Search results for "polymerization"

1993

The influence of lithium tert-butoxide (tBuOLi) and of lithium chloride on the oligomerization of tert-butyl acrylate (tBuA) initiated by tert-butyl α-lithioisobutyrate (tBiB-Li) was investigated. These additives affect both the kinetics and the product distribution. Whereas the addition of LiCl leads to a narrower molecular-weight distribution (MWD) the presence of tBuOLi induces broader MWD's, characterized by a very high fraction of the dimer. Both additives decrease the rates of propagation to different degrees. These effects are discussed on the basis of the formation of aggregates and adducts, the lithiated dimer having a higher tendency to form aggregates than the other oligomers. Th…

Die Herstellung einer molekulareinheitlichen Tri-, Tetra- und Pentamethacrylsäure. V. Mitt. Modelle für Matrizenreaktionen

1968

Vom p-Kresol sowie einer phenolischen Zwei- und einer Dreikernverbindung wurden mit verschiedenen Acylierungsmethoden Methacrylsaureester erhalten; die Zweikernverbindung enthielt danach zwei und die Dreikernverbindung drei Methacrylreste. Loste man diese Methacrylsuureester in groser Verdunnung in siedendem Benzol und lies gleichzeitig einen grosen Uberschus an Radikalen aus α.α′-Azoisobuttersauredinitril einwirken, so wurde beim Methacrylsaure-p-kresylester eine Polymerisation unterdruckt. Bei den mehrfachen Estern der Mehrkernverbindungen wurde die polyrmerisationsahnliche Additionsreaktion auf die einzelnen Molekule begrenzt (intramolckulare Polymerisation); sie ergab neben einer cyclis…

Die kationische ɛ-caprolactam-polymerisation. IV. Isolierung und strukturermittlung der oligomeren als beitrag zur aufklärung des polymerisationsmech…

1966

Molekulareinheitliche Oligomere von Polykondensations- und Polyadditionsreaktionen konnen zur Aufklarung von Struktur und Bildungsmechanismus der Polymeren dienen. Auf diesem Wege wird der fruher vorgeschlagene Mechanismus der kationischen Lactampolymerisation mit wasserfreien Sauren erhartet, der in einer Acylierung des Lactams durch Lactamsalz unter Bildung von Aminoacyllactamsalz und nachfolgendem Kettenwachstum durch Addition weiterer Lactammolekule an die entstandene und immer wieder neu gebildete Ammonium-Endgruppe besteht. Dazu werden aus Caprolactam und Chlorwasserstoff als Initiator unter geeigneten Bedingungen Oligomerengemische gewonnen und elektrophoretisch aufgetrennt. Mikropra…

2014

Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta react…

ChemInform Abstract: Radical Addition to Iminium Ions and Cationic Heterocycles

2015

Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta react…

Performance of amines as silanol suppressors in reversed-phase liquid chromatography

2016

In reversed-phase liquid chromatography, cationic basic compounds yield broad and asymmetrical peaks, as a result of their ionic interaction with the anionic free silanol groups present in the silica-based stationary phases (commonly derivatised with C18 groups). A simple way to improve the peak shape is the addition to the hydro-organic mobile phase of a reagent (usually called additive) with cationic character. This associates with the stationary phase to prevent the access of analytes to the free silanol groups. Cationic additives may interact electrostatically with the anionic silanols. The hydrophobic region of the additive may also associate with the alkyl chains bound to the stationa…

Cocaine abuse determination by ion mobility spectrometry using molecular imprinting

2016

A cocaine-based molecular imprinted polymer (MIP) has been produced by bulk polymerization and employed as selective solid-phase extraction support for the determination of cocaine in saliva samples by ion mobility spectrometry (IMS). The most appropriate conditions for washing and elution of cocaine from MIPs were studied and MIPs were characterized in terms of analyte binding capacity, reusability in water and saliva analysis, imprinting factor and selectivity were established and compared with non-imprinted polymers. The proposed MIP-IMS method provided a LOD of 18μgL-1 and quantitative recoveries for blank saliva samples spiked from 75 to 500μgL-1 cocaine. Oral fluid samples were collec…

Magnetic molecularly imprinted polymers for the selective determination of cocaine by ion mobility spectrometry

2018

Abstract Magnetic molecularly imprinted polymers (MMIPs) were prepared for cocaine recognition by bulk polymerization in the presence of magnetic nanoparticles (MNPs). Two reagents (polyethylene glycol (PEG) and 3-(trimethoxysilyl)propyl methacrylate (V)) were used for MNPs modification. MMIPs were characterized and compared in terms of loading capacity, reusability, accuracy and precision for the extraction of cocaine from saliva samples. It was observed that V-MMIPs gave higher physical stability than PEG-MMIPs. Thus, V-MMIP were used for the analysis of cocaine users saliva. The developed procedure based on ion mobility spectrometry (IMS) provided limits of detection and quantification o…

Organo-catalyzed synthesis of aliphatic polycarbonates in solvent-free conditions

2012

A new efficient and expeditious route to the synthesis of aliphatic polycarbonates, in solvent-free conditions and using 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) as a catalyst precursor, is described. The protocol consists of a two-step polymerization process involving the transesterification of dimethyl carbonate (DMC) with linear alkane diols and leading to high molecular weight homopolymers. The reaction went to completion quantitatively with the liberation of methanol as the only by-product. The in situ formation of N-heterocyclic carbene species resulting from BMIM-2-CO2 decarboxylation is suggested to be a key feature of the condensation process. The protocol was then …

Comparative chemistry of 18-electron Mo(II) and 17-electron Mo(III) compounds containing only carbon-based ligands

1998

International audience; The chemical reactivity of various kinetically stable isomers of compound CpMo(η3-C3H5)(η4-C4H6), 1, and its oxidation product [1]+, as well as the bis-allyl Mo(III) complex CpMo(η3-C3H5)2, 2, and the bis-diene Mo(II) complex [CpMo(η4-C4H6)2]+, 3, is reviewed. The inertness toward isomerization processes of the allyl and butadiene ligands in the Mo(II) complexes has allowed a study of the relative reactivity toward both electrophilic and nucleophilic addition processes as a function of coordination mode. The dependence of various reaction pathways on the metal oxidation state has also been investigated. Of particular interest is the discovery that the electronically …