Organometallic polymers. XIV. Copolymerization of vinylcyclopentadienyl manganese tricarbonyl and vinylferrocene withN‐vinyl‐2‐pyrrolidone

Abstract

synopsisN-Vinyl-Zpyrrolidone(1) has been copolymerized with vinylferrocene(I1) and vinylcyclopentadienyl mar,ganese tricarbonyl(II1) in degassed benzene solutions with the use of azobisisobutyronitrile (AIBN) as the initiator. The polymerizations proceed smoothly, and the relative reactivity ratios were determined as rl = 0.66,r~ = 0.40 (for copolymerization of I with 11, MI defined a s 11) and rl = 0.14 and rz = 0.09 (for copolymerization of I with 111, MI defined as 111). These copolymers were soluble in benzene, THF, chloroform, CClr, and DMF. Molecular weights were determined by viscosity and gel-permeation chromatography studies (universal calibration technique.)The copolymers exhibited values of a,, between 5 X 108 and 10 X loa and aw between 7 X 108 and 17 X 108 with aw/an < 2. Upon heating to 260°C under Ns, copolymers of 111 underwent gas evolction and weight loss. The weight loss was enhanced at 300"C, and the polymers became increasingly insoluble. Copolymers of vinylferrocene were oxidized to polyferricinium salts upon treatment with dichlorodicyanoquinone (UDQ) or 0-chloranil (o-CA) in benzene. Each cnit of qLinone incorporated into the polysalts had been reduced to its radical anion. The ratio of ferrocene to ferricinium units in the polysalts was determined. The polysalts did not melt at 360°C and were readily soluble only in DMF.

Metal-Containing Polymers

“…The monomer easily copolymerizes with styrene, acrylonitrile, and vinyl-ferrocene, dissolved in benzene or ethyl acetate, in the presence of AIBN as an initiator [86,87] to give copolymers of fairly high molecular weight. Similar results have been obtained by copolymerizing (8) with N-vinyl-2-pyrrolidone[88] under identical conditions.…”

Synthesis of Air‐Stable Cyclopentadienyl Fe(CO)2 (Fp) Polymers by a Host–Guest Interaction of Cyclodextrin with Air‐Sensitive Fp Pendant Groups

“…Synthesis of MCPs containing air‐sensitive metal carbonyl complexes was attempted as early as in 1960s, but only resulted in poorly characterized polymer‐like materials in many cases –. Despite the challenge, several groups have made significant progress in recent years.…”

“…synthesized side chain metal carbonyl block copolymers by living ring‐opening metathesis polymerization . Owing to the inherent instability of metal carbonyl complexes,–, the resultant polymers usually decompose after exposing to air for an extended period of time . The processibility of the polymers is therefore limited.…”

Organometallic Polymers of the Transition Metals

“…[90][91][92][93][94][95][96] The polymerization of vinylferrocene in solution and bulk was examined, along with the physical, chemical and electrical properties of the resulting polymers. [90][91][92][93][94][95][96][97][98][99] In 1999, Frey and coworkers reported the copolymerization of vinylferrocene with styrene using the ''living'' radical initiator 2,2,6,6-tetramethyl-1-pyperidinyl-1-oxy (TEMPO). [100] These reactions resulted in the production of block copolymers with narrow polydispersities.…”