Vinyl Monomers, Polymers and Supramolecular Assemblies from Aminocaprolactam

Abstract

Summary: a-Aminocaprolactam is a ''green'' monomer in two ways: it is a fermentation product from sugars, and its derivatives are naturally biocompatible and biodegradable. In this overview, the synthesis of a variety of a-amino-e-caprolactam (ACL) derivatives through reaction with acid chlorides, anhydrides, and alkyl halides is described first. The product vinyl and divinyl derivatives were then polymerized using free radical initiators, and the obtained polymers characterized by solution NMR spectroscopy, differential scanning calorimetry, and thermal gravimetric analysis. The homopolymers of these monomers displayed surprisingly high glass transition temperature (T g ) values plus unexpectedly large sub-T g transitions that are believed due to relaxation of hydrogen bonding of pendent ACL units that allows group rotation. Finally, bis-and tetra-caprolactams of various diacid chlorides and diisocyantes were synthesized and shown to form self-assembled polymers and networks with excellent physical and thermal properties.

Influence of cyclodextrin on the UCST- and LCST-behavior of poly(2-methacrylamido-caprolactam)-co-(N,N-dimethylacrylamide)

“…Racemic α-amino-ε-caprolactam ( 2 ) was obtained according to literature via cyclocondensation of L-lysine ( 1 ) [ 15 ]. Through amidation of the primary amine ( 2 ) with methacryloyl chloride ( 3 ) the polymerizable 2-methacrylamido-caprolactam ( 4 ) was obtained ( Scheme 1 ) [ 14 ]. Free radical copolymerization of 4 in various comonomer compositions with N , N -dimethylacrylamide ( 5 ) leads to copolymers 6a–i ( Scheme 1 ).…”

“…In the present study we evaluate the thermoresponsive behavior of solutions of polymers containing 2-methacrylamido-caprolactam as a comonomer. The used α-amino-ε-caprolactam is obtained from biomass through a combination of biological fermentation and chemical processes [ 14 ].…”

Controlled synthesis of crosslinked polyamide 6 using a bis-monomer derived from cyclized lysine

“…1,1 0 -carbonyl-bis-caprolactam, as chain extender, improving in particular the strain at break of PA6 [29,30]. Recently, Mathias and co-workers proposed the synthesis of vinyl monomers from a-amino-ε-caprolactam for the preparation of new vinyl polymers and supramolecular assemblies [31]. The shortage of examples arises from the difficulties to synthesize new ε-caprolactam derivatives monomers which are generally obtained by rather complex and time consuming procedures.…”

New types of associating monomers and polymers from α‐aminocaprolactam and 2‐isocyanatoethyl (meth)acrylate: properties in condensed phase and in solution

“…Vinyl and divinyl derivatives of natural l ‐lysine‐based α ‐aminocaprolactam as well as bis‐ and tetracaprolactams were reported earlier . In these publications, surprisingly high glass transition temperatures ( T g ) and self‐association of the polycaprolactams due to formation of hydrogen bonds were reported.…”

“…18 Vinyl and divinyl derivatives of natural L-lysine-based -aminocaprolactam as well as bis-and tetracaprolactams were reported earlier. 19,20 In these publications, surprisingly high glass transition temperatures (T g ) and self-association of the polycaprolactams due to formation of hydrogen bonds were reported. Recently, we showed that solutions of poly(meth)acrylamide copolymers bearing -aminocaprolactam moieties directly attached to the backbone can change the thermo-responsive behaviour from LCST to UCST by variation of the solvent from water to alcohol.…”