Search results for "polymer chemistry"

Electrochemistry, spectroelectrochemistry, chloride binding, and O2 catalytic reactions of free-base porphyrin-cobalt corrole dyads.

2005

Three face-to-face linked porphyrin-corrole dyads were investigated as to their electrochemistry, spectroelectrochemistry, and chloride-binding properties in dichloromethane or benzonitrile. The same three compounds were also investigated as to their ability to catalyze the electroreduction of dioxygen in aqueous 1 M HClO4 or HCl when adsorbed on a graphite electrode. The characterized compounds are represented as (PCY)H2Co, where P = a porphyrin dianion; C = a corrole trianion; and Y = a biphenylenyl, 9,9-dimethylxanthenyl, or anthracenyl spacer, which links the two macrocycles in a face-to-face arrangement. An axial binding of one or two Cl- ligands to the cobalt center of the corrole is …

A fluorescent chemosensor based on a ruthenium(II)-terpyridine core containing peripheral amino groups that selectively sense ATP in an aqueous envir…

2000

The selective sensing of the ATP anion in an aqueous environment over phosphate, sulfate, and chloride using a fluorescence chemosensor based on Ru(tpy)22+ cores attached to polyammonium groups is reported.

N-Alkyl Ammonium Resorcinarene Chloride Receptors for Guest Binding in Aqueous Environment

2016

Host systems with guest binding ability in water and/or biological fluids are a current challenge in supramolecular host–guest chemistry. Here we present the first syntheses of water-soluble N-ethanol ammonium resorcinarene chlorides (NARCls) with terminal hydroxyl groups at the upper rim. The NARCls possess deep cavities and are shown to bind a variety of guest molecules such as linear and cyclic alkanes, linear halogenated alkanes, and aromatic fluorophores (naphthalene, p-(phenylazo)phenol) in water through hydrophobic interactions, as well as 1,4-dioxane (a water soluble guest) via hydrogen bonds. The receptors are monomeric in aqueous media and form 1:1 host–guest complexes with bindin…

Cure kinetics of a cobalt catalysed dicyanate ester monomer in air and argon atmospheres from DSC data

2004

A kinetic analysis of the cyclotrimerisation reaction of a dicyanate ester monomer catalysed by cobalt(II) acetylacetonate and nonylphenol in air and argon atmospheres has been carried out by differential scanning calorimetry (DSC). Dynamic and isothermal DSC scans as well as the glass transition temperature are the experimental data obtained. From isothermal scans a higher cyanate conversion in air than in argon was obtained. The cyanate conversions are satisfactorily described with a second-order kinetic equation in the kinetically controlled region, and by m-order (m<1) equation after vitrification is reached. Activation energies determined by different procedures agree among them, showi…

Aparatūra “Lotoss” poliuretāna plastmasas detaļu atliešanai kosmosā

2020

1980. gadā kosmosa stacijā “Salūts” pirmoreiz kosmonautikas vēsturē tika realizēts putupoliuretāna ieguves eksperiments mikrogravitācijas apstākļos, kura rezultāta tika iegūtas jaunas atziņas par ķīmiski tehnoloģisko procesu norisi kosmosā. Kosmosā tapa Maskavas olimpisko spēļu simbola lācīša figūra. Iekārtu "Lotoss", kas pašreiz atrodas Latvijas Ķīmijas vēstures muzeja krājumā, LPSR Zinātņu Akadēmijas Koksnes ķīmijas institūtā izstrādājis latviešu ķīmiķis, ķīmijas doktors, izgudrotājs un gleznotājs Arnolds Alksnis, un tā domāta polimerizācijas reakciju pētīšanai bezsvara stāvoklī.

Determination of the glass transition temperature of poly(cyclohexyl acrylate) from oxygen permeability measurements

1993

Abstract The glass transition temperature ( T g ) of poly(cyclohexyl acrylate) (PCA) has been obtained from measurements of the oxygen permeability ( P = 0.60 barrers, T g = 23.5 ± 2.0°C) using a potentiostatic electrochemical sensor, and from the oxygen diffusion coefficient ( D = 0.12 × 10 −8 cm 2 s −1 , T g = 24.0 ± 1.8°C) by the time-lag method. A T g of 25 ± 1°C was found by differential scanning calorimetry and a T g of 25.0 ± 3.5°C was obtained from the specific volume by dilatometry. The fractional free volume ( v f ) at T g is 0.020 ± 0.002, which is slightly below (∼ 20%) most glassy polymers. A linear correlation has been observed between ln D and the reciprocal of v f , which su…

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…

Solidification behavior of the theta system 2-propanol/poly(n-butyl methacrylate) I. Influences of thermoreversible gelation on stationary flow

1994

Zero shear viscosities, η0, were determined by means of a magnetoviscometer for melts of poly(n-butyl methacrylate) (M = 8.7 to 450 kg/mol, T =53.5 to 200°C) and for concentrated solutions of the highest molecular weight sample in isopropanol (T = 34.8 to 131.5 °C). Master curves can be constructed in both cases if the reference temperature is set proportional to the gelation temperature of the particular fluid. Special intersegmental interactions (eventually leading to thermoreversible gelation) can above all be felt in η0 (T) and in M c , the critical molecular weight determined in plots of log η0 vs. log M. As the temperature is lowered, the behavior changes from WLF to Arrhenius, and M …

Fragmentation of polycarbonate macroinitiators in solution and in the bulk state

1990

The diphenylethane initiator 3,4-diethyl-3,4-(p-methoxyphenyl)-hexane (T–OCH3) was synthesized. By cocondensation of bisphenol A or C and the bisphenol derivative (“T”) of T–OCH3 with phosgene, polycarbonate macroinitiators PC(TxA1-x) and PC(TxC1-x) with different compositions x were made. The thermal fragmentation of T–OCH3 and the copolycarbonates was investigated with and without a radical scavenger both in solution and in the bulk state. The primary dissociation of T–OCH3 is a monomolecular Arrhenius process with a characteristic temperature of T* (τ = 1h) = 140°C (τ: average life time of the intact molecule). When the radicals are not intercepted, the dissociation is excessively revert…

1986

The kinetics of polyamidation was investigated for the reaction of diphenyl terephthalate as activated diester with trimethylhexamethylenediamine (1 : 1 mixture of 2,2,4- and 2,4,4-trimethyl isomers) in dimethyl sulfoxide. The good solubility of the resulting polyamide (Trogamid®(poly(iminoterephthaloylimino-x,y,z-trimethylhexamethylene))) assured a reaction in which all reactants, especially the polyamide, were soluble. The conversion was followed by analysis of the phenol set free and by measuring the number-average degree of polymerization Pn of the polyamide. The reaction obeyed an overall second order with the principle of equal reactivity of functional groups fulfilled for Pn ≿ 16. De…