Polyvinylamine at last

Abstract

A sustained effort to develop and commercialize a practical radical addition route to amine functional polymers (AFPs) resulted, after almost 20 years, in the successful completion of a world scale monomer plant to produce N‐vinylformamide (NVF). NVF is readily polymerized and its polymers are easily hydrolyzed to reactive and atom economical polyvinylamine (PVAm) or its salts. This highlight touches on work by many companies, but focuses on efforts at Air Products and Chemicals, tracing the origins, rational, challenges, technical and commercial advances, and failures. Practical routes to new AFPs, copolymers, and derivatives across the entire molecular weight range (MW < 103 to >106) were achieved. NVF offers access to multiple water soluble, water dispersible, and nonwater soluble polymer markets, including papermaking additives and coatings, water treatment polymers, enhanced oil recovery polymers, radiation cure monomers, stabilizers, dispersing agents, surfactants, and crosslinkers. Lessons learned along the road to commercializing major new chemical technologies are also highlighted. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2257–2283, 2010

Far beyond primary poly(vinylamine)s through free radical copolymerization and amide hydrolysis

“…Then, the copolymer was solubilized in water and purified by dialysis (membrane cut off 1kDa) against water for three days before lyophilization. P(NVAstat-VIm) was collected as a white powder and characterized by 1 Table 3)…”

“…Next, the copolymer was solubilized in water and purified by dialysis (membrane cut off 1kDa) against water for three days before lyophilization. P(NMVA-stat-VIm) was collected as a white solid and characterized by 1 Table 3) Synthesis of P(NVA 0.32 -stat-NMVA 0.34 -stat-VIm 0.34 ). NVA (2.47 g, 29 mmol) and V70 (416mg, 1.3mmol) were placed under argon and dissolved by a degassed methanol (15mL) followed by addition with a syringe of distilled and degassed 1-Vim (1.8 mL, 1.84 g, 19.6 mmol) and NMVA (8.9 mL, 8.53 g, 86.4 mmol).…”

“…Then, the copolymer was solubilized in water and dialyzed (membrane cut off 1kDa) against pure water for three days before lyophilization. P(NVA-stat-NMVA-stat-VIm) was collected as an off-white solid and characterized by 1 Table 3) In general, the compositions of the terpolymers were successfully predicted based on the Alfrey-Goldfinger (AG) 42 equation (See Table 2). …”

Controlled Synthesis of Poly(vinylamine)-Based Copolymers by Organometallic-Mediated Radical Polymerization

“…7 The basic characteristics of this polymer that makes it such a success are metal binding capacity, 8,9 polyelectrolyte complexation, 10 water solubility, and pH-responsiveness. 11 However, the inherent instability of vinylamine, which is involved in a tautomeric equilibrium with the corresponding imine, prohibits its direct polymerization.…”

Rylene bisimide-based nanoparticles with cross-linked core and thermoresponsive shell using poly(vinyl amine)-based block copolymers

“…Poly(vinyl amine) is one of the simplest and most important primary amine-containing polymers, due to very high content of primary amine groups and significant modification possibilities [44,45]. In this study, we employed poly(vinyl amine)-based block copolymer, which was synthesized by RAFT polymerization of N-vinylphthalimide (NVPI) followed by deprotection (Scheme 2) [46,47].…”