Controlled/Living Ring-Opening Polymerization of e-Caprolactone with Salicylic Acid as the Organocatalyst

被引：32
作者：
Xu, Jinbao [1 ]
Song, Junzhe [2 ]
Pispas, Stergios [3 ]
Zhang, Guangzhao [1 ,2 ]
机构：
[1] S China Univ Technol, Fac Mat Sci & Engn, Guangzhou, Guangdong, Peoples R China
[2] Univ Sci & Technol China, Dept Chem Phys, Hefei Natl Lab Phys Sci Microscale, Hefei 230026, Peoples R China
[3] Natl Hellen Res Fdn, Inst Theoret & Phys Chem, GR-11635 Athens, Greece
来源：
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY | 2014年 / 52卷 / 08期
关键词：
biodegradable; block copolymerization; epsilon-caprolactone; controlled ring-opening polymerization; end functionality; living polymerization; polyesters; salicylic acid; MONOMER CATIONIC-POLYMERIZATION; N-HETEROCYCLIC CARBENES; EPSILON-CAPROLACTONE; ETHYLENE-OXIDE; ORGANIC CATALYSTS; PHOSPHAZENE BASES; BLOCK; COPOLYMER;
D O I：
10.1002/pola.27104
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
Ring-opening polymerization (ROP) of epsilon-caprolactone (CL) using salicylic acid (SAA) as the organocatalyst and benzyl alcohol as the initiator in bulk at 80 degrees C successfully proceeded to give a narrowly distributed poly(epsilon-caprolactone) (PCL). In addition, 2-hydroxyethyl methacrylate, propargyl alcohol, 6-azido-1-hexanol, and methoxy poly(ethylene glycol) were also used as functional initiators. The H-1 NMR, SEC, and MALDI-TOF MS measurements of the PCL clearly indicate the presence of the initiator residue at the chain end, implying that the SAA-catalyzed ROP of CL was through the activated monomer mechanism. The kinetic experiments confirmed the controlled/living nature of the SAA-catalyzed ROP of CL. Furthermore, the block copolymerization of CL and -valerolactone successfully proceeded to give poly(epsilon-caprolactone)-block-poly(-valerolactone). (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1185-1192
引用
收藏
页码：1185 / 1192
页数：8
相关论文
共 44 条
[1]   MALDI-TOF MS Reveals the Molecular Level Structures of Different Hydrophilic-Hydrophobic Polyether-esters [J].
Adamus, Grazyna ;
Hakkarainen, Minna ;
Hoglund, Anders ;
Kowalczuk, Marek ;
Albertsson, Ann-Christine .
BIOMACROMOLECULES, 2009, 10 (06) :1540-1546
[2]   Nucleophilicities and carbon basicities of DBU and DBN [J].
Baidya, M. ;
Mayr, Herbert .
CHEMICAL COMMUNICATIONS, 2008, (15) :1792-1794
[3]   Cationic copolymerization of ε-caprolactone and L,L-lactide by an activated monomer mechanism [J].
Basko, Maigorzata ;
Kubisa, Przemysiaw .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2006, 44 (24) :7071-7081
[4]   Activation in anionic polymerization: Why phosphazene bases are very exciting promoters [J].
Boileau, S. ;
Illy, N. .
PROGRESS IN POLYMER SCIENCE, 2011, 36 (09) :1132-1151
[5]   ω-Pentandecalactone Polymerization and ω-Pentadecalactone/ε-Caprolactone Copolymerization Reactions Using Organic Catalysts [J].
Bouyahyi, Miloud ;
Pepels, Mark P. F. ;
Heise, Andreas ;
Duchateau, Rob .
MACROMOLECULES, 2012, 45 (08) :3356-3366
[6]   Amidine-Mediated Zwitterionic Polymerization of Lactide [J].
Brown, Hayley A. ;
De Crisci, Antonio G. ;
Hedrick, James L. ;
Waymouth, Robert M. .
ACS MACRO LETTERS, 2012, 1 (09) :1113-1115
[7]  
BRZEZINSKA K, 1986, MAKROMOL CHEM-RAPID, V7, P1
[8]   Controlled/living ring-opening polymerization of E⟩-caprolactone catalyzed by phosphoric acid [J].
Chen ChunXia ;
Xu Rong ;
Li Bin .
SCIENCE CHINA-CHEMISTRY, 2012, 55 (07) :1257-1262
[9]   Catalytic insights into acid/base conjugates: highly selective bifunctional catalysts for the ring-opening polymerization of lactide [J].
Coady, Daniel J. ;
Fukushima, Kazuki ;
Horn, Hans W. ;
Rice, Julia E. ;
Hedrick, James L. .
CHEMICAL COMMUNICATIONS, 2011, 47 (11) :3105-3107
[10]   First example of N-heterocyclic carbenes as catalysts for living polymerization:: Organocatalytic ring-opening polymerization of cyclic esters [J].
Connor, EF ;
Nyce, GW ;
Myers, M ;
Möck, A ;
Hedrick, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (06) :914-915
12345