Kinetics of Free Radical Copolymerization. V. Copolymerization of Ethyl Acrylate with Styrene. Composition of Copolymers

The composition of copolymers formed at 50°C in ethyl acrylate/ styrene/azo-bis-isobutyronitrile/benzene systems of different composition was investigated. The experimental composition data (based on the elementary analysis of copolymers) were evaluated by the η-ζ transformation method. Finite monomer conversions were taken into account. The classical composition equation was found to describe the system under investigation. The reactivity ratios are p ₁ = 0.152 ± 0.006; p ₂ = 0.787 ± 0.023. The free radical copolymerization of ethyl acrylate and styrene has been investigated in benzene solution at 50°C. Our results on the initiation kinetics were disclosed in our recent publication [1]. Now we are reporting on our studies concerning the composition of ethyl acrylate/styrene copolymers.     

Kinetic Investigation of Poly(ethylene glycol) Hydrogel Formation via Perfusion‐Based Frontal Photopolymerization: Influence of Free‐Radical Polymerization Conditions on Frontal Velocity and Swelling Gradients

Poly(ethylene glycol) diacrylate (PEGDA) hydrogels are extensively used as scaffolds in tissue engineering. The ability to spatially control hydrogel properties is critical for designing scaffolds that direct cell behavior and tissue regeneration. To this end, we have recently developed a polymerization technique, perfusion‐based frontal photopolymerization, to generate tunable gradients in PEG hydrogels. This study explores the effects of polymerization conditions on the velocity of the propagating front and its influence on gradients in hydrogel swelling. Alterations in photoinitiator perfusion rate result in the largest variations in frontal velocity and in the magnitude of the swelling gradient among all polymerization conditions investigated.

     

Intramolecular Ketone-Olefin Radical Cyclization with Low-Valent Titanium Reagent: Synthesis of Benzopyrans

A novel protocol for intramolecular ketyl-olefin radical cyclization with low-valent titanium reagent is outlined. It allows the formation of the benzopyran nucleus from ortho-allyloxy propiophenones as the sole product in moderate yields via intramolecular radical cyclization.     

Synthesis of high molecular weight and narrow molecular weight distribution poly(acrylonitrile) via RAFT polymerization

Well‐defined polyacrylonitrile (PAN) of high viscosity‐average molecular weight (M_η = 405,100 g/mol) was successfully synthesized using reversible addition‐fragmentation chain transfer polymerization. The polymerization exhibits controlled characters: molecular weights of the resultant PANs increasing approximately linearly with monomer conversion and keeping narrow molecular weight distributions. The addition of 0.01 equiv (relative to monomer acrylonitrile) of Lewis acid AlCl₃ in the polymerization system afforded the obtained PAN with an improved isotacticity (by 8%). In addition, the influence of molecular weights and molecular weight distributions of PANs on the morphology of the electrospun fibers was investigated. The results showed that, under the same conditions of electrospinning, average diameter (247–1094 nm) of fibers increased with molecular weights of PANs, and it was much easier to get “uniform” diameter fibers while using PANs with narrow molecular weight distributions as the precursor of electrospinning. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Radical Reactivity of the Biradical [⋅P(μ-NTer)2P⋅] and Isolation of a Persistent Phosphorus-Cantered Monoradical [⋅P(μ-NTer)2P-Et]

The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)₂P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)₂P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)₂P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)₂P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)₂P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)₂P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)₂P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity.     

Recent Progress in Direct Introduction of Fluorinated Groups on Alkenes and Alkynes by means of CH Bond Functionalization

The direct introduction of fluorine and fluorinated building blocks has recently attracted a lot of attention and particularly the direct functionalization of alkenes and alkynes. This review will highlight the major progress recently made in that field, with a focus on photocatalyzed transformations, base‐promoted processes, and transition metal‐catalyzed functionalization of alkenes and alkynes. Special attention will be paid to explanations of the reaction mechanisms.     

Asymmetric Coupling of Carbon-Centered Radicals Adjacent to Nitrogen: Copper-Catalyzed Cyanation and Etherification of Enamides

The first copper-catalyzed asymmetric cyanation and etherification reactions of enamides have been established, where a carbon-centered radical adjacent to a nitrogen atom (CRAN) is enantioselectively trapped by a chiral copper(II) species. Moreover, the asymmetric cyanation of vinyl esters was disclosed as well. These reactions feature very mild reaction conditions and high functional group tolerance, and give a series of chiral α-cyano amides, α-cyano esters and α-hemiaminals in good yields with excellent enantioselectivity. The chiral α-cyano amides can be easily converted into enantioenriched 1,2-diamines and amino acids.     

Effective Utilization of NIR Wavelengths for Photo‐Controlled Polymerization: Penetration Through Thick Barriers and Parallel Solar Syntheses

This contribution details an efficient and controlled photopolymerization regulated by far‐red (λ=680 nm) and NIR (λ=780 and 850 nm) light in the presence of aluminium phthalocyanine and aluminium naphthalocyanine. Initiating radicals are generated by photosensitization of peroxides affording an effective strategy that provides controlled polymerization of a variety of monomers with excellent living characteristics. Critically, long wavelength irradiation provides penetration through thick barriers, affording unprecedented rates of controlled polymerization that can open new and exciting applications. Furthermore, a more optimized approach to performing solar syntheses is presented. By combining the narrow Q‐bands of these photocatalysts with others possessing complementary absorptions, layered, independent polymerizations and organic transformations may be performed in parallel under a single broadband emission source, such as sunlight.     

Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane

Boron‐containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface‐mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure‐dependent relative formation of the main product propylene and by‐product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium‐based catalysts.     

Experimental and Modeling Investigation of Radical Homopolymerization of 2‐(Methacryloyloxyethyl) Trimethylammonium Chloride in Aqueous Solution

The radical homopolymerization kinetics of 2‐(methacryloyloxyethyl) trimethylammonium chloride (TMAEMC) in aqueous solution is investigated across a wide range of initial monomer contents (5–35 wt%), ionic strengths, and pH levels using an in‐situ NMR technique to track monomer consumption over the complete conversion range. Molar mass distributions (MMD) of the final homopolymers are also examined, with additional batch and semi‐batch experiments conducted in a stirred vessel. The rates of monomer conversion and polymer MMDs are dependent on initial monomer content but almost entirely independent of pH and the presence of salts, with some acceleration of rate observed for low monomer levels at very high salt concentration. To aid with the interpretation of these results, the conductivity and counterion activity of monomer and polymer mixtures are measured to determine the extent of electrostatic interactions at various levels of conversion. These results are combined with recently reported measurements of TMAEMC homopropagation kinetics to develop a TMAEMC homopolymerization model that captures the systematic decrease in rates of monomer conversion observed with increased initial monomer content during batch polymerization as well as provides a good representation of semi‐batch polymerization.