Styrenetricarbonylchromium (IV) has been synthesized. Monomer IV did not homopolymerize with free‐radical initiation but copolymerized with styrene, methyl acrylate, and vinylcymantrene. The copolymerizations were carried out in benzene solutions at 70°C with azobisisobutyronitrile as the initiator. The relative reactivity ratios were determined for the styrene and methyl acrylate copolymerizations. They were (defining M1 as monomer IV) r1 ≅ 0, r2 ≅ 1.39 for styrene copolymerizations and r1 ≅ 0, r2 ≅ 0.75 for methyl acrylate copolymerization. Polystyrene reacted with chromium‐hexacarbonyl in refluxing DME to produce a polymer in which about 32% of the benzene rings were complexed with Cr(CO)3 units. The use of a polystyrene of narrow molecular weight distribution in this reaction demonstrated that no decomposition of the polystyrene chains occurred.
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.
synopsisVinylferrocene (MI) has been copolymerized with N-vinylcarbazole (112) using azobisisobutyronitrile as the initiator. In benzene at 70"C, the reactivity ratios rl = 0.47 and r2 = 0.20 were obtained. Using an e value of -1.34 for N-vinylcarbazole, the calculated value e for vinylferrocene is about -2.8, in general agreement with the large negative e values vinylferrocene exhibits with other monomers which are electron rich. These copolymers were treated with trinitrofluororenone to give copolymers with carbazole-trinitrofluorenone charge-transfer complex sites (type B). The copolymers were oxidized with dichlorodicyanoquinone to give a series of copolymers with both ferrocenium and ferrocene sites in them (type C). In addition, type C copolymers were further treated with trinitrofluorenone to give a class of polymers having ferrocene, ferrocenium, and carbazole-trinitrofluorenone charge-transfer sites (type D). Introducing ferrocene and ferrocenium sites into the poly(vinylcarbazo1e-trinitrofluorenone) polymers resulted in an increase in their conductivity, but the polymers were no longer photoconducting.
A number of new dialkyl 2-(5-trisubstitutedsilyl)thienylphosphonates and thiophosphonates as well as dialkyl 2-(5-trisubstitutedsilyl)furylphosphonates and thiophosphonates were prepared via reaction of the 5-(trisubstitutedsilyl)-2-lithiothiophenes and furans with dialkyl chlorophosphate and dialkyl chlorothiophosphate. Moreover, some diethy124 5(trisubstitutedsilyl)-2thienyl ]ethyl thiophosphates are reported.
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