Trang 1 NGUYEN THI NHANMINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY --- Nguyen Thi Nhan CHEMICAL SCIENCESYNTHESIS OF POLYCAPROLACTONE USING MAGNESIUM COM
NGUYEN THI NHAN MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY - Nguyen Thi Nhan CHEMICAL SCIENCE SYNTHESIS OF POLYCAPROLACTONE USING MAGNESIUM COMPOUNDS AS CATALYSTS BY RINGOPENING POLYMERIZATION MASTER THESIS OF CHEMICAL SCIENCE MAJOR: CHEMICAL ENGINEERING CH2016B Hanoi - 2018 Tai ngay!!! Ban co the xoa dong chu nay!!! 17051113838981000000 MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY Nguyen Thi Nhan SYNTHESIS OF POLYCAPROLACTONE USING MAGNESIUM COMPOUNDS AS CATALYSTS BY RING-OPENING POLYMERIZATION Major: Chemical engineering MASTER THESIS OF CHEMICAL SCIENCE MAJOR: CHEMICAL ENGINEERING SCIENCE ADVISORS: Prof Dr Tran Thi Thuy Dr Esteban Mejia Hanoi-2018 Acknowledgment I would first like to thank my thesis advisors: Prof Dr Tran Thi Thuy of the School of Chemical Engineering at Hanoi University of Science and Technology and Dr Esterban Mejia of the Polymer Department at Leibniz Institute for Catalysis They consistently allowed this paper to be my own work, but steered me in the right the direction whenever they thought I needed it I really respect those useful advices, which help me to have more motivation in my research I would also like to thank Dr Swarup Ghosh, who taught me enthusiastically and help me broaden my knowledge I would also like to acknowledge RoHan Project and DAAD, having brought me a great opportunity to experience the studying in Germany That was meaningful time, and left me many valuable lessons This research would not have been possible without the project Finally, I must express my very profound gratitude to my parents and my sister, brother and all best friends for providing me with unfailing support and continuous encouragement throughout my years of study and through the process of researching and writing this thesis Thank you Hanoi, May 2018 Nguyen Thi Nhan ASSURANCE I pledge that this is my own independent scientific research The data used in the dissertation analysis has a clear, published source in accordance with the regulations The research results in the thesis are self-study, analyzing honestly, and objectively These results have not been published in any other study Author Nguyen Thi Nhan LIST OF SYMBOLS AND ABBREVIATIONS Abbreviation Explanation AM Activated monomer AROP Anionic ring-opening polymerization BnOH Benzyl alcohol Catalyst Dibutyl magnesium, nBu2 Mg Catalyst Etyl n-butyl magnesium, (Et)Mg(nBu) Catalyst CDCl n-Butyl n-octyl magnesium, (nBu)Mg( nOct) Chloroform D CROP Cationic ring-opening polymerization DCM Dichloromethane DEPT DPE Distortionless Enhancement by Polarization Transfer 1,1-diphenylethylene DSC Differential scanning calorimetry FT-IR Fourrier Transformation InfraRed GPC Gel permeation chromatography Mn Molar mass averages of the number Mw Molar mass averages of the weight NMR Nuclear magnetic resonance PCL Polycaprolactone PDI Polydispersity index (weight distribution) PET Polyethylene terephthalate PGA Poly(glycolic acid) PHB Polyhydroxybutyrate PLA Poly(lactide acid) ROP Ring-opening polymerization SEC Size exclusion chromatography Tg Glass transition temperature THF Tetrahydrofuran Tm Melting point XRD X-Ray Diffraction ε-CL Caprolactone monomer LIST OF TABLES Table Number of publications in the past 110-year period Table Properties of PCL Table Examining kinetic of reactions 23 Table ROP of ɛ-caprolactone catalyzed by catalyst 1, 2, in dichloromethane 23 Table Oligomer of ɛ-caprolactone 24 Table Oligomer of ɛ-caprolactone with presence of BnOH 24 Table Effect of the molar ratio of monomer and catalyst on the ROP 25 Table Effect of the mole ratio of monomer and catalyst on the ROP 25 Table ROP of ɛ-caprolactone with the presence of benzyl alcohol as a co-initiator 26 Table 10 The effect of co-initiator, BnOH .38 LIST OF SCHEMES Scheme Synthesis of CL by condensation method Scheme ROP of CL Scheme Ring-opening polymerization 11 Scheme General mechanism of AROP 12 Scheme ROP of lactones .13 Scheme AROP mechanism 13 Scheme Propose mechanism of ROP initiated by dibutylmagnesium 14 Scheme CROP of CL 15 Scheme Coordination-insertion ring-opening polymerization 16 Scheme 10 ROP with the presence of alcohols as co-initiators .17 Scheme 11 Polymer from the reaction with catalyst 27 Scheme 12 Polymer from the reaction with catalyst and the presence of BnOH 27 Scheme 13 ROP of CL without BnOH 28 Scheme 14 ROP of CL with the presence of BnOH 28 Scheme 15 Proposed mechanism of polymerization without BnOH .41 Scheme 16 Proposed mechanism of polymerization with the presence of BnOH 42 LIST OF FIGURES Figure Applications of PCL Figure Bruker Avance 400 21 Figure GPC equipment 21 Figure DSC curves of PCLs 28 Figure The GPC spectrum of Oligomer of ε-CL 29 Figure The GPC spectrum of PCL at ratio 200:1 29 Figure The GPC spectrum of PCL at ratio 200:1 with the presence of BnOH .30 Figure Semi-logarithmic plots of ε-CL and conversion in time: [M]o/[Cat 1]o = 200 at 40 °C .32 Figure The plot of the initial rate vs the concentration of catalyst for the ROP of ε-CL 33 Figure 10 The effect of catalysts on Mn of PCL 34 Figure 11 The effect of catalyst on PDI of PCL 35 Figure 12 The effect of molar ratio on ROP when using catalyst 36 Figure 13 The effect of molar ratio on ROP when using catalyst 36 Figure 14 : 1H NMR spectrum of PCL at ratio 20/1 39 Figure 15 13C NMR spectrum of PCL at ratio 20/1 40 TABLE OF CONTENTS Acknowledgment ASSURANCE LIST OF SYMBOLS AND ABBREVIATIONS LIST OF TABLES LIST OF SCHEMES LIST OF FIGURES INTRODUCTION .1 CHAPTER REVIEW OF LITERATURES .3 1.1 Biodegradable polyester, poly (ɛ-caprolactone) 1.1.1 Biodegradable polyester 1.1.2 Poly(ε-caprolactone) 1.2 Main-organometallic catalysts, magnesium complexes 1.3 Ring-opening polymerization (ROP) .10 1.3.1 Anionic ring-opening polymerization (AROP) of cyclic esters 12 1.3.3 Coordination-insertion Ring-opening polymerization .15 1.3.4 ROP with the presence of alcohols as co-initiators 16 1.3.5 Kinetics and mechanism 18 CHAPTER EXPERIMENT .20 2.1 Chemicals .20 2.2 Equipment .20 2.3 Polymerization of ɛ-caprolactone 21 2.4 Examining kinetic of reactions with catalysts 22 2.5 Attachments 23 CHAPTER RESULTS AND DISCUSSION .27 3.1 General ROP 27 3.2 The kinetic of ROP of PCL 31 3.3 Effect of catalysts on the polymer properties .33 3.4 Effect of mole ratio to ROP 35