Defined High Molar Mass Poly(2-Oxazoline)s

被引:74
作者
Monnery, Bryn D. [1 ]
Jerca, Valentin V. [1 ,2 ]
Sedlacek, Ondrej [1 ]
Verbraeken, Bart [1 ]
Cavill, Rachel [3 ]
Hoogenboom, Richard [1 ]
机构
[1] Univ Ghent, Dept Organ & Macromol Chem, Ctr Macromol Chem, Supramol Chem Grp, Krijgslaan 281-S4, B-9000 Ghent, Belgium
[2] Romanian Acad, Ctr Organ Chem Costin D Nenitzescu, Spl Independentei 202B, Bucharest 060023, Romania
[3] Maastricht Univ, Dept Data Sci & Knowledge Engn, Bouillonstr 8-10, NL-6211 LH Maastricht, Netherlands
关键词
cationic polymerisation; polymers; ring-opening polymerisation; tautomerisation; CYCLIC IMINO ETHERS; POLY(2-ETHYL-2-OXAZOLINE) NANODOTS; SOLAR-CELLS; POLYMERIZATION; TEMPERATURE; 2-METHYL-2-OXAZOLINE; MACROMONOMERS; TELECHELICS;
D O I
10.1002/anie.201807796
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Poly(2-alkyl-2-oxazoline)s (PAOx) are regaining interest for biomedical applications. However, their full potential is hampered by the inability to synthesise uniform high-molar mass PAOx. In this work, we proposed alternative intrinsic chain transfer mechanisms based on 2-oxazoline and oxazolinium chain-end tautomerisation and derived improved polymerization conditions to suppress chain transfer, allowing the synthesis of highly defined poly(2-ethyl-2-oxazoline) s up to ca. 50 kDa (dispersity (D) < 1.05) and defined polymers up to at least 300 kDa (D < 1.2). The determination of the chain transfer constants for the polymerisations hinted towards the tautomerisation of the oxazolinium chain end as most plausible cause for chain transfer. Finally, the method was applied for the preparation of up to 60 kDa molar mass copolymers of 2-ethyl2- oxazoline and 2-methoxycarbonylethyl-2-oxazoline.
引用
收藏
页码:15400 / 15404
页数:5
相关论文
共 30 条
[1]   POLYMERIZATION OF CYCLIC IMINO ETHERS .I. OXAZOLINES [J].
BASSIRI, TG ;
LEVY, A ;
LITT, M .
JOURNAL OF POLYMER SCIENCE PART B-POLYMER LETTERS, 1967, 5 (9PB) :871-&
[2]   Low temperature processed, high-performance and stable NiOx based inverted planar perovskite solar cells via a poly(2-ethyl-2-oxazoline) nanodots cathode electron-extraction layer [J].
Chen, Wei ;
Zhang, Gui-ning ;
Xu, Lei-ming ;
Gu, Rui ;
Xu, Zheng-he ;
Wang, Hai-jiang ;
He, Zhu-bing .
MATERIALS TODAY ENERGY, 2016, 1-2 :1-10
[3]   Poly(2-oxazoline)s: A comprehensive overview of polymer structures and their physical properties [J].
Glassner, Mathias ;
Vergaelen, Maarten ;
Hoogenboom, Richard .
POLYMER INTERNATIONAL, 2018, 67 (01) :32-45
[4]   DECOMPOSITION OF 2-METHYL-DELTA2-OXAZOLINE IN AQUEOUS SOLUTION [J].
GREENHALGH, R ;
HEGGIE, RM ;
WEINBERGER, MA .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1963, 41 (07) :1662-&
[5]   50 years of poly(2-oxazoline)s [J].
Hoogenboom, Richard .
EUROPEAN POLYMER JOURNAL, 2017, 88 :448-450
[6]   REACTION OF 2-METHYL-2-OXAZOLINE WITH TRIMETHYLSILYL INITIATORS - AN UNUSUAL MODE OF RING-OPENING [J].
HRKACH, JS ;
MATYJASZEWSKI, K .
MACROMOLECULES, 1992, 25 (08) :2070-2075
[7]   RING-OPENING POLYMERIZATION OF 2-SUBSTITUTED 2-OXAZOLINES [J].
KAGIYA, T ;
NARISAWA, S ;
MAEDA, T ;
FUKUI, K .
JOURNAL OF POLYMER SCIENCE PART B-POLYMER LETTERS, 1966, 4 (7PB) :441-&
[8]   Thermoresponsive Polymer and Fluorescent Dye Hybrids for Tunable Multicolor Emission [J].
Kim, Joo-Ho ;
Jung, Yongseok ;
Lee, Dajung ;
Jang, Woo-Dong .
ADVANCED MATERIALS, 2016, 28 (18) :3499-+
[9]   SYNTHESIS OF ACRYL-TYPE AND METHACRYL-TYPE MACROMONOMERS AND TELECHELICS BY UTILIZING LIVING POLYMERIZATION OF 2-OXAZOLINES [J].
KOBAYASHI, S ;
MASUDA, E ;
SHODA, S ;
SHIMANO, Y .
MACROMOLECULES, 1989, 22 (07) :2878-2884
[10]   POLYMERIZATION OF CYCLIC IMINOETHERS .4. OXAZOLINE POLYMERIZATION IN SOLVENTS CONTAINING DIFFERENT FUNCTIONAL GROUPS [J].
LEVY, A ;
LITT, M .
JOURNAL OF POLYMER SCIENCE PART A-1-POLYMER CHEMISTRY, 1968, 6 (1PA1) :63-&