Gram-scale free radical polymerization of an azaborine vinyl monomer

Abstract

The gram-scale polymerization of a novel azaborine vinyl monomer is reported. We describe an efficient and high-yielding synthesis of B-vinyl-2,1-borazanaphthalene. Homopolymers and co-polymers with 2-vinylnaphthalene are characterized by heteronuclear NMR and absorbance spectroscopy.

A BN Aromatic Ring Strategy for Tunable Hydroxy Content in Polystyrene

“…[15,[27][28][29][30][31] We described the synthesis and gram-scale free radical polymerization of BN 2-vinylnaphthalene (BN2VN), as well as the preparation of copolymers with 2-vinylnaphthalene (2VN). [26,32,33] We prepare BN2VN in high overall yield and in two steps from commercially available starting materials.T he multistep syntheses of monocyclic azaborine vinyl monomers limit polymerizations to the milligram scale. [26,32,33] We prepare BN2VN in high overall yield and in two steps from commercially available starting materials.T he multistep syntheses of monocyclic azaborine vinyl monomers limit polymerizations to the milligram scale.…”

“…Since PS is transparent at 310 nm, if two homopolymers were present, only one peak should be observed at 310 nm. [26] As imilar calibration curve was constructed for BN2VN and styrene (Supporting Information, Figure S2). [9] In our prior work on BN2VN-2VN copolymerization, we described aU V/Vis absorbance spectroscopy assay for BN2VN incorporation based on the differential absorption of naphthalene and BN-naphthalene at 320 nm.…”

“…[26] BN2VN polymers are attractive candidates for investigating the proposed borapolyolefin oxidation owing to the scalable monomer synthesis. [26,32,33] We prepare BN2VN in high overall yield and in two steps from commercially available starting materials.T he multistep syntheses of monocyclic azaborine vinyl monomers limit polymerizations to the milligram scale. [24,25] Thesuccessful copolymerization of BN2VN and 2VN suggests the feasibility of copolymerization of styrene and BN2VN (PBN2VN-co-PS).…”

“…[9] In our prior work on BN2VN-2VN copolymerization, we described aU V/Vis absorbance spectroscopy assay for BN2VN incorporation based on the differential absorption of naphthalene and BN-naphthalene at 320 nm. [26] As imilar calibration curve was constructed for BN2VN and styrene (Supporting Information, Figure S2). Ap lot of extinction coefficient at 320 nm (e 320 )v ersus the wt %P BN2VN in binary mixtures of the homopolymers yields astraight line.A linear regression analysis of the data yields Equation (1) in…”

A BN Aromatic Ring Strategy for Tunable Hydroxy Content in Polystyrene

“…Polymerization of azaborine vinyl monomers is promising given their increased stability relative to other boranes . Building on Sneddon's description of the polymerization of vinyl borazine, several groups have recently reported free radical polymerization of azaborine vinyl monomers . This complements progress on inorganic main chain BN polymers and azaborine‐derived conjugated polymers .…”