Summary
The π-allylnickel-catalyzed living coordination polymerization of methylallene gave polymers with predictable molecular weight and narrow molecular weight distribution in high yields. The polymers possessing various microstructural units (i.e., the ratio of the 1,2- and the 2,3-polymerizations), produced by varying the nature of the catalyst and the solvents, were subjected to the hydroboration with borane reagents such as borane tetrahydrofuran complex (BH3•THF) and 9-borabicyclo[3.3.1]nonane (9-BBN). Subsequent oxidation gave poly(alcohol)s whose hydroxy-content could be varied by the borane reagents used. For example, the quantitative conversion of the double bonds in poly(methylallene) into the hydroxy group was attained by the hydroboration using an excess amount of BH3•THF. Thermal properties of poly(alcohol)s were found to be dependent upon the microstructure and the hydroxy-content of the polymers.
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References and Notes
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To demonstrate the possibility of the chemical modification of the double bonds in the poly(allene)s, we described the hydrosilylation reaction of poly(allene) (poly(1,2-propadiene)) to give polymers having silane-coupling units. In this case, the 75% of the exomethylene units (> C=CH2) was silylated under the heating conditions. See, Taguchi M, Tomita I, Endo T (2000) Macromol Chem Phys 201:2322
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The microstructure of the polymers from substituted allenes is controllable by the anionic ligands (X), neutral ligands (L), and the polymerization solvents. We would like to report the details in the forth-coming paper.
If the polymer was isolated by precipitation without washing carefully by permeable membrane, the polymer became barely soluble in organic solvents probably by the cross-linking reaction between the hydroxy groups in the polymer and boric acid derivatives.
The hydroboration of both α,α-disubstituted and α,α,β-trisubstituted olefins (e.g., CH2=C(CH3)C2H5 and CH3CH=C(CH3)2, respectively) by BH3•THF is known to give the anti-Markovnikov adducts in more than 98% selectivity. Thus, the present polymer reactions are believed to proceed in an analogous selectivity, resulting in the preferential formation of less substituted alcohol units. See: Brown HC and Zweifel G (1960) J Am Chem Soc 82:4708.
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Kino, T., Tomita, I. Synthesis of Poly(alcohol)s by Hydroboration/Oxidation of Poly(methylallene) Prepared by π-Allylnickel-Catalyzed Living Coordination Polymerization. Polym. Bull. 55, 251–258 (2005). https://doi.org/10.1007/s00289-005-0435-9
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DOI: https://doi.org/10.1007/s00289-005-0435-9