Insights on the Atmospheric-Pressure Plasma-Induced Free-Radical Polymerization of Allyl Ether Cyclic Carbonate Liquid Layers

Plasma-induced free-radical polymerizations rely on the formation of radical species to initiate polymerization, leading to some extent of monomer fragmentation. In this work, the plasma-induced polymerization of an allyl ether-substituted six-membered cyclic carbonate (A6CC) is demonstrated and emphasizes the retention of the cyclic carbonate moieties. Taking advantage of the low polymerization tendency of allyl monomers, the characterization of the oligomeric species is studied to obtain insights into the effect of plasma exposure on inducing free-radical polymerization. In less than 5 min of plasma exposure, a monomer conversion close to 90% is obtained. The molecular analysis of the oligomers by gel permeation chromatography coupled with high-resolution mass spectrometry (GPC-HRMS) further confirms the high preservation of the cyclic structure and, based on the detected end groups, points to hydrogen abstraction as the main contributor to the initiation and termination of polymer chain growth. These results demonstrate that the elaboration of surfaces functionalized with cyclic carbonates could be readily elaborated by atmospheric-pressure plasmas, for instance, by copolymerization.

Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

Allylation of nucleophiles with highly reactive electrophiles like allyl halides can be conducted without metal catalysts. Less reactive electrophiles, such as allyl esters and carbonates, usually require a transition metal catalyst to facilitate the allylation. Herein, we report a unique transition-metal-free allylation strategy with allyl ether electrophiles. Reaction of a host of allyl ethers with 2-azaallyl anions delivers valuable homoallylic amine derivatives (up to 92%), which are significant in the pharmaceutical industry. Interestingly, no deprotonative isomerization or cyclization of the products were observed. The potential synthetic utility and ease of operation is demonstrated by a gram scale telescoped preparation of a homoallylic amine. In addition, mechanistic studies provide insight into these C(sp3)–C(sp3) bond-forming reactions.

Chemodivergent assembly of ortho-functionalized phenols with tunable selectivity via rhodium(III)-catalyzed and solvent-controlled C-H activation

Ortho-functionalized phenols and their derivatives represent prominent structural motifs and building blocks in medicinal and synthetic chemistry. While numerous synthetic approaches exist, the development of atom-/step-economic and practical methods for the chemodivergent assembly of diverse ortho-functionalized phenols based on fixed catalyst/substrates remains challenging. Here, by selectively controlling the reactivities of different sites in methylenecyclopropane core, Rh(III)-catalyzed redox-neutral and tunable C-H functionalizations of N-phenoxyacetamides are realized, providing access to both ortho-functionalized phenols bearing linear dienyl, cyclopropyl or allyl ether groups, and cyclic 3-ethylidene 2,3-dihydrobenzofuran frameworks under mild cross-coupling conditions. These divergent transformations feature broad substrate compatibility, synthetic applications and excellent site-/regio-/chemoselectivity. Experimental and computational mechanistic studies reveal that distinct catalytic modes involving selective β-C/β-H elimination, π-allylation, inter-/intramolecular nucleophilic substitution cascade and β-H’ elimination processes enabled by different solvent-mediated and coupling partner-controlled reaction conditions are crucial for achieving chemodivergence, among which a structurally distinct Rh(V) species derived from a five-membered rhodacycle is proposed as the corresponding active intermediates.

Building biobased, degradable, flexible polymer networks from vanillin via thiol–ene “click” photopolymerization

A new biobased allyl ether monomer with acetal groups is synthesized from renewable vanillin for building flexible transparent thiol–ene networks with good degradability under mild acidic conditions.

Substantiation of the Erdenetiyn-Ovoo copper-molybdenum ore flotation technology with the use of tertiary acetylene alcohol

The article presents the results of a study of the factors affecting the efficiency of the copper-molybdenum ore flotation. The objective of this work was to substantiate and develop a reagent mode for flotation of the Erdenetiyn-Ovoo porphyry copper ores, which makes possible extracting main copper and molybdenum minerals into corresponding concentrates more fully and selectively. It is shown that the use of a DC-80 (2-methyl-3-butin-2-ol) flotation reagent in assosiation with the main base mode reagents — an AERO MX-5152 (a mixture of allyl ethers of xanthogenic acids with n-butyloxycarbonyl-O-n-butylthionocarbamate) combined nonionized collector, a BK-901B (a composition of dialkyldithiophosphate and O,N-dialkyldithiocarbamate) blending ionized collector; diesel fuel; a MIBC (methyl isobutyl carbinol) frother; sodium sulphide Na2S as a modifier and lime СаО as a pH regulator of the medium allows obtaining a noticeable, economically sound additional recovery of both copper and molybdenum. Quantum chemical calculations have permitted to establish an important feature of the mechanism of interaction between the DC-80 molecules that can form stronger complexes based on -bonds with metal cations of sulfide minerals in comparison with allyl ethers of xanthogenic acids. The energy indicators of the formation of bonds between Cu2S, the DC-80 molecules and allyl ether of xanthic acid were calculated. There were shown the models of the assumed interaction of small mineral particles with air bubbles during flotation, which are determined by physical and chemical properties of the molecules of acetylene-containing reagents. The principal difference between the properties of the foam bubbles formed by acetylene-containing molecules for at least 50% and that of the ordinary foam bubbles formed by standard frothers has been demonstrated in the view of the mechanism of their fixing on the surface of small particles of sulfide minerals and the surface of the bubbles. The optimal flotation mode, comprising a DC-80 reagent, BK-901B and AERO MX-5152 base collectors has been developed. The application of this mode will allow increasing the copper and molybdenum recovery into concentrates by 0.62% and 5.76%, respectively, reducing the flotation time by 35–40%, and improving the quality of resulting concentrates. Based on the research results, it is recommended to incorporate the DC-80 acetylene reagent into the basic flotation mode for conducting pilot tests at the Erdenet Mining Corporation enterprises (Mongolia).

Carbon Fabric Reinforced Addition-Cure Phenolic Resins Based on Propargyl and Allyl Ether Functional Novolac Produced

Composites consisting of propargyl- and allyl/propargyl- modified novolac resins and carbon fabric were obtained by the vacuum infusion molding process. It was established that the presence of potassium cations remaining after the synthesis increase the resin melt viscosity, and acid washing is needed to obtain resins suitable for cost-effective injection techniques of composite fabrication. The mechanical properties of all composites such as compressive strength, tensile strength, in plane shear strength, and interlaminar shear strength were determined at 25, 200 and 230 °С. The carbon fiber reinforced plastics (CFRPs) retained their mechanical properties at temperatures up to 200 °C. It was shown that the use of the obtained allyl-containing polymer matrices improved mechanical properties and increased the thermal stability of the CFRPs in comparison with the propargylated novolac matrices. The composite material with novolac matrices modified by 18% propargyl and 23% allyl groups retains only up to 70% of the initial interlaminar shear strength values at 230 °C which corresponds to the data of the dynamic mechanical analysis of neat cured resins.