Polymerization Using Electron Acceptors

Deposition on fibers or fabrics Vapor phase deposition Deposition in nanoscale matrices Photochemically initiated polymerization Enzyme-catalyzed polymerization Polymerization using electron acceptors Miscellaneous polymerization methods Routes to more processible polyanilines Emulsion polymerization Colloidal polyaniline dispersions Substituted polyanilines... 

This section describes polymerizations of monomer(s) where the initiating radicals are formed from the monomer(s) by a purely thermal reaction (/.e. no other reagents are involved). The adjectives, thermal, self-initialed and spontaneous, are used interchangeably to describe these polymerizations which have been reported for many monomers and monomer combinations. While homopolymerizations of this class typically require above ambient temperatures, copolymerizations involving certain electron-acceptor-electron-donor monomer pairs can occur at or below ambient temperature. 

Variations in ferritin protein coats coincide with variations in iron metabolism and gene expression, suggesting an Interdependence. Iron core formation from protein coats requires Fe(Il), at least experimentally, which follows a complex path of oxidation and hydrolytic polymerization the roles of the protein and the electron acceptor are only partly understood. It is known that mononuclear and small polynuclear Fe clusters bind to the protein early in core formation. However, variability in the stoichiometry of Fe/oxidant and the apparent sequestration and stabilization of Fe(II) in the protein for long periods of time indicate a complex microenvironment maintained by the protein coats. Full understanding of the relation of the protein to core formation, particularly at intermediate stages, requires a systematic analysis using defined or engineered protein coats. 

Other examples of the use of electron acceptors whose ion radicals are unstable with respect to fragmentation to an anion and a radical capable of initiation of polymerization were provided by Eaton (63,101,102). It was shown that -nitrobenzyl halides could be used in dye-sensitized compositions of semiconductor pigments such as Ti02 and CdS to induce polymerization of vinyl monomers using visible light. The sequence of events is outlined in eqs. 46-49 and Scheme 6 ... 

Aryliodonium salts have been found to be coinitiators for photooxidizable dye sensitization (105). Smith polymerized aerylamide-bis(acrylamide) mixtures using acridine, xanthene, or cyanine dyes and, for example, diphenyllodonium chloride as an electron acceptor. Reduction of the salt results in the formation of phenyl radicals. 

This review has demonstrated that a wide variety of organic and organometallic electron donors and a smaller number of electron acceptors can function as coinitiators for the photo-induced polymerization of monomers using photoreducible or photooxidizable dyes as absorbers of incident light. These compositions can be used for a number of applications in the printing, graphics arts, and electronics industries where sensitivity to visible wavelengths is necessary. 

The photochemistry of 1,3-dienes can be highly dependent on the diene structure and reaction conditions. Important variables include the ground state conformation [22,23], the reaction concentration, the use (or not) and properties of a triplet sensitizer [14] or an electron acceptor [18], and solvent polarity. The simplest dienes also often yield the most complex chemistry. For example, 1,3-butadiene 3 undergoes unimolecular isomerization in dilute solution to give only cyclobutene 4 and bicyclobutane 5 (Sch. 2), and polymerization in concentrated solution [24]. At intermediate... 

As discussed above, monomer molecules are capable of functioning either as it-electron donors and n-electron acceptors (e.g. C=C double bond containing compounds), respectively, or as n-electron donors (e.g. epoxides). Therefore, their ground or excited states can interact with donor or acceptor molecules, which are unable to polymerize. For that interaction the general Scheme 3 holds, too. Clearly, in these cases only a homopolymerization of the monomer used takes place. The mechanism of that reaction depends on the electronic properties existing (e.g. monomer acts as donor or acceptor), and on the structural conditions in both molecules. Again, in some cases a proton transfer reaction could occur. 

Foulds and Lowe (1986) combined mass production of the base sensor and enzyme immobilization as follows. Using gold or platinum ink, a working and counter electrode were deposited on a ceramic substrate. After thermal treatment of the electrode material a solution containing GOD and a pyrrole derivative of ferrocene was electrochemically polymerized at the electrode. The pyrrole component forms a conducting polymer and the immobilized ferrocene acts as electron acceptor for GOD. The structured immobilization permits this technique to be used for successive enzyme fixation to multiparameter sensors. 

An interesting application is photosensitized polymerization of pyrrole (431) using [Ru(bpy)3]3 + to give a conducting polymer, polypyrrole (432), in aqueous solution or in a polymer matrix (Scheme 6.205).1236 The acting ground-state electron acceptor, [Ru(bpy)3]3 +, is obtained in the initial electron transfer step between an excited [Ru(bpy)3]2+ and [Co(NH3)5C1]2+ ion. 

Kang and coworkers76 have also used organic electron acceptors such as 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and chloranil. A solvent effect was observed when polymerization was carried out using DDQ. Polymerization in acetonitrile gave the lowest conductivity, and in water it was slightly better. A similar solvent dependence was observed for chloranil oxidations. 

Ethyl chloride, methylene chloride, difluorodichloromethane, tetrafluoromethane, etc. are generally used as solvents for cationic polymerization. For the quantitative characterization of electrophilic (electron acceptor) and nucleophilic (electron donor) solvents, acceptor (AN) and donor (DN) numbers, respectively, are proposed. 

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