Search results for "Reactivity"
showing 10 items of 880 documents
Effect of the Substituent Position on the Anionic Copolymerization of Styrene Derivatives: Experimental Results and Density Functional Theory Calcula…
2019
In a combined synthetic, kinetic and theoretical study, the living anionic copolymerization of styrene and its ring-methylated derivatives ortho-, meta-, and para-methylstyrene (MS) was examined by real-time 1H NMR spectroscopy in the nonpolar solvents toluene-d8 and cyclohexane-d12 as well as by density functional theory calculations. Based on the NMR kinetics data, reactivity ratios for each comonomer pair were determined by the Kelen–Tudős method and numerical integration of the copolymerization equation (Contour software). The reaction pathway was modeled and followed by density functional theory (DFT) calculations to validate and predict the experimentally derived reactivity ratios. Un…
Towards bio-based tapered block copolymers: the behaviour of myrcene in the statistical anionic copolymerisation
2019
To explore the potential of myrcene (Myr) as a bio-based monoterpene comonomer for styrenic copolymers and to establish its general applicability for the carbanionic copolymerisation, several statistical copolymerisations of myrcene and common monomers like isoprene (I), styrene (S) and 4-methylstyrene (4MS) were carried out in cyclohexane and monitored by in situ1H NMR spectroscopy. Real-time NMR kinetic studies permitted the determination of the reactivity ratios and the composition profile for each monomer combination. While the copolymerisation of Myr/I yielded a gradient copolymer and reactivity ratios of moderate disparity (rMyr = 4.4; rI = 0.23), the statistical copolymerisation of M…
Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity …
2022
Detailed understanding of the monomer distribution in copolymers is essential to tailor their properties. For the first time, we have been able to utilize in situ 1H NMR spectroscopy to monitor the monomer-activated anionic ring opening copolymerization (AROP) of ethylene oxide (EO) with a glycidyl ether comonomer, namely, ethoxy ethyl glycidyl ether (EEGE). We determine reactivity ratios and draw a direct comparison to conventional oxyanionic ROP. Surprisingly, the respective monomer reactivities differ strongly between the different types of AROP. Under conventional oxyanionic conditions similar monomer reactivities of EO and EEGE are observed, leading to random structures (rEO = 1.05 ± 0…
Copolymerization Kinetics of Glycidol and Ethylene Oxide, Propylene Oxide, and 1,2-Butylene Oxide: From Hyperbranched to Multiarm Star Topology
2016
Copolymerization of established epoxide monomers with glycidol (G) is a key reaction to prepare branched or hyperbranched polyethers. The kinetics of the multibranching anionic ring-opening copolymerization of glycidol (a cyclic latent AB2 monomer) with ethylene oxide (EO), propylene oxide (PO), and 1,2-butylene oxide (BO; cyclic latent AB monomers), respectively, in dimethyl sulfoxide was studied. Online 1H NMR spectroscopy was employed for in situ monitoring of the individual monomer consumption during the entire course of the statistical copolymerization. Varying the counterion, both the cesium alkoxide and potassium alkoxide initiated copolymerization were studied and compared. From the…
Effect of hydrogen on the ethylene polymerization process over Ziegler-Natta catalysts supported on MgCl2(THF)2. II. Kinetic studies
2000
This article reports on a study of the effects of hydrogen on the activity of vanadium and titanium catalysts supported on MgCl 2 (THF) 2 in ethylene polymerization. It was found that hydrogen did not change the stable nature of the active sites and the polydispersity index of the polyethylene obtained. The propagation rate, expressed as k p , was found to be independent of the presence and concentration of hydrogen, indicating that this reacting agent does not modify the reactivity of the active sites. However, the presence of hydrogen in the polymerization medium is responsible for partial deactivation of the active sites just before polymerization is initiated.
Mechanism of anionic polymerization of (meth)acrylates in the presence of aluminium alkyls, 2. Kinetic investigations with methyl methacrylate in tol…
1995
The kinetics of the polymerization of methyl methacrylate initiated by lithium alkyls (tert-butyllithium or ethyl α-lithiobutyrate) was investigated in the presence of aluminium alkyls (triethylaluminium or triisobutylaluminium) in toluene at −78°C. The rate of polymerization decreases considerably once the living dimer is formed. This suggests that the aluminate end-group coordinates with the penultimate ester group of the polymer chain, thus decreasing reactivity. The results are at variance with an activated monomer mechanism.
Hydroxamic Acid: An Underrated Moiety? Marrying Bioinorganic Chemistry and Polymer Science
2020
Even 150 years after their discovery, hydroxamic acids are mainly known as the starting material for the Lossen rearrangement in textbooks. However, hydroxamic acids feature a plethora of existing and potential applications ranging from medical purposes to materials science, based on their excellent complexation properties. This underrated functional moiety can undergo a broad variety of organic transformations and possesses unique coordination properties for a large variety of metal ions, for example, Fe(III), Zn(II), Mn(II), and Cr(III). This renders it ideal for biomedical applications in the field of metal-associated diseases or the inhibition of metalloenzymes, as well as for the separ…
Stimuli-Responsive Tertiary Amine Functional PEGs Based on N,N-Dialkylglycidylamines
2014
Amine-functional poly(ethylene glycol) (PEG) copolymers have been prepared that exhibit thermo- and pH- responsive behavior in aqueous solution. Three novel tertiary di(n-alkyl)glycidylamine monomers have been introduced for anionic ring-opening copolymerization (AROcP) with ethylene oxide (EO): N,N-di(n-butyl)glycidylamine (DButGA), N,N-di(n-hexyl)glycidylamine (DHexGA), and N,N-di(n-octyl)glycidylamine (DOctGA). Via controlled AROcP we synthesized well-defined (Mw/Mn = 1.05–1.14), water-soluble block- and gradient-type PEG copolymers, containing up to 25 mol % of the respective dialkylglycidylamine comonomer. Molecular weights ranged from 4900 to 12 000 g mol–1. Detailed in-situ 1H NMR ki…
Capitalizing on Protecting Groups to Influence Vinyl Catechol Monomer Reactivity and Monomer Gradient in Carbanionic Copolymerization
2017
everal vinyl catechol-based monomers with systematically varied acetal protecting groups suitable for carbanionic polymerization are introduced. All monomers are based on the 4-vinyl benzodioxole or 5-vinyl benzodioxole structure and differ in the nature of the protecting group for the catechol functionalities. Different symmetric ketones are used for the protection of the diol functionality. Polymers with average molecular weight from 2500 to 25 000 g mol−1 (Mw/Mn < 1.15) are obtained from homopolymerization of the protected monomers. All monomers are examined regarding the influence of the protecting group on the copolymerization behavior with styrene, using in situ 1H NMR kinetic studies…
α-Chymotrypsin-Catalyzed Reaction Confined in Block-Copolymer Vesicles
2010
Herein the reactivity of the enzyme α-chymotrypsin in the confinement of polystyrene-block-poly(acrylic acid) (PS-b-PAA) vesicles was investigated. Enzyme and substrate molecules were encapsulated in PS-b-PAA vesicles with internal diameters ranging from 26 nm to 165 nm during the formation of the vesicles. While the loading efficiencies of enzyme and substrate molecules were practically identical for vesicles of identical size, they were found to increase with decreasing vesicle size. The kinetics of the α-chymotrypsin catalyzed hydrolysis of N-succinyl-Ala-Ala-Phe-7-amido-4-methylcoumarin (AMC) was evaluated following the increase of the absorption of the product 7-amino-4-methylcoumarin …