Controlled synthesis of thermoresponsive polymers derived from l‐Lysine, a biorenewable resource

Abstract

Renewable lysine was cyclized to its corresponding α‐amino‐ε‐caprolactam and then underwent the reaction with acryloyl chloride to harvest a 2‐acrylamido‐caprolactam (ACL) monomer. Subsequent reversible addition–fragmentation chain transfer copolymerization of the obtained monomer with oligo(ethylene glycol)acrylate (OEGA) gave well‐defined P(ACL‐co‐OEGA) with low distribution. Nuclear magnetic resonance , size exclusion chromatography, and matrix‐assisted laser desorption ionization–time‐of‐flight–mass spectrometry measurements indicated the controlled feature of the polymerization. Moreover, the resultant copolymers demonstrated thermoresponsiveness, and the cloud points (Tcp) can be adjusted from 34 to 79 °C, by changing pH values, and the fraction of cyclic lysine. These results suggested that these lysine‐based thermoresponsive polymers might be used as new materials in biomedical fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 862–868

Thermosetting Resins Based on a Self-Crosslinkable Monomer/Polymer Possessing Meldrum's Acid Groups

“…This feature of DA/retro-DA reactions has been widely applied to build up DA-adduct-based self-healing polymers. [35][36][37][38] Similar to our previous work, [34] the MA-SCP polymer chain might be "partially" broken down to generate some furan and maleimide groups, both involved in the following ketene-mediated crosslinking reactions (Scheme 1). As a result, the occurrence of retro-DA reaction might result in some low-molecular-weight MA-SCP.…”

“…Taking the advantage of Diels-Alder (DA) reaction between furan and maleimide groups, MA-bisF is first polymerized with a BMI compound to result in a MAcontaining self-crosslinkable polymer (MA-SCP) through DA reaction (Scheme 1). [34] Consequently, thermally crosslinking MA-SCP results in a crosslinked resin of MA-BisF and BMI. Formation of long chain precursor (MA-SCP) of MA-bisF and BMI, rather than directly crosslinking their physical mixture, in the preparation route of the MA-bisF/BMI resin provides processing convenience/flexibility and enhances the domain compatibility between the two monomers.…”

Preparation of Boron Nitride Nanoplatelets via Amino Acid Assisted Ball Milling: Towards Thermal Conductivity Application

“…The strong peaks at 190.1 and 190.2 eV were coming from the B-N bond, and the weak peaks at 191.0 and 190.8 eV were ascribed to the B-O bond [ 11 , 15 , 29 ]. The N 1s spectra of Lys@BNNP and Glu@BNNP can be quantitatively differentiated into three different nitrogen species, which are C-N, B-N and B···N [ 18 , 19 , 26 , 27 , 30 ]. Notably, the emergence of new peaks of C 1s and O 1s were also observed with respect to amino acid moieties, in Figure S1 .…”

“…Recently, amino acids (AAs) have attracted considerable interest because they have the advantage of origin from biomass sources and are cheap and readily available [ 19 , 20 ]. Owing to their multifunctional groups, AAs have also been widely used in constructing polymer materials with various properties [ 21 , 22 ].…”

Recent advances in RAFT polymerization of monomers derived from renewable resources

“…RAFT polymerization of an amino acid-derived monomer based on lysine was reported by Tao and coworkers. 52,53 L-Lysine was cyclized and reacted with 2,5-hexanedione, before imparting vinyl functionality through reaction with acetylene to give a 2,5-dimethylpyrrole protected N-vinylcaprolactam (MPVCL). 52 A xanthate CTA, O-ethyl-S-(1-methoxycarbonyl)ethyl dithiocarbonate, was used to homopolymerize MPVCL and copolymerize it with N-vinylcaprolactam (VCL) by macromolecular design via interchange of xanthates (MADIX).…”