanadium (IV) complexes with salen-type ligands for ethylene polymerization

2008

Vanadium complexes with tetradentate salen-type ligands were first time explored in ethylene polymerizations. The effects of the vanadium complex structure, the alkyl aluminum cocatalysts type (EtAlCl2, Et2AlCl, Et3Al, and MAO), and the polymerization conditions (Al/V molar ratio, temperature) on polyethylene yield were explored. It was found that EtAlCl2 in conjunction with investigated vanadium complexes produced the most efficient catalytic systems. It was shown, moreover, that the structural changes of the tetradentate salen ligand (type of bridge which bond donor nitrogen atoms and type of substituent on aryl rings) affected activity of the catalytic system. The complexes containing li…

Ethylenebis(5-chlorosalicylideneiminato)vanadium dichloride immobilized on MgCl2 -based supports as a highly effective precursor for ethylene polymer…

2009

Ethylenebis(5-chlorosalicylideneiminato)vanadium dichloride supported on MgCl2(THF)2 or on the same carrier modified by EtnAlCl3−n, where n = 1–3, was used in ethylene polymerization in the presence of MAO or a common alkylaluminium compounds as a cocatalyst. The support type alter vanadium loading and also change the characteristic of the catalytic active sites. Et2AlCl is the best activator for a catalyst which has been immobilized on a nonmodified support, whereas the systems which contain a carrier which has been modified by an organoaluminium compound reveal the highest activity in conjunction with MAO. That difference, together with different temperature effects on polymerization effi…

Ethylene polymerization with FI complexes having novel phenoxy-imine ligands: Effect of metal type and complex immobilization

2011

A series of bis(phenoxy-imine) vanadium and zirconium complexes with different types of R3 substituents at the nitrogen atom, where R3 = phenyl, naphthyl, or anthryl, was synthesized and investigated in ethylene polymerization. Moreover, the catalytic performance was verified for three supported catalysts, which had been obtained by immobilization of bis[N-(salicylidene)-1-naphthylaminato]M(IV) dichloride complexes (M = V, Zr, or Ti) on the magnesium carrier MgCl2(THF)2/Et2AlCl. Catalytic performance of both supported and homogeneous catalysts was verified in conjunction with methylaluminoxane (MAO) or with alkylaluminium compounds (EtnAlCl3−n, n = 1–3). The activity of FI vanadium and zirc…

Styrene polymerization using nickel(II) complexes as catalysts

2005

International audience; Styrene polymerization is investigated with neutral and cationic Ni(II) complexes, i.e. Ni(bipy)Me-2, 1, Ni(bipy)Br-2, 2, Ni(phen)Br-2, 3, or Ni(Me(2)phen)Br-2, 4, Ni(acac)(2), 5, (bipy = 2,2 '-bipyridine, phen = phenanthroline, Me,phen = 2,9-dimethyl-1, 10-phenanthroline, acac acetylacetonate), activated by [NHMe2Ph][B(C6F5)(4)] or B(C6F5)(3) as cocatalysts, in the presence of AlMe3. The influence on the polystyrene features and the reaction kinetics of the nickel complex and boron activator, the Al/Ni or B/Ni molar ratios as well as the monomer concentration are studied. Catalytic systems derived from 2, 3 or 5 and [NHMe2Ph][B(C6F5)(4)] at a Ni:B:Al ratio of 1: 1:5…

Cyclodextrins in Polymer Synthesis:  Influence of Acrylate Side Groups on the Initial Rate of Radical Polymerization of Various Acrylate/Methylated β…

2001

Methylated β-cyclodextrin was used to complex the hydrophobic monomers n-propyl acrylate (1), n-butyl acrylate (2), n-pentyl acrylate (3), n-hexyl acrylate (4), and cyclohexyl acrylate (5) respectively yielding the corresponding water-soluble host/guest-complexes 1a−5a. The complexes were polymerized in water by free radical mechanism and the initial polymerization rates (v0) determined. We found that v0 increases as follows:  1a (12.5), 2a (27.5), 3a (44.2), 5a (49.4), 4a (75.8 × 10-6 mol·L-1·s-1). To investigate the influence of the hydrophobic character of the guest monomers on the reaction rate, the water solubilities of the uncomplexed monomers 1−5 were determined by HPLC measurements.…

Synthesis and characterization of well-defined poly(tert-butyl acrylate) star polymers

2009

Abstract Star polymers with different numbers and lengths of poly(tert-butyl acrylate) (PTBA) arms were obtained via atom transfer radical polymerization. Aliphatic alcohols with different number of hydroxyl groups varying from 3 to 6 and calix[4]arenes based on pyrogallol with 12 and 16 phenol groups were transformed to bromoester derivatives to prepare multifunctional ATRP initiators used as the cores of the stars. The star polymers were characterized by GPC with refractive index, multiangle laser light scattering and viscosimetric detectors. The molar masses of the stars reached 70,000 g/mol and the molar mass dispersities did not exceed 1.2. To elucidate the compact structure of the sta…