Synthesis of Functional Poly(ε-caprolactone)s via Living Ring-Opening Polymerization of ε-Caprolactone Using Functionalized Aluminum Alkoxides as Initiators

被引：10
作者：
Piskun, Yulia A. [1 ]
Vasilenko, Irina V. [1 ]
Zaitsev, Kirill V. [2 ]
Oprunenko, Yuri F. [2 ]
Kostjuk, Sergei V. [1 ]
机构：
[1] Belarusian State Univ, Res Inst Phys Chem Problems, 14 Leningradskaya St, Minsk 220006, BELARUS
[2] Moscow MV Lomonosov State Univ, Dept Chem, B-234 Leninskie Gory 1, Moscow 119991, Russia
来源：
MACROMOLECULAR CHEMISTRY AND PHYSICS | 2017年 / 218卷 / 07期
关键词：
aluminum alkoxides; graft copolymer; macromonomer; poly(epsilon-caprolactone); ring-opening polymerization; CYCLIC ESTERS; NMR-SPECTROSCOPY; TIN(II) OCTOATE; L-LACTIDE; COMPLEXES; POLYLACTIDES; KINETICS; MECHANISM; LIGANDS; COPOLYMERIZATION;
D O I：
10.1002/macp.201600580
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
The new aluminum compounds 1-3 modified by unsaturated alcohol, Me3-nAl(O(CH2)(4)OCH=CH2)(n) (n = 1 (1), 2 (2), 3 (3)), are synthesized and investigated by multinuclear (H-1, C-13, Al-27) NMR spectroscopy. The compounds 1-3 initiate living ring-opening poly-merization of epsilon-caprolactone in bulk at 40-80 degrees C to afford polyesters with controlled molecular weight (M-n up to 35 000 g mol(-1)) and relatively narrow molecular weight distribution (M-w/M-n < 1.8). Among initiators studied here, aluminum trialkoxide shows the highest activity, whereas aluminum dialkoxide is a less active. In all cases, the fragment of unsaturated alcohol is transferred to the end of the polymeric chain with high degree of functionality (>85%) yielding macromonomers. These macromono-mers are copolymerized with maleic anhydride to give poly(vinyl ether-co-maleic anhydride)g- poly(epsilon-caprolactone) graft copolymers.
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页数：10
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共 47 条
[1]   Metal catalysts for ε-caprolactone polymerisation [J].
Arbaoui, Abdessamad ;
Redshaw, Carl .
POLYMER CHEMISTRY, 2010, 1 (06) :801-826
[2]   Synthesis of Aluminum Complexes of Triaza Framework Ligands and Their Catalytic Activity toward Polymerization of ε-Caprolactone [J].
Bakthavachalam, K. ;
Reddy, N. Dastagiri .
ORGANOMETALLICS, 2013, 32 (11) :3174-3184
[3]   HIGH-RESOLUTION METAL-NMR SPECTROSCOPY OF ORGANOMETALLIC COMPOUNDS [J].
BENN, R ;
RUFINSKA, A .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1986, 25 (10) :861-881
[4]   Aluminum Complexes of Fluorinated Dialkoxy-Diimino Salen-like Ligands: Syntheses, Structures, and Use in Ring-Opening Polymerization of Cyclic Esters [J].
Bouyahyi, Miloud ;
Grunova, Ekaterina ;
Marquet, Nicolas ;
Kirillov, Evgueni ;
Thomas, Christophe M. ;
Roisnel, Thierry ;
Carpentier, Jean-Francois .
ORGANOMETALLICS, 2008, 27 (22) :5815-5825
[5]   Ring-opening polymerization of ε-caprolactone initiated with titanium n-propoxide or titanium phenoxide [J].
Cayuela, J ;
Bounor-Legaré, V ;
Cassagnau, P ;
Michel, A .
MACROMOLECULES, 2006, 39 (04) :1338-1346
[6]   Gallium and indium complexes for ring-opening polymerization of cyclic ethers, esters and carbonates [J].
Dagorne, Samuel ;
Normand, Mickael ;
Kirillov, Evgeny ;
Carpentier, Jean-Francois .
COORDINATION CHEMISTRY REVIEWS, 2013, 257 (11-12) :1869-1886
[7]   Ring-Opening Polymerization of L-Lactide and ε-Caprolactone Utilizing Biocompatible Zinc Catalysts. Random Copolymerization of L-Lactide and ε-Caprolactone [J].
Darensbourg, Donald J. ;
Karroonnirun, Osit .
MACROMOLECULES, 2010, 43 (21) :8880-8886
[8]   Controlled ring-opening polymerization of lactide and glycolide [J].
Dechy-Cabaret, O ;
Martin-Vaca, B ;
Bourissou, D .
CHEMICAL REVIEWS, 2004, 104 (12) :6147-6176
[9]   HYDROPHOBIC BONDING IN ALTERNATING COPOLYMERS OF MALEIC ACID AND ALKYL VINYL ETHERS [J].
DUBIN, PL ;
STRAUSS, UP .
JOURNAL OF PHYSICAL CHEMISTRY, 1970, 74 (14) :2842-&
[10]   MACROMOLECULAR ENGINEERING OF POLYLACTONES AND POLYLACTIDES .4. MECHANISM AND KINETICS OF LACTIDE HOMOPOLYMERIZATION BY ALUMINUM ISOPROPOXIDE [J].
DUBOIS, P ;
JACOBS, C ;
JEROME, R ;
TEYSSIE, P .
MACROMOLECULES, 1991, 24 (09) :2266-2270
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