Radical addition-fragmentation chemistry in polymer synthesis

Mechanistic implications of plastic degradation

Unperturbed dimensions of stereoregular polymers.- Reinforcement of rubber by carbon black.- Transformations of phenolic antioxidants and the role of their products in the long-term properties of polyolefins.

Properties of polymers

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

This critical review is devoted to semiconducting and high spin polymers which are of great scientific interest in view of further development of the organic electronics and the emerging organic spintronic fields. Diversified synthetic strategies are discussed in detail leading to high molecular mass compounds showing appropriate redox (ionization potential (IP), electron affinity (EA)), electronic (charge carrier mobility, conductivity), optoelectronic (electroluminescence, photoconductivity) and magnetic (magnetization, ferromagnetic spin interactions) properties and used as active components of devices such as n- and p-channel field effect transistors, ambipolar light emitting transistors, light emitting diodes, photovoltaic cells, photodiodes, magnetic photoswitches, etc. Solution processing procedures developed with the goal of depositing highly ordered and oriented films of these polymers are also described. This is completed by the description of principal methods that are used for characterizing these macromolecular compounds both in solution and in the solid state. These involve various spectroscopic methods (UV-vis-NIR, UPS, pulse EPR), electrochemistry and spectroelectrochemistry, magnetic measurements (SQUID), and structural and morphological investigations (X-ray diffraction, STM, AFM). Finally, four classes of polymers are discussed in detail with special emphasis on the results obtained in the past three years: (i) high IP, (ii) high |EA|, (iii) low band gap and (iv) high spin ones.

Polymers for electronics and spintronics

Kinetic and ESR studies on the radical polymerization of Di-n-butyl itaconate in benzene

Solvent effect on the polymerization of di-n-butyl itaconate (DBI) with dimethyl azobisisobutyrate (MAIB) was investigated at 50 and 61°C. The solvents used were found to affect significantly the polymerization. The polymerization rate (Rp) and the molecular weight of the resulting polymer are lower in more polar solvents. The initiation rate (Ri) by MAIB, however, shows a trend of being rather higher in polar solvents. The stationary state concentration of propagating poly(DBI) radical was determined by ESR in seven solvents. The rate constants of propagation (kp) and termination (kt) were evaluated by using Rp, Ri, and the polymer radical concentration observed. The kp value decreases fairly with increasing polarity of the solvent used, whereas kt is not so influenced by the solvents. The solvent effect on kp is explained in terms of a difference in the environment around the terminal radical center of the growing chain. Copolymerization of DBI with styrene (St) was also examined in three solvents with different physical properties. The poly(DBI) radical shows a lower reactivity toward St in a more polar solvent.

Solvent effect on the radical polymerization of di‐n‐butyl itaconate

Polymerization of dialkyl itaconates with dimethyl azoisobutyrate (5) was studied in benzene at 50°C by means of electron spin resonance (ESR). The monomers used are dimethyl (1), diethyl (2), dibutyl (3) and di-2-ethylhexyl (4) itaconates. All the polymerization systems involve ESR-observable propagating polymer radicals under the actual polymerization conditions. The polymerization rate (Rp) and degree of polymerization of the resulting polymer increase in going from shorter to longer alkyl groups. The ESR-determined rate constants of propagation (kp) and termination (kt) decrease as the alkyl chain becomes longer. kp of 1 is 3,3 times higher than that of 4, while kt of 1 is 590 times higher than that of 4. Thus, the steric effect due to the alkyl group suppresses much more termination than propagation, leading to the fact that Rp increases as the alkyl group becomes larger.

Effect of alkyl groups on the rate constants of propagation and termination in the radical polymerization of dialkyl itaconates

Observation of a persistent methacrylate radical in the decomposition of methyl 2,2'-azobis(isobutyrate) and the polymerization of methyl methacrylate

Phenethyl 2-(methoxycarbonylmethyl)acrylate (methyl penethyl itaconate) (1) was prepared and its polymerization with dimethyl 2,2′-azoisobutyrate (2) was investigated kinetically in benzene. The polymerization rate (Rp) was found to be expressed by Rp = k·[2]0,5·[1]1,8 (at 50°C). Further, a higher dependence of Rp (2nd order) on the concentration of 1 was observed at 61°C. The overall activation energy of the polymerization was calculated to be a low value of 50,3 kJ/mol. The initiator efficiency (f) of 2 was determined to be 0,48 to 0,22 at 50°Cand 0,50 to 0,28 at 61°C. f decreases with increasing monomer concentration due to the high viscosity of 1. The poly(1) radical is stable enough to be observable by ESR at high temperatures (50–60°C). Rate constants of propagation (kp) and termination (kt) were estimated using the poly(1) radical concentration determined by ESR. kp [6,0 to 121/(mol·s) at 50°Cand 7,1 to 15 1/(mol·s) at 61°C] shows a trend to increase with the concentration of 1. On the other hand, kt [2,9·104 to 17·1041/(mol·s) at 50°Cand 6,9·104 to 45·1041/(mol. s) at 61°C] decreases with increasing MPI concentration. This behavior is responsible for the high order with respect to monomer concentration. Copolymerization of 1 (M1) with styrene (M2) at 50°Cgave the following results: r1 = 0,36, r2 = 0,40, Q1 = 0,82 and e1 = + 0,59. Using the above results, the rate constants of the cross-propagations were estimated to be k12 = 22 1/(mol·s) and k21 = 308 1/(mol·s) at 50°C.

Hitoshi Tanaka

Papers

Kinetic and ESR studies on the radical polymerization of Di-n-butyl itaconate in benzene

Solvent effect on the radical polymerization of di‐n‐butyl itaconate

Effect of alkyl groups on the rate constants of propagation and termination in the radical polymerization of dialkyl itaconates

Observation of a persistent methacrylate radical in the decomposition of methyl 2,2'-azobis(isobutyrate) and the polymerization of methyl methacrylate

ESR determination of rate constants for the radical polymerization of methyl phenethyl itaconate