Synthesis of Functional Polycaprolactones via Passerini Multicomponent   Polymerization of 6-Oxohexanoic Acid and Isocyanides

doi:10.1021/acs.macromol.6b00096

CORC > 北京大学 > 化学与分子工程学院

	Synthesis of Functional Polycaprolactones via Passerini Multicomponent Polymerization of 6-Oxohexanoic Acid and Isocyanides
	Zhang, Jian ; Zhang, Mei ; Du, Fu-Sheng ; Li, Zi-Chen
刊名	MACROMOLECULES
	2016
关键词	RING-OPENING POLYMERIZATION INTRAMOLECULAR CYCLIZATION BIOMEDICAL APPLICATIONS POLY(ETHYLENE GLYCOL) ALIPHATIC POLYESTERS TRIBLOCK COPOLYMERS CLICK CHEMISTRY POLY(EPSILON-CAPROLACTONE) DRUG RELEASE
DOI	10.1021/acs.macromol.6b00096
英文摘要	We describe a straightforward strategy for a new family of functional polycaprolactones (PCL) via the Passerini multicomponent polymerization (P-MCP) of 6oxohexanoic acid and various isocyanides. Room temperature polymerization of tert-butyl isocyanide (1), 2,6-dimethylphenyl isocyanide (2), mOEG4 isocyanide (3), 5-isocyanopent-1-ene (4), and 5-isocyanopent-1-yne (5) with 6-oxohexanoic acid in CH2C12 generated PCL analogues (Pl P5) with different pendent groups amide-linked to the epsilon-position of PCL backbone. Furthermore, copolymerization of a mixture of isocyanides 1 and 3 in different molar ratios with 6oxohexanoic acid produced copolymers (P6 P9) with adjustable properties. To demonstrate the high versatility of this platform polymer, polymer P4 with pendent alkene group was further modified with glucose via the thiol ene click reaction. The structures of these (co)polymers were confirmed by H-1 NMR, C-13 NMR, and matrix-assisted laser desorption ionization mass spectroscopy. The thermal properties of these (co)polymers were examined by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). All these polymers are amorphous with variable glass transition temperatures (T-g) depending on the side groups. For the copolymers, the dependence of T(g)s on comonomer composition was well predicted by the Fox equation. Degradation of water-soluble polymer P3 in aqueous solutions was investigated by H-1 NMR and SEC. It was revealed that P3 was stable in D2O or pD = 5.8 phosphate buffer (PB) up to 15 days, while it completely degraded in basic condition over a period of 6 h and in acidic condition over a period of 24 h. Interestingly, polymer P3 even degraded steadily in pD = 7.4 PB by a random hydrolysis mechanism. Two polymer samples were examined to be nontoxic. Thus, this novel class of PCL analogues can be easily engineered to tailor its material properties and degradation behavior and may have great potential as new degradable materials to meet biomedical applications.; National Natural Science Foundation of China [21225416, 21534001]; SCI(E); ARTICLE; zcli@pku.edu.cn; 7; 2592-2600; 49
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/438299]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Zhang, Jian,Zhang, Mei,Du, Fu-Sheng,et al. Synthesis of Functional Polycaprolactones via Passerini Multicomponent Polymerization of 6-Oxohexanoic Acid and Isocyanides[J]. MACROMOLECULES,2016.
APA	Zhang, Jian,Zhang, Mei,Du, Fu-Sheng,&Li, Zi-Chen.(2016).Synthesis of Functional Polycaprolactones via Passerini Multicomponent Polymerization of 6-Oxohexanoic Acid and Isocyanides.MACROMOLECULES.
MLA	Zhang, Jian,et al."Synthesis of Functional Polycaprolactones via Passerini Multicomponent Polymerization of 6-Oxohexanoic Acid and Isocyanides".MACROMOLECULES (2016).