A new graphically-evaluable linear method is suggested for the determination of the reactivity ratios of copolymerization. The proposed new equation is very well adaptable for visual determination of the applicability of the copolymer composition equation. If the experimental data are adequate to the composition equation, the procedure offers a simple and reliable method for the graphical determination of copolymerization constants.

Analysis of the Linear Methods for Determining Copolymerization Reactivity Ratios. I. A New Improved Linear Graphic Method

Electrochemical reduction of an exemplary ATRP catalyst, C 11 Br 2 /Me 6 TREN, is shown to be an efficient process to mediate and execute an ATRP. The onset of polymerization occurs only through passage of a cathodic current achieved under a reductive potential to form Cu 1 Br 2 /Me 6 TREN, within the reaction medium. Unprecedented control over the polymerization kinetics can be attained through electrochemical methods by modulating the magnitude of the applied potential allowing polymerization rate enhancement or retardation. Additional polymerization control is gained through electrochemical “dials” allowing polymerization rate enhancements achieved by larger applied potentials and the ability to successfully switch a polymerization “on” and “off between dormant and active states by application of multistep intermittent potentials.

https://science.sciencemag.org/content/sci/332/6025/81.full.pdf

Electrochemically mediated atom transfer radical polymerization

There are many reactions in which CC bonds are formed by addition of free radicals to alkenes. Information about the mechanism is important for the synthesis of specific target molecules. The rate of addition of alkyl radicals to alkenes is controlled by steric and polar effects. The stabilities of the educts and products are of only limited importance, since the transition states for these exothermic reactions occur very early on the reaction coordinate. Variations in reactivity and selectivity can be described using frontier orbital theory: for nucleophilic radicals the dominant interactions are those between SOMO's and LUMO's, and for electrophilic radicals those between SOMO's and HOMO's. The large differences in the steric effects of α - and β- substituents of alkenes can be explained by postulating an unsymmetrical transition state— the radical approaches one of the C atoms preferentially. Regioand stereoselectivities can be predicted and are determined, in general, by steric effects.

Formation of CC Bonds by Addition of Free Radicals to Alkenes

The successful exploitation of syntheses involving the generation of new carbon-carbon bonds by radical reactions rests on some prior knowledge of the rate constants for the addition of carbon-centered radicals to alkenes and other unsaturated molecules, and of the factors controlling them. Two former classical reviews in Angewandte Chemie by Tedder (1982) and by Giese (1983) provided mechanistic insight and led to various qualitative rules on the complex interplay of enthalpic, polar, and steric effects. In the meantime, the field has experienced very rapid progress: many more experimental absolute rate constants have become available, and there have been major advances in the efficiency and reliability of quantum-chemical methods for the accurate calculation of transition structures, reaction barriers, and reaction enthalpies. Herein we review this progress, recommend suitable experimental and theoretical procedures, and display representative data series for radical additions to alkenes. On this basis, and guided by the pictorial tool of the state-correlation diagram for radical additions, we then offer a new and more stringent quantification of the controlling factors. Our analysis leads to a partial revision of the previous qualitative rules, and it more clearly exhibits the interplay of the reaction enthalpy effects, polar charge-transfer contributions, and steric substituent effects on the reaction energy barrier. The various contributions are cast into the form of new, simple, and physically meaningful but non-linear, predictive equations for the preestimation of rate constants. These equations prove successful in several tests but call for additional theoretical and experimental foundation. The kinetics of related reactions such as polymer propagation, copolymerization, and the addition of radicals to alkynes and aromatic compounds is shown to follow the same principles.

Factors Controlling the Addition of Carbon‐Centered Radicals to Alkenes—An Experimental and Theoretical Perspective

The configurational entropy of a mixture of solvent and polymer molecules composed of segments connected by flexible bonds has been derived for the case in which the lattice they occupy contains limited regions of perfect order (i.e., the crystallites), which are reserved for occupancy by polymer segments exclusively. Although the derivation is carried out primarily for polymer chains of uniform length, modifications required for the treatment of heterogeneous polymers are included. An expression for the free energy of fusion ΔFf of the semicrystalline mixture of polymer and solvent is derived assuming a vanLaar heat of mixing term.The equilibrium (average) crystallite length ζe, derived by differentiation of ΔFf, depends principally on the ``nucleation parameter'' D which, though it evades explicit evaluation from theory, represents the relative ease with which the first layer of a crystallite tends to form; ζe may depend to a lesser extent on the degree of crystallinity. The equilibrium degree of crysta...

Thermodynamics of Crystallization in High Polymers. IV. A Theory of Crystalline States and Fusion in Polymers, Copolymers, and Their Mixtures with Diluents

Frederick M. Lewis

Papers

Copolymerization. I. A Basis for Comparing the Behavior of Monomers in Copolymerization; The Copolymerization of Styrene and Methyl Methacrylate

Copolymerization. IV. Effects of Temperature and Solvents on Monomer Reactivity Ratios

Copolymerization. VIII. The Relation Between Structure and Reactivity of Monomers in Copolymerization1

Decomposition of Aliphatic Azo Compounds

Copolymerization. II. The Copolymerization of Acrylonitrile, Methyl Methacrylate, Styrene and Vinylidene Chloride