Search results for "Anionic addition polymerization"

1989

The reaction kinetics for the group transfer polymerization (GTP) of tert-butyl methacrylate (TBMA) using a silyl ketene acetal initiator and a nucleophilic catalyst are investigated. The reaction is shown to be of first order in both monomer and catalyst concentrations. The “livingness” of this system appears to be influenced by the reaction temperature. At temperatures above −20°C, deactivation is observed, with its severity increasing with increasing temperature. This deactivation is attributed to a depletion of catalyst by side reactions. It was demonstrated that reactivation is made possible by the addition of more catalyst. This result is in contrast to the anionic polymerization of T…

1981

The anionic polymerization of tert-butyl methacrylate (TBMA) in tetrahydrofuran, using Na+ and Cs+ as counterions proceeds without side reactions even at room temperature. The resulting molecular weight distributions are nearly monodisperse (Mw/Mn ⩽ 1,01). The rate constants for the propagation of ion pairs were measured in the range from + 15 to −100°C. The Arrhenius plots are linear, but different for the two counterions, resulting in the following numerical values for the frequency exponent A and the activation energy Ea: A = 8,5 and Ea = 7,2 kcal/mol = 30 kJ/mol for Na+; A = 9,5 and Ea = 5,6 kcal/mol = 23 kJ/mol for Cs+. The difference between the counterions, which is in contrast to th…

Controlled radical polymerization of styrene in miniemulsion polymerization using reversible addition fragmentation chain transfer

2003

Abstract Miniemulsion polymerizations of styrene in the presence of two reversible addition–fragmentation chain-transfer (RAFT) agents were studied. The rates were significantly retarded by the presence of a RAFT agents S -(thiobenzoyl)thioglycolic acid, 1 , or dithiobenzoic acid 1-phenylethyl ester, 2 . Control in miniemulsion polymerization is not as good as for bulk polymerizations. The miniemulsions could also be stabilized against Ostwald ripening by a polymer terminated by a dithiobenzoic moiety. In this case, the polymerization was not controlled because of the generation of renucleated particles. To cite this article: I. Uzulina et al., C. R. Chimie 6 (2003).

The “Needle in the Haystack” Makes the Difference: Linear and Hyperbranched Polyglycerols with a Single Catechol Moiety for Metal Oxide Nanoparticle …

2014

Multifunctional linear (CA-linPG) and hyperbranched polyglycerols (CA-hbPG) bearing a single catechol unit were synthesized by use of an acetonide-protected catechol initiator for the anionic polymerization of ethoxyethyl glycidyl ether (EEGE) and glycidol, respectively. A key feature for the synthesis of the hyperbranched structures was a selective, partial acetal deprotection step. The single catechol unit among a large number of aliphatic 1,2- and 1,3-diol moieties (i.e., the “needle in the haystack”) in both linear and hyperbranched polyglycerols permits dispersion of transition metal oxide nanoparticles in brine, as demonstrated for manganese oxide (MnO) nanoparticles. Molecular weight…

Indication of an order-order-transition by a partial disordering in ABC-triblock copolymers

1996

Poly(ethylene-alt-propylene)-block-polyethylethylene-block-polystyrene (PEP-b-PEE-b-PS) triblock copolymers were synthesized by anionic polymerization and subsequent hydrogenation of poly-1,4-isoprene-block-poly-1,2-butadiene-block-polystyrene triblock copolymers (1,4PI-b-1,2PB-b-PS). Differential scanning calorimetry and dynamic mechanical spectroscopy reveal an order-order transition which is induced by the mixing of PEP and PEE above their respective order-disorder transition (ODT).

Zur kinetik der anionischen polymerisation von methyl-methyacrylat in tetrahydrofuran bei −75°C

1973

Die anionische Polymerisation von Methylmethacrylat (MMA) in Tetrahydrofuran (THF) verlauft bei −75°C mit Cumylcasium bzw. oligomerem α-Methylstyrylcasium als Initiatoren ohne erkennbare Nebenreaktionen analog der anionischen Polymerisation von unpolaren Monomeren in atherischen Losungsmitteln. Als Beweis wird hauptsachlich die enge Molekulargewichtsverteilung der unter diesen Bedingungen hergestellten Polymethylmethacrylate angefuhrt. Bei −75°C betragen die Geschwindigkeitskonstanten fur die Monomeranlagerung an das Ionenpaar kw(±) = 80 dm3 mol−1 s−1 und an das freie Anion etwa kw(−) ≈ 6 · 104 dm3 mol−1 s−1. Leitfahigkeitsmessungen ergeben, das die Dissoziationskonstante des Polymethylmeth…

1992

The kinetics and the molecular weight distributions (MWD) in the anionic polymerization of tert-butyl acrylate (tBuA) in tetrahydrofuran at 23 ± 3°C were investigated. Tert-butyl α-lithioisobutyrate (tBiB-Li) was used as the initiator in the absence and presence of the additives lithium chloride and lithium tert-butoxide (tBuOLi). A flow tube reactor was used which allowed very rapid mixing of reagents, within milliseconds. The polymerization is extremely fast, half-lives being 0,01 s for the system without additive, 0,05 s for LiCl and 3 s for tBuOLi as an additive. The rate of termination was estimated from the strong UV absorption of the enolized β-oxoester end group formed. The number-a…

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation.

2015

The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazen…

Introducing an amine functionality at the block junction of amphiphilic block copolymers by anionic polymerization strategies

2011

A series of block copolymers bearing a single amino in-chain functionality was synthesized via anionic polymerization of styrene and ethylene oxide. By means of both a conventional and a continuous setup, living polystyrene was quantitatively end functionalized with an oxirane (DBAG) prior to the polymerization of the poly(ethylene oxide) segment. The in-chain amine was conjugated with a fluorescent dye.

Amino Functional Poly(ethylene glycol) Copolymers via Protected Amino Glycidol

2010

The synthesis of poly(ethylene glycol) (PEG) copolymers with multiple amino functionalities within the chain is described, relying on an epoxide comonomer bearing a protected amino group. N,N-dibenzyl amino glycidol (DBAG) and ethylene oxide (EO) were copolymerized via anionic polymerization, leading to well-defined polymers with varied comonomer content and low polydispersities (Mw/Mn in the range of 1.1 to 1.2). Subsequent hydrogenolysis with Pearlman’s catalyst afforded poly(ethylene glycol-co-amino glycerol)s (PEG-co-PAG) with a precisely adjusted number of randomly incorporated amino groups in the range of 2−15%. For the first time, the kinetics of an EO copolymerizations have has been…