High‐pressure‐synthesis of poly(isopropenyl alcohol) and its biocompatibilities

Abstract

Free radical polymerization under ambient conditions gives very low‐molecular weight homopolymer of isopropenyl acetate (IPAc). On the other hand, poly (isopropenyl acetate) (PIPAc) with a weight average molecular weight over 104 was found to be synthesized by high‐pressure (1 GPa) radical polymerization. Poly(isopropenyl alcohol) (PIPOH) was then derived from PIPAc by saponification. The structure and properties of PIPAc and PIPOH were investigated using X‐ray diffraction, thermal analyses, X‐ray photoelectron spectroscopy, and dynamic contact angles. Though PIPOH is insoluble in water, the surface free energy (55 mJ/m2) was comparable with that of poly(vinyl alcohol). To utilize the peculiar combination of “aqueous insolubileity and high hydrophilicity” of PIPOH, biocompatibilities of PIPOH surface was investigated. The PIPOH surface was found to show high repellencies to albumin adsorption, whole thrombogenesis, and cell adhesion. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 754–761, 2009

An Alkenyl Boronate as a Monomer for Radical Polymerizations: Boron as a Guide for Chain Growth and as a Replaceable Side Chain for Post‐Polymerization Transformation

“…PMVA has received increasing attention due to its amphiphilicity and potential applicability in biocompatible materials . Since the radical polymerization of IPOAc would lead to frequent DCT (see above), high‐pressure (1 GPa) conditions are needed to obtain high‐molecular‐weight PMVA ( M n =5000) . It was expected that the oxidation of boronyl pendants for replacement with hydroxy groups would allow more efficient synthesis of PMVA.…”

“…Subsequently, we examined the potential replacement of the boronyl pendants to synthesize polymers that are inaccessible by conventional methods. PMVA has received increasing attention due to its amphiphilicity and potential applicability in biocompatible materials . Since the radical polymerization of IPOAc would lead to frequent DCT (see above), high‐pressure (1 GPa) conditions are needed to obtain high‐molecular‐weight PMVA ( M n =5000) .…”

Elucidating Monomer Character of an Alkenyl Boronate through Radical Copolymerization Leads to Copolymer Synthesis beyond the Limitation of Copolymerizability by Side-Chain Replacement

“…The Bpin pendant can be replaced with a hydroxy group, yielding the α-methyl vinyl alcohol (MVA) unit. The unit seems be introducible via (co)polymerization of isopropenyl acetate (IPOAc) followed by saponification, 14 but the unconjugated monomer shows poor copolymerization ability with conjugated comonomers. Indeed, the conversion of IPOAc in radical copolymerization with styrene was extremely low (conv.…”

An Alkenyl Boronate as a Monomer for Radical Polymerizations: Boron as a Guide for Chain Growth and as a Replaceable Side Chain for Post‐Polymerization Transformation

“…Subsequently,w ee xamined the potential replacement of the boronyl pendants to synthesize polymers that are inaccessible by conventional methods.P MVAh as received increasing attention due to its amphiphilicity and potential applicability in biocompatible materials. [10] Since the radical polymerization of IPOAc would lead to frequent DCT (see above), [9,11] high-pressure (1 GPa) conditions are needed to obtain high-molecular-weight PMVA( M n = 5000). [10] It was expected that the oxidation of boronyl pendants for replacement with hydroxy groups would allow more efficient synthesis of PMVA.…”

“…[10] Since the radical polymerization of IPOAc would lead to frequent DCT (see above), [9,11] high-pressure (1 GPa) conditions are needed to obtain high-molecular-weight PMVA( M n = 5000). [10] It was expected that the oxidation of boronyl pendants for replacement with hydroxy groups would allow more efficient synthesis of PMVA. Our efforts were also directed to synthesis of poly(a-methyl vinyl amine) (PMVAm) through replacement of the boronyl pendants with amino groups.O xidation or amination [12] reactions were studied with poly(IPBpin) synthesized through free-radical polymerization (Figure 4a, Schemes S15-S16).…”