Ferric chloride polymerization

The homopolymerization ofl consists of a room-temperature reaction of the monomer dissolved in nitrobenzene in the presence of anhydrous ferric chloride. Polymerizations were carried out under a stream of dry nitrogen. As depicted in Scheme 2, the homopolymerization of 1 to form 6FNE takes place by means of the Scholl reaction. The mechanism of the Scholl reaction was assumed to proceed through a radical-cation intermediate derived from the single-electron oxidation of the monomer and its subsequent electrophilic addition to the nucleophilic monomer. The reaction releases two hydrogens, both as protons, to form the... 

Ferric chloride polymerizes propylene oxide, a monomer with an asymmetric carbon atom, with retention of asymmetry in the backbone. The products of polymerization contain either optically active polymers or racemic mixtures, depending upon the monomers used. When only a pure optical isomer monomer is used the products are crystalline polymers composed of the same optically active units ... 

This adhesive group has been promoted for use as a sealant. The adhesives used are acrylate acid diesters (polyester-acrylic). They are essentially monomeric thin liquids that polymerize to form a tough plastic bond when confined between closely fitting metal joints. Contact with air before use keeps the monomeric adhesive liquid. Metal surfaces accelerate the polymerization in the absence of air (anaerobic conditions). These materials will bond all common metals, glass, ceramics, and thermosetting plastics to each other. Phenolic plastics and some plated metals, such as cadmium and zinc, require a primer such as ferric chloride. Polymerization is essentially a free-radical-type addition polymerization. " ... 

The situation is different in solutions of aluminium chloride in phosphorus oxychloride, deriving from a higher affinity of aluminium chloride towards 0-coordination than in the case of ferric chloride. Polymeric species seem to be present according to the results of precise conductivity measurements , the high surface tensions and high viscosities. Conductometric, potentiometric, spectro-photometric and preparative investigations have shown that aluminium chloride reacts in phosphorus oxychloride and in phenylphosphonic dichloride with considerable formation of autocomplex ions. Chloride ions are released by ionization of aluminium chloride due to preferred 0-coordination by the solvent. These chloride ions may react with other solvate molecules to give the chloro-complex ... 

Incineration in an approved combustion plant is the preferred method of disposal. Wastewater from succinic acid processes is suitable for biological degradation by activated sludge (188). Polymeric sorbents (189) and ferric chloride treatment processes (190) can also be used for wastes containing... 

Polymerization of ethylene oxide can occur duriag storage, especially at elevated temperatures. Contamination with water, alkahes, acids, amines, metal oxides, or Lewis acids (such as ferric chloride and aluminum chloride) can lead to mnaway polymerization reactions with a potential for failure of the storage vessel. Therefore, prolonged storage at high temperatures or contact with these chemicals must be avoided (9). 

Dining chlorination of styrene in carbon tetrachloride at 50°C, a violent reaction occurred when some 10% of the chlorine gas had been fed in. Laboratory examination showed that the eruption was caused by a rapid decomposition reaction catalysed by ferric chloride [1], Various aromatic monomers decomposed in this way when treated with gaseous chlorine or hydrogen chloride (either neat, or in a solvent) in the presence of steel or iron(III) chloride. Exotherms of 90°C (in 50% solvent) to 200°C (no solvent) were observed, and much gas and polymeric residue was forcibly ejected. 

Another system under investigation is the iron/ chromium redox flow battery (Fe/Cr RFB) developed by NASA. The performance requirements of the membrane for Fe/Cr RFB are severe. The membrane must readily permit the passage of chloride ions, but should not allow any mixing of the chromium and iron ions. An anionic permselective membrane CDIL-AA5-LC-397, developed by Ionics, Inc., performed well in this system. ° It was prepared by a free radical polymerization of vinylbenzyl chloride and dimethylaminoethyl methacrylate in a 1 1 molar ratio. One major issue with the anionic membranes was its increase in resistance during the time it was exposed to a ferric chloride solution. The resistance increase termed fouling is related to the ability of the ferric ion to form ferric chloride complexes, which are not electrically repelled by the anionic membrane. An experiment by Arnold and Assink indicated that... 

Cationic mechanisms are much more characteristic of the polymerization of oxygen heterocycles, both ethers and acetals. A wide variety of catalysts has been used, including protonic acids, such Lewis acids as boron trifluoride, phosphorus pentafluoride, stannic chloride, antimony pentachloride, titanium tetrachloride, zinc chloride, and ferric chloride, and salts of carbocations or tri-alkyloxonium ions having anions derived from Lewis acids. Some complex, coordination catalysts that appear to operate by a mechanism... 

In 1955, Pruitt and Baggett (4,5) reported the polymerization of propylene oxide catalyzed by the reaction product of ferric chloride and propylene oxide, i.e., Pruitt-Baggett catalyst . Polypropylene oxide obtained from DL-monomer could be fractionated into two parts, one rubbery and another resinous. The latter fraction gave a discrete crystalline X-ray diffraction pattern. 

Korshak and coworkers20 polymerized levoglucosan in p-dioxane at 80-90°, using, as the catalyst, benzenesulfonic acid or such Lewis acids as boron trifluoride, ferric chloride, or aluminum chloride. Highly branched, amorphous products having Ma 38,000-68,000 (by light-scattering) were obtained. 

Ferric chloride is sometimes an important constituent of the hydrolyzing mixture. The formation of gels during polymerization can be controlled. Patents are in existence covering the hydrolysis of chlorosilanes by pouring their solutions onto the surface of a swirling solution of the active electrolyte. 

Outside of vinyl addition polymerizations some crystallizable stereoregular polymers also have been prepared. An example is isotactic polymer from propylene oxide made by using ferric chloride com-... 

Bamford, C. H., A. D. Jenkins and R. Johnston Studies in polymerization. XI. Reactions between polymer radicals and ferric chloride in non-aqueons media. Proc. Roy. Soc. A239, 214—229 (1957). 

As an example, thermosensitive PVME microgels can be used as template and stabilizer for the synthesis of composite polypyrrole (PPy) particles [32], The PVME microgels were obtained by electron beam irradiation above the phase transition temperature as described in Sect. 3.2.1 [3,4], Pyrrole (Py) was polymerized by oxidative polymerization with ferric chloride in the presence of the PVME microgels in water/ethanol mixtures as reaction medium. For comparison, the synthesis was also carried out in the presence of uncross-linked PVME. 

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