Polymerization with iron chloride

Benzene can be oxidative-cationically polymerized to brown or black products with iron chloride, aluminum trichloride/copper dichloride, etc. at mild temperatures. The insoluble material can be compressed at high pressures into mold inserts. 

Poly(30) was prepared by electrochemical polymerization and chemical polymerization with iron(III) chloride [61]. While 50% of the chemically prepared polymer was soluble in chloroform and contained a large number of irregular 2-4 and 4-4 bonding defects and about 40% head-to-head coupling, the electrochemically prepared polymer essentially consisted of 2-5 and head-to-tail linkages and solubility was limited to 20%. The latter showed 250 mV lower oxidation potential in the cyclic voltammograms. 

Monomer (39) was polymerized with iron(III) chloride in the presence of sodium trifluoromethane-sulfonate to improve monomer solubility. Poly(39) was... 

Reynolds et al. prepared poIy(56), poly(59) and poly(60) by oxidative polymerization with iron(III) chloride [119]. It was clarified from IR and CP-MAS NMR spectra that these polymers contained no... 

M. F. Planche, J. C. Thieblemont, N. Mazars, and G. Bidan, Kinetic study of pyrrole polymerization with iron(lH) chloride in water, J. Appl. Polym. Sci. 52 1867(1994). 

Surprisingly, oxidative polymerization with iron(III) chloride is a sufficient method for preparing neutral, fully undoped PEDOT molecules, although only moderate yields are achievable. Neutral PEDOT (PEDOT ) is clearly the intermediate in the course to doped, highly conductive PEDOT and can be isolated by adjusting special reaction conditions (Figure 6.8). 

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... 

At elevated temperatures will decompose to carbon tetrachloride, sulfur chloride, and heavy oily polymers Ignition Temperature (deg. F) Not pertinent Electrical Hazard Not pertinent Burning Rale Not pertinent. Chemical Reactivity Reactivity with Water Reacts only when hot to give carbon dioxide, hydrochloric acid, and sulfur Reactivity with Common Materials Reacts with iron or steel, evolving carbon tetrachloride. Corrosive to most metals Stability During Transport Stable Neutralizing Agents for Acids and Caustics Flush with water, rinse with dilute sodium bicarbonate or lime solution Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

ArsenX"p is a sorbent that consists of porous (300-1200 pm diameter) polymeric beads that have been impregnated with iron (oxy)(hydr)oxide nanoparticles (Sylvester el al., 2007 Sarkar et al., 2007). The high porosity, surface area, and iron content of the beads allow them to reduce As(V) concentrations to below 10 pgL-1 in water (Tables 7.1 and 7.2). Sulfate, chloride, fluoride, and bicarbonate do not substantially interfere with the removal of As(V). However, like other iron-based sorbents, dissolved silica at pH > 7.5 and phosphate may interfere (Sylvester et al., 2007, 106). ArsenX7 is regenerated with a proprietary process, which involves rinsing the sorbent with a warm caustic solution and then neutralizing the surface charges on the beads (Sylvester et al., 2007, 109). 

To fight fire, use alcohol foam, CO2, dr) chemical. Violent polymerization occurs on contact with ammonia, alkali hydroxides, amines, metallic potassium, acids, covalent halides (e.g., aluminum chloride, iron(III) chloride, tin(IV) chloride, aluminum oxide, iron oxide, rust). Explosive reaction with glycerol at 200°. Rapid compression of the vapor with air causes explosions. Incompatible with bases, alcohols, air, m-nitroaniline, trimethyl amine, copper, iron chlorides, iron oxides, magnesium perchlorate, mercaptans, potassium, tin chlorides, contaminants, alkane thiols, bromoethane. When heated to... 

In vinyl compound polymerization of vinyl acetate, alcohol, bromide, chloride, or carbonate, ascorbic acid can be a component of the polymerization mixture (733-749). Activators for the polymerization have been acriflavine (734), other photosensitive dye compounds (737,738), hydrogen peroxides (740,741,742), potassium peroxydisulfate (743), ferrous sulfate, and acyl sulfonyl peroxides (747). Nagabhooshanam and Santappa (748) reported on dye sensitized photopolymerization of vinyl monomers in the presence of ascorbic acid-sodium hydrogen orthophosphate complex. Another combination is vinyl chloride with cyclo-hexanesulfonyl acetyl peroxide with ascorbic acid, iron sulfate, and an alcohol (749). Use of low temperature conditions in emulsion polymerization, with ascorbic acid, is mentioned (750,751). Clarity of color is important and impact-resistant, clear, moldable polyvinyl chloride can be prepared with ascorbic acid as an acid catalyst (752) in the formulation. 

METHYL-l-PHENYL-ETHYLENE (98-83-9) C9H10 Flammable liquid. Forms explosive mixture with air [explosion limits in air (vol %) 0.9 to 6.1 flash point 129°F/54°C autoignition temp 1066°F/574°C Fire Rating 2], Easily polymerizable. Unless inhibited, forms unstable peroxides. Reacts with heat and/or lack of appropriate inhibitor concentration. Reacts with catalysts for vinyl or ionic polymerization, such as aluminum, iron chloride or 2,5-dimethyl-2,5-di(ieri-butylperoxy)hexane. Violent reaction with strong oxidizers, butyl lithium, oleum, xenon tetrafluoride. Incon atible with acids. The uninhibited monomer vapor may block vents and confined spaces by, forming a solid polymer material. Attacks aluminum and copper. On small fires, use dry chemical powder (such as Purple-K-Powder), foam, or CO2 extinguishers. 

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