title: Thermoplastic cellulose-graft-poly(L-lactide) copolymers homogeneously synthesized in an ionic liquid with 4-dimethylaminopyridine catalyst.
abstract: An effective method for grafting L-lactide (LA) from unmodified cellulose by ring-opening polymerization (ROP) in homogeneous mild conditions is presented. By using 4-dimethylaminopyridine (DMAP) as an organic catalyst, cellulose-graft-poly(L-lactide) (cellulose-g-PLLA) copolymers with a molar substitution (MS(PLLA)) of PLLA in a range of 0.99-12.28 were successfully synthesized in ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) at 80 degrees C. The amount and length of grafted PLLA in cellulose-g-PLLA copolymers were controlled by adjusting the molar ratios of LA monomer to cellulose. The structure and thermal properties of cellulose-g-PLLA copolymers were characterized by (1)H NMR, (13)C NMR, wide-angle X-ray powder diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and optical microscopy. The DSC results revealed that the copolymers exhibited a single glass transition temperature, T(g), which sharply decreased with the increase of MS(PLLA) up to MS(PLLA) = 8.28 (DS(PLLA) = 2.19) and increased a little with a further increase of the lactyl content. When MS(PLLA) was above 4.40, the graft copolymers exhibited thermoplastic behavior, indicating the intermolecular and intramolecular hydrogen bonds in cellulose molecules had been effectively destroyed. By using a conventional thermal processing method, fibers and disks of cellulose-g-PLLA copolymers were prepared.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Key Laboratory of Engineering Plastics, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Chenghu
authors.initials: C
authors.lastname: Yan
authors.forename: Jinming
authors.initials: J
authors.lastname: Zhang
authors.forename: Yuxia
authors.initials: Y
authors.lastname: Lv
authors.forename: Jian
authors.initials: J
authors.lastname: Yu
authors.forename: Jin
authors.initials: J
authors.lastname: Wu
authors.forename: Jun
authors.initials: J
authors.lastname: Zhang
authors.forename: Jiasong
authors.initials: J
authors.lastname: He
mesh_terms: D015761:4-Aminopyridine / Q000031:analogs & derivatives* / Q000737:chemistry; D002152:Calorimetry, Differential Scanning; D002384:Catalysis; D002482:Cellulose / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D011091:Polyesters / Q000737:chemistry*; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D052578:Ionic Liquids; D011091:Polyesters; D011108:Polymers; C033616:poly(lactide); D002482:Cellulose; D015761:4-Aminopyridine; C003885:4-dimethylaminopyridine