Search results for "Chain transfer"
showing 10 items of 85 documents
Facilitating polymer conjugation via combination of RAFT polymerization and activated ester chemistry
2010
The synthesis of block copolymers via polymer conjugation of well-defined building blocks offers excellent control over the structures obtained, but often several coupling strategies need to be explored to find an efficient one depending on the building blocks. To facilitate the synthesis of polymers with adjustable functional end-groups for polymer conjugation, we report on the combination of activated ester chemistry with RAFT polymerization using a chain transfer agent (CTA) with a pentafluorophenyl ester (PFP-CTA), which allows for flexible functionalization of either the CTA prior to polymerization or the obtained polymer after polymerization. Different polymethacrylates, namely PMMA, …
1971
The anionic polymerization of β-propiolactone at 25°C in ethanol initiated by the betain was investigated. Macrozwitterions of the structure were produced, n being intentionally as low as ca. 11. The structure of the product was proven by the nitrogen content of the reprecipiated polymer, by IR and NMR spectroscopy and by titration of the carboxylate endgroups. Some carboxylic acid endgroups were formed by chain transfer with the solvent ethanol. The positive charge at the polymer chain was proven by electrophoresis of polymer after esterification of the carboxylate chain end. Furthermore the dielectric constant of dilute solutions of the polymer in CHCl3 was determined and is discussed. Th…
Synthesis of Heterotelechelic α,ω Dye-Functionalized Polymer by the RAFT Process and Energy Transfer between the End Groups
2009
The synthesis of a vinyl polymer with two different fluorescent dye end groups using reversible addition-fragmentation chain transfer (RAFT) polymerization is described. Use of a pentafluorophenyl (PFP) activated ester chain transfer agent (CTA) provided a polymer with an R end group that was reactive toward amines and a dithioester ω end group. The R PFP ester was amidated with Oregon Green Cadaverin. This did not harm the ω dithioester, which was subsequently aminolyzed with an excess of n-propylamine in the presence of Texas Red-2-sulfonamidoethyl methanethiosulfonate, resulting in a disulfide bond connecting the second dye to the polymer chain. Excess dyes and side products were removed…
Synthesis of Photoreactive Block Copolymers Based on 1-Iminopyridinium Ylides
2010
Two photoreactive pyridinium ylide containing monomers, {[2-(metacryloyloxy)ethoxy]carbonyl}(pyridinium-1-yl)azanide (M1) and pyridinium-1-yl-(4-vinylbenzoyl)azanide (M2), were synthesized. Both monomers were polymerized under controlled radical polymerization conditions, i.e. reversible addition–fragmentation chain transfer polymerization (M1 and M2) and nitroxide-mediated polymerization (M2). Further block copolymers PMMA-b-PM1 and PS-b-PM2 were successfully synthesized and their molecular weight, Mn, and block ratio could be determined by 1H NMR analysis, thereby opening the synthetic possibilities of photoreactive ylides in block copolymer syntheses.
Polymerization of methyl and phenyl oxazoline initiated with alkyl chloroformates
2010
It has been shown that alkyl chloroformates are capable of initiating the polymerization of oxazolines. Esters itself initiate rather slowly and the polymerization proceeds via covalent growing species. Exchange of counter ions with triflate or iodide anions leads to faster initiation and higher reaction rates. The polymerization is of living character.
Kinetics of Group Transfer Polymerization
1987
The group transfer polymerization (GTP) of methyl methacrylate (MMA) and tert.-butyl methacrylate (TBMA), catalyzed by bifluoride, is of first order with respect to monomer and catalyst concentrations. A slightly negative order with respect to initiator concentration is observed, indicating an inhibitive function of the initiator. Termination reactions occur at lower catalyst concentrations. They are very pronounced for TBMA and result in incomplete conversions. For MMA, at lower catalyst and higher initiator concentrations, induction periods are observed which increase when lowering the temperature. This is related with the formation of active chains. The Arrhenius plots for the propagatio…
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…
Übertragungskonstante und konstitution des polymethylmethacrylates
1957
Die Ubertragungsreaktion am Polymeren, d. h. der Ubergang eines H-Atoms von Polymeren an ein Radikal, ist ein Vorgang, dessen Messung Aufschlus uber den Bau des Polymermolekuls erlaubt. Am Polymethacrylat (PMM) wurde fruher gefunden, das langs der Kette nur sehr schwache Ubertagung stattfindet, das aber am Ende des Molekuls eine sehr ubertragungsaktive Endgruppe liegt. Die hier mitgeteilten Messungen am PMM, welches im Block, in verschiedenen Losungsmitteln und bei verschiedenen Temperaturen radikalisch und ionisch polymerisiert wurde, zeigen, das die im Innern der Kette liegenden Monomereinheiten kaum starker ubertragen, als das reine Monomere. Die stark ubertragungsaktive Endgruppe wird b…
Die thermische Polymerisation von Methylmethacrylat, 1. Polymerisation in Substanz
1978
Special purification of the monomer and careful preparation of the reaction setup allowed a thorough study of the spontaneous thermal polymerization of methyl methacrylate over a wide range of temperatures (0–140°C). The rates of polymerization are notably lower than the few data previously reported in literature, and the degrees of polymerization slightly higher. The thermal initiation reaction is superimposed by radical production due to the natural ionising radiation (cosmic radiation etc.). This additional initiation becomes significant at temperatures below 60°C. New and more reliable monomer chain transfer constants are given.
Über die polymerisation von p-jodstyrol
1962
Die radikalische Polymerisation von p-Jodstyrol wird in Substanz und in benzolischer Losung untersucht. Die Poly-p-jodstyrole lassen sich durch Austausch des Jods gegen Lithium und anschliesende Hydrolyse quantitativ in Polystyrole uberfuhren; deren Polymerisationsgrade konnen in bekannter Weise viskosimetrisch bestimmt werden. Dadurch ist die Aufstellung einer Viskositats-Polymerisationsgrad-Beziehung fur Poly-p-jodstyrol auf indirektem Wege durch polymeranaloge Umsetzung von Poly-p-jodstyrol zu Polystyrol moglich. Aus kinetischen Messungen wird die Ubertragungskonstante des monomeren p-Jodstyrols zu 1,9·10−4 bestimmt. Fur die Copolymerisation von Styrol und p-Jodstyrol bei 50°C gelten fol…