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        Facile Synthesis of Block Copolymers from a Cinnamate Derivative by Combination of AGET ATRP and Click Chemistry

        Chuanjie Cheng,Xiongxiong Bai,Xu Zhang,Ming Chen,Qinghua Huang,Zhongyu Hu,Yuanming Tu 한국고분자학회 2014 Macromolecular Research Vol.22 No.12

        An azido- and bromo-containing compound derived from naturally occurring ethyl cinnamate was usedsuccessfully to prepare block copolymers by a combination of ‘activator generated by electron transfer atom transferradical polymerization’ (AGET ATRP) and Huisgen “click” reactions in emulsion. First, azido-end poly(methyl methacrylate)and alkyne-end polystyrene were prepared under AGET ATRP conditions, then, poly(methyl methacrylate) blockpolystyrene (PMMA-b-PS) diblock copolymer was formed by Huisgen 1,3-dipolar cycloaddition. Finally, polystyreneblock poly(methyl methacrylate) block polystyrene (PS-b-PMMA-b-PS) triblock copolymer was synthesizedvia simultaneous AGET ATRP and click reactions, catalyzed by the same copper-based catalyst. The polymers werecharacterized by 1H nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC),which confirmed the successful synthesis of the corresponding polymers.

      • KCI등재

        Emulsifier-Free Synthesis of Crosslinkable ABA Triblock Copolymer Nanoparticles via AGET ATRP

        Chuanjie Cheng,Liang Shen,Quanlei Fu,Zhongbin Liu,Yongluo Qiao,Changqing Fu 한국고분자학회 2011 Macromolecular Research Vol.19 No.10

        A crosslinkable ABA triblock copolymer was synthesized from allylic methacrylate (AMA) monomer using a poly(ethylene oxide)-based macromolecule as both an initiator and emulsifier. The “two-step” controlled/living radical polymerization can be conducted via activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). Cheap and commercially available N,N-dimethyldodecylamine (DMDA) was found to be a good ligand for the AGET ATRP reaction. The linear ABA triblock copolymer that contains pendent allylic groups can undergo crosslinking under UV irradiation conditions, which indicates that the environmentally friendly method has potential applications in UV curing coatings and UV curing inks, etc..

      • KCI등재

        Thermally Healable Polyurethanes Based on Furfural-Derived Monomers via Baylis-Hillman Reaction

        Qinghua Huang,Fanghong Yang,Xingxing Cao,Zhongyu Hu,Chuanjie Cheng 한국고분자학회 2019 Macromolecular Research Vol.27 No.9

        Two novel acrylate monomers with diol group, 2-hydroxyethyl 2-(furan- 2-yl(hydroxy)methyl)acrylate and methyl 2-(hydroxy(5-(hydroxymethyl)furan-2- yl)methyl)acrylate, were synthesized via Baylis-Hillman reaction in moderate yields. The monomer 2-hydroxyethyl 2-(furan-2-yl(hydroxy)methyl)acrylate was obtained from furfural and 2-hydroxyethyl acrylate (HEA); methyl 2-(hydroxy(5-(hydroxymethyl)furan- 2-yl)methyl)acrylate was prepared from 5-hydroxymethl furfural (HMF) and methyl acrylate. The monomer 2-hydroxyethyl 2-(furan-2-yl(hydroxy)methyl)acrylate reacted with toluene diisocyanate (TDI)-derived or hexamethylene diisocyanate (HDI)-derived diisocyanate oligomers to obtain the corresponding linear polyurethane oligmers PU-1T and PU-1H. Similarly, the diol methyl 2-(hydroxy(5-(hydroxymethyl)furan- 2-yl)methyl)acrylate reacted with TDI- or HDI-derived diisocyanate oligomers to obtain the corresponding linear polyurethane oligmers PU-2T and PU-2H. The numberaverage molecular weights of the linear polyurethane oligomers are approximately 300-350 Da. There are furan groups in the linear polyurethane oligomers PU-1T, PU-1H, PU-2T and PU-2H, which makes them capable of undergoing reversible Diels-Alder reaction with 4,4'- bismaleimidodiphenylmethane (BMI) to form the corresponding crosslinked polyurethanes CPU-1T, CPU-1H, CPU-2T and CPU-2H. Pencil hardness of CPU-1T, CPU-1H, CPU-2T and CPU-2H are 3H, 2H, 2H and HB, respectively. Glass transition temperatures of CPU-1T, CPU- 1H, CPU-2T and CPU-2H are 104.8, 97.6, 5.1 and 1.2 oC, respectively. TGA analysis shows that Td90 values of the CPUs range from 180 to 250 oC. Furthermore, the reversible crosslinked polyurethanes CPU-1T and CPU-1H can be completely self-healed at 90 oC for 3 h, while CPU-2T and CPU-2H can self-heal at 80 oC for 3 h presumably due to their low glass transition temperatures.

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