Search results for "Chain transfer"

Hydroxyfunctional oxetane-inimers with varied polarity for the synthesis of hyperbranched polyether polyols via cationic ROP

2014

Novel initiating systems for the living polymerization of acrylates and methacrylates

1998

The polymerization of methyl methacrylate with lithiated initiators in the presence of aluminium alkyls in toluene has living character but it deviates from conventional first-order kinetics and the polymers have fairly broad molecular weight distributions. This results from the formation and precipitation of a coordinative polymer network in which the lithium ions of the living chain ends are coordinated to the in-chain ester carbonyl groups. Thus, the network formation can be prevented by adding Lewis bases like methyl pivalate which coordinate to the living chain ends instead ofthe polymer. Alternatively, one can introduce tetraalkylammonium salts aiming at an exchange of the lithium ion…

Influence of End Groups on the Stimulus-Responsive Behavior of Poly[oligo(ethylene glycol) methacrylate] in Water

2010

The influence of the chemical structure of both end groups onto the lower critical solution temperature (LCST) of poly[oligo(ethylene glycol) monomethyl ether methacrylate] (POEGMA) in water was systematically investigated. POEGMA of Mn = 3550 g/mol and Mw/Mn = 1.14 prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization was equipped with two different functional end groups in a one-step postpolymerization reaction combining activated esters, functional amines, and functional methane thiosulfonates. As end groups, n-propyl, n-hexadecyl, di(n-octadecyl), poly(ethylene glycol)-550 (PEG), 1H,1H-perfluorononyl, azobenzene, and trimethylethylammonium groups were system…

Group transfer and anionic polymerization: A critical comparison

1990

The mechanism of group transfer polymerization (GTP) of methacrylates in THF is investigated by using data on kinetics of homo- and copolymerization, polymer microstructure and molecular weight distribution. By comparison with corresponding data on anionic polymerization it is concluded that the mechanisms of monomer addition to the active chain end is very similar for both anionic and group transfer polymerization and that GTP is ionic in character. On the other hand, GTP uniquely is characterized by the existence of a catalyst exchange equilibrium. The position of this equilibrium determines the rates of polymerization, and the dynamics determine the molecular weight distribution.

Preparation of Hyperbranched Polyacrylates by Atom Transfer Radical Polymerization. 2. Kinetics and Mechanism of Chain Growth for the Self-Condensing…

1997

The self-condensing vinyl polymerization (SCVP) of 2-((2-bromopropionyl)oxy)ethyl acrylate (BPEA) has resulted in the formation of hyperbranched polyacrylates. The polymerization mechanism used to polymerize the BPEA was atom transfer radical polymerization (ATRP), a “living”/controlled radical polymerization. This paper details the study of the kinetics of polymerization and the growth of the macromolecule during the polymerization. The results obtained in the polymerization were compared to the theoretical predictions for SCVP. It was determined that the polymerization deviated from the ideal case, as a consequence of the establishment of a dynamic equilibrium in ATRP resulting in the add…

Polymerization of 3-alkylthiophenes with FeCl3

1992

We report on the mechanism of direct oxidation of 3-alkylthiophenes using ferric chloride (FeCl3) as the polymerization oxidant/catalyst to produce high molecular weight poly(3-alkylthiophenes) (P3ATs), conjugated polymers that have potential as electrically and optically active polymers. This study shows that the FeCl3 must exist in the solid state in the reaction mixture to be active as an oxidant in the polymerization of P3AT. A feasible polymerization mechanism for 3-alkylthiophene was developed on the basis of the crystal structure of FeCl3 and quantum chemical computations of thiophene derivatives. The polymerization is hypothesized to proceed through a radical mechanism rather than a…

Maleimide Glycidyl Ether: A Bifunctional Monomer for Orthogonal Cationic and Radical Polymerizations.

2015

A novel bifunctional monomer, namely maleimide glycidyl ether (MalGE), prepared in a four-step reaction sequence is introduced. This monomer allows for selective (co)polymerization of the epoxide group via cationic ring-opening polymerization, preserving the maleimide functionality. On the other hand, the maleimide functionality can be copolymerized via radical techniques, preserving the epoxide moiety. Cationic ring-opening multibranching copolymerization of MalGE with glycidol was performed, and a MalGE content of up to 24 mol% could be incorporated into the hyperbranched polymer backbone (Mn = 1000-3000 g mol(-1)). Preservation of the maleimide functionality during cationic copolymerizat…

Synthesis of SBC, SC and BC block copolymers based on polystyrene (S), polybutadiene (B) and a crystallizable poly(ɛ-caprolactone) (C) block

1996

The sequential anionic polymerization of polystyrene-block-polybutadiene-block-poly(e-caprolactone) (SBC) triblock copolymers as well as polystyrene-block-poly(e-caprolactone) (SC) and polybutadiene-block-poly(e-caprolactone) (BC) diblock copolymers was achieved in benzene. To initiate the polymerization of the highly reactive e-caprolactone, the nucleophilicity of the carbanion has to be reduced. For this purpose 1,1-diphenylethylene (DPE) was used. To avoid inter- and intramolecular transesterification reactions of the growing caprolactone block, the reaction time of this monomer in the block copolymers was strictly controlled. The reaction between polybutadienyl anions and DPE is too slo…

Combining Ring-Opening Multibranching and RAFT Polymerization: Multifunctional Linear–Hyperbranched Block Copolymers via Hyperbranched Macro-Chain-Tr…

2013

The synthesis of a hyperbranched macro-chain-transfer agent for RAFT polymerization of functional methacrylate or methacrylamide monomers was achieved by selectively attaching one single CTA onto hyperbranched polyglycerol dendron analogues. The combination of ring-opening multibranching polymerization of glycidol and subsequent RAFT polymerization of the hyperbranched macro-chain-transfer agents created a new route to a variety of multifunctional linear–hyperbranched block topologies. All linear–hyperbranched block copolymers could be synthesized with controlled molecular weight (Mn = 3.2–43.7 kg/mol) and low polydispersity (PDI = 1.15–1.34). As first examples for this universal approach, …

Sequential conversion of orthogonally functionalized diblock copolymers based on pentafluorophenyl esters

2010

Statistic and block copolymers exhibiting activated ester side groups were synthesized by reversible addition-fragmentation chain transfer polymerization in the presence of cumyl dithiobenzoate, benzyl dithiobenzoate, and 4-cyano-4-((thiobenzoyl)sulfanyl)pentanoic acid as chain transfer agents. Pentafluorophenyl methacrylate and pentafluorophenyl 4-vinylbenzoate were used to enable a sequential functionalization of the obtained copolymers by conversion of the activated esters with different amines. 1H NMR spectroscopy, 19F NMR spectroscopy, and FTIR spectroscopy showed the successful step-by-step conversion of the different activated esters by aniline followed by aliphatic amines, thereby r…