Enzymatic polymerization of biobased polyesters and polyamides Jiang, Yi

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1 University of Groningen Enzymatic polymerization of biobased polyesters and polyamides Jiang, Yi IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2016 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Jiang, Y. (2016). Enzymatic polymerization of biobased polyesters and polyamides [Groningen]: University of Groningen Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date:

2 Enzymatic Polymerization of Biobased Polyesters and Polyamides Yi Jiang

3 Enzymatic Polymerization of Biobased Polyesters and Polyamides Yi Jiang PhD Thesis University of Groningen, the Netherlands. Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, the Netherlands. Zernike Institute PhD thesis series ISSN: ISBN: (Book) (PDF without DRM) The research presented in this thesis was performed in the research group of Macromolecular Chemistry and New Polymeric Materials of the Zernike Institute for Advanced Materials at the University of Groningen, the Netherlands. This research forms part of the research programme of the Dutch Polymer Institute (DPI), project #727c polymers go even greener. Cover photo: Binbing Liu Layout: Yi Jiang Cover Layout: Ridderprint BV, Printing: Ridderprint BV,

4 Enzymatic Polymerization of Biobased Polyesters and Polyamides PhD thesis to obtain the degree of PhD at the University of Groningen on the authority of the Rector Magnificus Prof. E. Sterken and in accordance with the decision by the College of Deans. This thesis will be defended in public on Friday 4 March 2016 at hours by Yi Jiang born on 21 February 1980 in Guangxi, China

5 Supervisor Prof. K.U. Loos Assessment Committee Prof. H.J. Heeres Prof. A. Gandini Prof. X. Zhu

6 How Confucius was affected by a running stream: the passage of time is just like the flow of water, which goes on day and night. Dedicated to my beloved parents and wife.

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8 Table of Contents Chapter 1 Enzymatic Synthesis of Biobased Polyesters and Polyamides Polymers: from Petrol-Based to Biobased and Beyond Polyesters and Polyamides Biobased Monomers Used in this Research Biobased Aliphatic Diacids Biobased Aliphatic Diols and Polyols Biobased Aliphatic Diamine Biobased Furan Monomers Lipases Enzymatic Polymerization of Polyesters Enzymatic Polymerization of Polyamides Lipase-Catalyzed Synthesis of Sustainable Polyesters and Polyamides from Biobased Monomers Biobased Saturated Aliphatic Poly(alkylene dicarboxylate)s Biobased Unsaturated Aliphatic Polyesters Biobased Polyamides Furan Polyesters and Furan Polyamides Scope of this Thesis References Chapter 2 Enzyme-Catalyzed Synthesis of Biobased Unsaturated Aliphatic Polyesters: Effects of Polymerization Conditions and their Thermal Properties Introduction... 40

9 Table of Contents 2.2 Experimental Section Materials General Procedure for CALB-Catalyzed Co-Polymerization of Succinate, Itaconate and 1,4-Butanediol in Solution Control Reactions H-NMR Investigation of CALB-Catalyzed Oligomerization of Diethyl Succinate, Dimethyl Itaconate and 1,4-Butanediol in Diphenyl Ether Instrumental Methods Calculation of the Molar Composition of PBSI from 1 H-NMR Calculation of the Number Average Molecular Weight of PBSI from 1 H- NMR Results and Discussion Effects of Polymerization Conditions on CALB-Catalyzed Co- Polymerization of Diethyl Succinate, Dimethyl Itaconate and 1,4-Butanediol Effect of Itaconate Structure on CALB-Catalyzed Synthesis of PBSI in Diphenyl Ether CALB-Catalyzed Synthesis of PBSI Using the Optimal Polymerization Conditions Thermal Properties of the Obtained PBS and PBSIs Conclusions References Chapter 3 Enzymatic Synthesis of Fully Biobased Saturated and Unsaturated Aliphatic Polyesters by Using Different Monomer Substrates and Polymerization Methods Introduction Experimental Section Chemicals Page II

