Search results for "Polymerization"

Branched and Functionalized Polybutadienes by a Facile Two-Step Synthesis

2008

Anionic polymerization was used to prepare silane-endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9 000 to 34000 g .mol- 1 . These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB 2 + A type "pseudocopolymerization" method. All branched polymers were analyzed by SEC, SEC-MALLS, SEC-viscosimetry…

Kinetic Analysis of “Living” Polymerization Processes Exhibiting Slow Equilibria. 5. Effect of Monomer Transfer in Cationic Polymerization and Simila…

1996

This work deals with the kinetics of polymerization processes with chain transfer to monomer and reversible formation of dormant species. Such a mechanism is typical for cationic polymerization in the presence of Lewis acids as co-initiators. The expressions of number- and weight-average degrees of polymerization and polydispersity index are derived rigorously for a mechanism with free ions as the active species, but it is also applied to other mechanisms, e.g., ion pairs as active species. Plots of polydispersity index versus monomer conversion can be easily computed on a PC computer even though the expressions for the weight-average degree of polymerization and the concentration of residu…

Reaktionskinetik der Polymerisationshemmung durch molekularen Sauerstoff

1957

Die Polymerisationshemmung geschieht bei Styrol nach demselben Mechanismus wie er kurzlich fur Methylmethacrylat berichtet wurde1. Wahrend der Inhibierungsperiode findet streng alternierende Copolymerisation zwischen molekularem Sauerstoff und dem monomeren Styrol statt. Die fur die Anlagerung von O2 an das Radikal RM · masgebende Konstante kMO2 ist etwa von der Grosenordnung 106–107, d. h. die Reaktionsfahigkeit des Sauerstoffs in dieser Reaktion entspricht der eines Radikals. Bruttogeschwindigkeit und kinetische Kettenlange wahrend der Inhibierungsperiode werden auf Grund des Reaktionsmechanismus berechnet und experimentell bestatigt. The inhibition mechanism in the polymerization of styr…

Solid-state polymerization of oxetanes. I. Lattice parameters and packing properties of the monomers

1973

The crystallographic unit cells of melt-crystallized 3,3-bischloromethyloxetane and 3,3-bisbromomethyloxetane were determined by the Weissenberg method. The two isomorphous lattices are triclinic with two molecules in the unit cell. 3,3-Bisfluoromethyloxetane forms plastic crystals in the temperature range between −36°C and +22°C, as shown by differential calorimetry and NMR broad-line spectroscopy. The Debye-Scherrer diagram and the general physical properties indicate the formation of a face-centered cubic lattice. No correlation between the lattice parameters of the monomer and polymer can be found On the basis of these results, the question is raised as to whether a topochemical polymer…

The calculation of the number-average degree of polymerization starting from intrinsic viscosity and overall rate

1962

The relation between the intrinsic viscosity [η] and the number-average degree of polymerization Pn is a function of the molecular weight distribution of the polymer. In a polymer in which the termination of polymer radicals occurs partly by combination of two growing chains, this molecular weight distribution depends on number and extent of additional reactions such as chain transfer; i.e., it is variable. Therefore Pn of such polymers cannot be obtained from intrinsic viscosity measurements by means of an equation of the type [η] = KPna. A new method is proposed which allows the evaluation of Pn in these cases, without necessity of osmotic (or related) measurements or fractionation. The v…

1980

Using a bifunctional initiator such as the tetrameric dianion of α-methylstyrene for the anionic polymerization of methyl methacrylate the rate constant is found to increase with conversion approaching that observed with a monofunctional initiator while the tacticity of the polymers obtained changes from that of an almost ideally atactic to a highly syndiotactic polymer. The results are explained by the assumption of an intramolecular association of the two terminal ion pairs yielding a new active species and gradually dissociating with increasing degree of polymerization of the chain. Using a polymeric dianion of α-methylstyrene as an initiator the association phenomenon is not observed.

Some kinetic effects in the polymerization of 1,3,5-trioxane

1960

Ordering kinetics in synthetic Mg(Al,Fe3+)2O4 spinels: Quantitative elucidation of the whole Al-Mg-Fe partitioning, rate constants, activation energi…

2014

A novel procedure, based on the application of the kinetics simulator Gepasi, has been successfully applied for modeling the cation ordering process in two synthetic Mg(Al2-yFe3+y)O4 spinels (y~ 0.39 and 0.54, samples F39 and F54, respectively). The kinetic profiles suggested a two-stage mechanism, with rapid inter-site exchange of Fe3+ with Mg followed by slow exchange of Al with Mg. The trial to apply the classical approaches, based on the explicit solutions of the differential equations corresponding to single-cation (Sha-Chappel model) or two-cation (Müller model) exchange reactions, proved not feasible in the whole time range, thus implying a lack of information about the exchange proc…

Characterization of the laccase-mediated oligomerization of 4-hydroxybenzoic acid

2016

Modifying inert poly(ethersulfone) membranes using laccase has proven to be an environmentally benign and easily applicable process to alter the membrane's surface properties. By this method phenolic acid monomers such as 4-hydroxybenzoic acid are grafted from the membrane surface to make it anti-fouling. In order to enhance the anti-fouling capabilities even further it is important to study the molecular details of this reaction. However, the nature of the products of laccase modification, either on a surface or in solution, has been studied only poorly. In this paper we report the formation of C3–C3′, C3–O and C1–C3′ linked dimers as the first products of the solution-phase laccase-mediat…

Organobase-Catalyzed Synthesis of Multiarm Star Polylactide With Hyperbranched Poly(ethylene glycol) as the Core

2011

Multiarm star copolymers consisting of the polyether-polyol hyperbranched poly(ethylene glycol) (hbPEG) as core and poly(L-lactide) (PLLA) arms are synthesized via the organobase- catalyzed ring-opening polymerization of lactide using hbPEG as a multifunctional macroinitiator. Star copolymers with high molecular weights up to 792 000 g mol−1 are prepared. Detailed 2D NMR analysis provides evidence for the attachment of the PLLA arms to the core and reveals that the adjustment of the monomer/initiator ratio enables control of the arm length. Size exclusion chromatography measurements show narrow molecular weight distributions. Thermal analysis reveals a lower glass transition temperature, me…