Synthesis of Novel Renewable Polyesters and Polyamides with Olefin Metathesis

被引：19
作者：
Dewaele, Annelies [1 ]
Meerten, Lotte [1 ]
Verbelen, Leander [2 ]
Eyley, Samuel [3 ]
Thielemans, Wim [3 ]
Van Puyvelde, Peter [2 ]
Dusselier, Michiel [1 ]
Sels, Bert [1 ]
机构：
[1] Katholieke Univ Leuven, Ctr Surface Chem & Catalysis, Celestijnenlaan 200F, B-3001 Heverlee, Belgium
[2] Katholieke Univ Leuven, Dept Chem Engn, Celestijnenlaan 200F, B-3001 Heverlee, Belgium
[3] Katholieke Univ Leuven, Dept Chem Engn, Campus Kulak Kortrijk,Etienne Sabbelaan 53, B-8500 Kortrijk, Belgium
来源：
ACS SUSTAINABLE CHEMISTRY & ENGINEERING | 2016年 / 4卷 / 11期
关键词：
Olefin metathesis; Biomass; Building blocks; Methyl vinyl glycolate; alpha-Hydroxyacids; Diacids; Biodegradable polymers; Polylactic acid; ALIPHATIC CARBOXYLIC-ACIDS; LACTIC-ACID; ALKALINE-DEGRADATION; SOFTWOOD POLYSACCHARIDES; MECHANICAL-PROPERTIES; CATALYTIC CONVERSION; BIOMASS CONVERSION; POLY(LACTIC ACID); METHYL LACTATE; ALKYL LACTATES;
D O I：
10.1021/acssuschemeng.6b00807
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Unsaturated and hydroxyl-functionalized C6-dicarboxylic acids were successfully synthesized via olefin metathesis from methyl vinyl glycolate (MVG), a renewable alpha-hydroxy C4-ester product from Lewis-acid carbohydrate conversion. Addition of a second-generation Hoveyda- Grubbs catalyst to neat MVG leads to a near quantitative yield of dimethyl-2,5-dihydroxy-3-hexenedioate (DMDHHD). Additional hydrolysis and hydrogenation steps form interesting polymer building blocks like 2,5-dihydroxy-3-hexenedioic acid (DHHDA) and 2,5-dihydroxyadipic acid (DHAA). Their use in polyester and polyamide synthesis is demonstrated after determination of their physical and spectroscopic characteristics. Copolymerization of DHHDA with L-lactic acid for instance produces a cross-linked poly(L-lactic acid-co-DHHDA) polyester. Proof of cross-links is ascertained by NMR and FTIR. Substantial impact on the melting, thermal, and polar properties of PLA are observed already at low amounts of DHHDA (0.1 mol %) in accord with the presence of cross-links in the polymer. Biobased polyamides were also synthesized by equimolar reaction of DHHDA with hexamethylenediamine, producing a renewable polyamide analogue of the petroleum-based nylon-6,6. Interestingly, the as-synthesized polyamide (alpha-bishydroxylated unsaturated polyamide, HUPA) possesses similar thermal stability as nylon-6,6 but shows different chemical properties as a result of the double bond and alpha-hydroxy functionality.
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收藏
页码：5943 / 5952
页数：10
相关论文
共 91 条
[1]   Ruthenium carbene complexes with imidazol-2-ylidene ligands:: Syntheses of conduritol derivatives reveals superior RCM activity [J].
Ackermann, L ;
El Tom, D ;
Fürstner, A .
TETRAHEDRON, 2000, 56 (15) :2195-2202
[2]  
ALEN R, 1988, CELL CHEM TECHNOL, V22, P507
[3]   FORMATION OF HYDROXY CARBOXYLIC-ACIDS FROM SOFTWOOD POLYSACCHARIDES DURING ALKALINE PULPING [J].
ALEN, R ;
LAHTELA, M ;
NIEMELA, K ;
SJOSTROM, E .
HOLZFORSCHUNG, 1985, 39 (04) :235-238
[4]  
ALEN R, 1988, CELL CHEM TECHNOL, V22, P443
[5]   Enhancing the melt stability of polylactide stereocomplexes using a solid-state cross-linking strategy during a melt-blending process [J].
Bai, Hongwei ;
Liu, Huili ;
Bai, Dongyu ;
Zhang, Qin ;
Wang, Ke ;
Deng, Hua ;
Chen, Feng ;
Fu, Qiang .
POLYMER CHEMISTRY, 2014, 5 (20) :5985-5993
[6]  
Biermann U, 2000, ANGEW CHEM INT EDIT, V39, P2206, DOI 10.1002/1521-3773(20000703)39:13<2206::AID-ANIE2206>3.0.CO
[7]  
2-P
[8]   Oils and Fats as Renewable Raw Materials in Chemistry [J].
Biermann, Ursula ;
Bornscheuer, Uwe ;
Meier, Michael A. R. ;
Metzger, Juergen O. ;
Schaefer, Hans J. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (17) :3854-3871
[9]   Technology development for the production of biobased products from biorefinery carbohydrates-the US Department of Energy's "Top 10" revisited [J].
Bozell, Joseph J. ;
Petersen, Gene R. .
GREEN CHEMISTRY, 2010, 12 (04) :539-554
[10]  
Burk MJ, 2011, US Patent, Patent No. [20110124911 A1, 20110124911]
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