Organocatalytic Ring-Opening Polymerization Toward Poly(γ-amide-ε-caprolactone)s with Tunable Lower Critical Solution Temperatures
journal contributionposted on 01.07.2020, 15:33 by Lianlei Wen, Shaoze Zhang, Yan Xiao, Jin He, Shuang Zhu, Jun Zhang, Zihan Wu, Meidong Lang
γ-Amide-ε-caprolactones including 7-oxo-N-propyloxepane-4-carboxamide (NNCL), N-isopropyl-7-oxooxepane-4-carboxamide (NICL), N,N-diethyl-7-oxooxepane-4-carboxamide (DECL), and 5-(pyrrolidine-1-carbonyl)oxepan-2-one (VPyCL) were initially designed and synthesized to achieve biodegradable and thermosensitive materials. Ring-opening polymerization (ROP) of these newly developed caprolactones was thoroughly investigated by both theoretical calculation and experimental verification. Density functional theory revealed that the ring-opening enthalpy of γ-amide-ε-caprolactones was more negative than that of γ-ester-ε-caprolactone (EMCL). Experimental results showed that ROP of NICL, DECL, and VPyCL catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene with benzyl alcohol (BnOH) as an initiator underwent in a living and controlled manner, while that of NNCL and EMCL did not. Computational calculation consistently proved that a variety of substitutions greatly affected the ROP process. PNICL, PDECL, and PVPyCL exhibited reversible lower critical solution temperature-type phase transitions tuned by manipulating the feed ratio and hydrophilicity of comonomers. Furthermore, poly(γ-amide-ε-caprolactone)s with excellent biodegradability and biocompatibility were demonstrated as an enzyme activity regulator, holding great promise for smart biomaterial application.
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NNCL7- oxopropyloxepane -4-carboxamideVPyCLCritical Solution Temperatures γPDECLExperimental resultsring-opening enthalpyEMCLbiomaterial applicationisopropyl -7-oxooxepanesolution temperature-type phase tra...ROP processthermosensitive materialsγ- amide -ε-caprolactonesPNICLbenzyl alcoholenzyme activity regulatorRing-opening polymerizationDECLOrganocatalytic Ring-Opening Polyme...diethyl -7-oxooxepaneComputational calculationfeed ratioNICL