10 Table of Contents General Procedure for CALB-Catalyzed Polymerization by Using Different Monomer Substrates and Polymerization Methods Instrumental Methods H- and 13 C-NMR Analysis of the Obtained Poly(butylene succinate), Poly(butylene succinate-co-itaconate)s, and Oligo(butylene itaconate) ATR-FTIR Analysis of Poly(butylene succinate), Poly(butylene succinate-co-itaconate)s, and Oligo(butylene itaconate) Cross-linking of Poly(butylene succinate-co-itaconate)s and their Mechanical Properties Characterizations Results and Discussion CALB-Catalyzed Dehydration Polycondensation of Succinic Acid, Itaconic Acid and 1,4-Butanediol via Different Polymerization Methods CALB-Catalyzed Polycondensation of Diethyl Succinate, Dimethyl Itaconate and 1,4-Butanediol via Different Polymerization Methods Microstructures of Poly(butylene succinate-co-itaconate)s from Different Polymerization Methods Crystalline Properties of the Obtained Polyesters Thermal and Mechanical Properties of the Cross-Linked Poly(butylene succinate-co-itaconate)s Conclusions Reference C Chapter 4 Environmentally Benign Synthesis of Saturated and Unsaturated Aliphatic Polyesters via Enzymatic Polymerization of Biobased Monomers Introduction Experimental Section Materials General Procedure for CALB-Catalyzed Synthesis of Biobased Saturated and Unsaturated Aliphatic Polyesters via a Two-Stage Method in Diphenyl Ether Page III

11 Table of Contents Solvent Casting of Unsaturated Aliphatic Polyester Films and UV Cross- Linking Instrumental Methods Results and Discussion CALB-Catalyzed Synthesis of Biobased Saturated and Unsaturated Aliphatic Polyesters via the Two-Stage Method in Diphenyl Ether Crystalline Properties of the Biobased Saturated and Unsaturated Aliphatic Polyesters Thermal Properties of the Biobased Saturated and Unsaturated Aliphatic Polyesters Thermal and Mechanical Properties of the UV Cross-Linked Unsaturated Aliphatic Polyesters Conclusions References Chapter 5 Enzymatic Synthesis of Renewable 2,5-Bis(hydroxymethyl)furan-Based Polyesters Introduction Experimental Methods Page IV Materials General Procedure for CALB-Catalyzed Polycondensation of Diacid Ethyl Esters and BHMF in Diphenyl Ether via a Two-Stage, Three-Step Method Control Reactions H-NMR Investigation of CALB-Catalyzed Polycondensation of BHMF and Diacid Ethyl Esters in Diphenyl Ether via the Two-Stage, Three-Step Method Instrumental Methods Results and Discussion CALB-Catalyzed Polycondensation of BHMF with Various Diacid Ethyl Esters in Diphenyl Ether

12 Table of Contents MALDI-ToF MS Analysis of the Obtained BHMF-Based Polyesters: Microstructures with Different End Groups Crystalline Properties of the Obtained BHMF-Based Polyesters Thermal Properties of the Obtained BHMF-Based Polyesters Conclusions References C Chapter 6 A Biocatalytic Approach Towards Sustainable 2,5-Furandicarboxylic Acid- Based Furanic-Aliphatic Polyesters Introduction Experimental Methods Materials General Procedure for CALB-Catalyzed Polycondensation of DMFDCA and Aliphatic Diols in Diphenyl Ether via a Two-Stage Method General Procedure for CALB-Catalyzed Polycondensation of DMFDCA and Aliphatic Linear Diols in Diphenyl Ether via a Temperature-Varied Two- Stage Method Control Reactions Instrumental Methods NMR Analysis of the Obtained Furanic-Aliphatic Polyesters ATR-FTIR Analysis of the Obtained Furanic-Aliphatic Polyesters Results and Discussion CALB-Catalyzed Synthesis of Furanic-Aliphatic Polyesters from DMFDCA and Aliphatic Diols via the Two-Stage Method CALB-Catalyzed Synthesis of Furanic-Aliphatic Polyesters from DMFDCA and α,ω-aliphatic Linear Diols via the Temperature-Varied Two- Stage Method MALDI-ToF MS Analysis of the Obtained Furanic-Aliphatic Polyesters: Microstructures and End Groups Crystalline Properties of the Obtained Furanic-Aliphatic Polyesters Page V

13 Table of Contents Thermal Stability of the Obtained Furanic-Aliphatic Polyesters Thermal Transitions of the Obtained Furanic-Aliphatic Polyesters Conclusions References Chapter 7 Enzymatic Polymerization of 2,5-Furandicarboxylic Acid-Based Furanic- Aliphatic Polyamides as Sustainable Alternatives to Polyphthalamides Introduction Experimental Section Chemicals General Procedure for N435-Catalyzed Polymerization of PA 8,F Control Reactions Instrumental Methods Results and Discussion Substrate Selection N435-Catalyzed Polymerization of PA 8,F via the One-Stage Method in Toluene N435-Catalyzed Polymerization of PA 8,F via the Temperature Varied Two-Stage Method in Diphenyl Ether Crystallinity and Thermal Properties of the Obtained P8AF Conclusions References Summary Samenvatting Publications Acknowledgements Page VI