Reference

Polymerizations initiated by boron fluoride etherate - III

Polymerizations initiated by boron fluoride etherate - III. The role of the electrodic processes in polymerizations under electric field. Cerrai, P.; Guerra, G.; Nucci, L.; Tricoli, M. (Cent. Stud. Processi Ionici Polimerizzazione sulle Prop. Fis. Tecnol. Sist. Macromol., Pisa I-56100, Italy). Eur. Polym. J., 21(5), 505-10 (English) 1985. CODEN: EUPJAG. ISSN: 0014-3057. DOCUMENT TYPE: Journal CA Section: 35 (Chemistry of Synthetic High Polymers) Section cross-reference(s): 76 The electrode processes occurring when a d.c. elec. field is applied to the prepn. of polystyrene [9003-53-6] and npoly(trans-anethole) [26795-32-4] initiated by BF3.Et2O [109-63-7] in 1,2-dichloroethane soln. were investigated. Retardation of polymn. by the field, sometimes overcoming the well-known field acceleration, was attributed to electrochem. reactions at the cathode. Linear and cyclic voltammetries on the various reactants showed that the field acceleration was due to anodic oxidn. of the monomer, that BF3.Et2O was easily reducible and that the electrolysis of water and of its complexes with BF3 was hardly relevant. Electrolyses of solns. of the etherate at their redn. potential, as well as the use of the electrolyzed solns. to initiate polymn., confirmed the cathodic formation of inhibiting species, among which Cl- was identified. A redn. mechanism of BF3.Et2O consistent with the exptl. results was proposed. The non-electrolytic component of the field acceleration in polymns. carried out in cells with external electrodes was discussed.

Electroconductive materials based on poly(b-diketone)

Electroconductive materials based on poly(b-diketone). Okamoto, Yoshiyuki; Hwang, E. F.; Wang, M. C. (Dep. Chem., Polytech. Inst. New York, Brooklyn, NY 11201, USA). J. Polym. Sci., Polym. Lett. Ed., 23(6), 285-7 (English) 1985. CODEN: JPYBAN. ISSN: 0360-6384. DOCUMENT TYPE: Journal CA Section: 36 (Physical Properties of Synthetic High Polymers) Section cross-reference(s): 35 The polymn. of diketene (I) with BF3OEt2 [109-63-7] or WCl6 catalysts in PhCl or CH2Cl2 produced an electroconductive poly(b-diketone) (II) having mol. wt. 2000-3000. I was also polymd. with AIBN [78-67-1] and Bz2O2 [13822-09-8] as catalysts. Other polymn. products were polyester and polydiketene mixts. The elec. conductivities of II doped with TCNQ and iodine were measured by an electrometric method using Ni electrodes. The cond. increased by 108-109 times upon doping. Silylation of II with Me2SiCl2 in pyridine produced a polymer with fixed double bonds and high soly. in CH2Cl2, THF, and acetone. Elemental anal. indicated that 30% of OH groups was silylated. The silylated product exhibited elec. cond. ~103 times that of the nonsilylated polymer.