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Methyl Methacrylate) by Activators Regenerated by Electron Transfer (ARGET) Atom Transfer Radical Polymerization (ATRP) Was Extensively Studied

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Methyl Methacrylate) by Activators Regenerated by Electron Transfer (ARGET) Atom Transfer Radical Polymerization (ATRP) Was Extensively Studied SYNTHESIS OF HIGH MOLECULAR WEIGHT POLY (METHYL METHACRYLATE) BY ARGET ATRP A Thesis Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Master of Science Jialin Qiu August, 2015 SYNTEHSIS OF HIGH MOLECULAR WEIGHT POLY (METHYL METHACRYLATE) BY ARGET ATRP Jialin Qiu Thesis Approved: Accepted: _____________________ ____________________ Advisor Department Chair Dr. Kevin A. Cavicchi Dr. Sadhan C. Jana _____________________ _____________________ Advisor Dean of the College Dr. Bryan D. Vogt Dr. Eric J. Amis _____________________ _____________________ Committee Member Interim Dean of the Graduate Dr. Sadhan C. Jana Dr. Rex D. Ramsier ____________________ _____________________ Committee Member Date Dr. Alamgir Karim ii ABSTRACT Synthesis of poly (methyl methacrylate) by activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) was extensively studied. It was observed that when the target molecular weight is higher, side reactions and terminations becomes more prominent. In this study, a facile method was used to synthesize high molecular weight PMMA by ARGET ATRP. The effect of solvent, catalyst and ligand were discussed systematically. Low molecular weight polyethylene glycol (PEG) (600 g/mol) as solvent significantly increased the reaction rate and provides molecular weight as high as 96 kDa within 2h reaction, Đ as low as 1.2. PEG can stabilize the catalyst by complexing to avoid the side reactions such as the reactions between catalyst and chain end. The terminal hydroxyl group could potentially increase the reaction rate. It was also observed that the results have PEG molecular weight dependence. As PEG molecular weight increased, viscosity increased which resulted in poor polymer chain diffusion. However PEG-metal stability constant increased when PEG molecular weight increased which provided better control. These factors competitively affected the polymerization kinetics. Optimum solvent was observed using PEG (600 Da). The comparison between two copper based catalysts CuBr2 iii and CuCl2 showed that shorter bond length of Cu-Br leaded to a faster reaction rate. For the comparison of ligands, N,N,N′,N′,N′′-pentamethyldiethylenetriamine (PMDETA) as a tridentate ligand had weaker reducing ability but stronger coordination ability compared to tetramethylethylenediamine (TMEDA) as bidentate ligand. Synthesized PMMA was used as macroinitiator to synthesize poly (methyl methacrylate)-block-polystyrene (PMMA-PS) block copolymer by bulk ARGET ATRP. With the increasing amount of styrene, PMMA diffusion became better and prematurely termination was reduced. PMMA-PS with molecular weight of 770 kDa and Đ of 1.32 was successfully synthesized. iv ACKNOWLEGEMENTS I would like to appreciate all those people who have helped me during my master study in University of Akron. Firstly I would like to give my great gratitude to my advisors, Prof. Bryan Vogt and Prof. Cavicchi, for their support in the research. They show their patience when teaching me how to do research. They provided me many ideas and show me the research method. I cannot work efficiently without their help. I would like to thank Prof. Karim for being my committee member and his most valuable comments on the thesis. There are a lot of people in our group who has helped me a lot and give me sincere suggestions when I got problems in research. I would like to thank Zhe Qiang, Junyan Wang, Guodong Deng, Jehoon Lee, Changhuai Ye for their help and discussion with me. And I would like to thank all my classmates and friends in University of Akron and University of Akron and Donghua University. They offer me the opportunity for doing research here. I got to learn much through 3+2 program. Lastly, I would like v to thank my family members: grandparents and parents. They supported me to study abroad and encourage me all the time. vi TABLE OF CONTENTS Page LIST OF FIGURES ................................................................................................ x LIST OF SCHEMES ............................................................................................. xii LIST OF TABLES ................................................................................................ xiii CHAPTER I. INTRODUCTION ................................................................................................ 1 1.1Introduction ................................................................................................... 1 1.1.2 Polymerization Method to Synthesize Poly (methyl methacrylate) ....... 2 1.1.3 High Molecular Weight Poly (methyl methacrylate) Synthesis ............ 11 II. SYNTHESIS OF HIGH MOLECULAR WEIGHT PMMA .................................. 16 2.1 Motivation ................................................................................................... 16 2.2 Introduction ................................................................................................ 17 2.2.2 Use of PEG as Solvent ....................................................................... 19 2.2.3 Use of PEG as Solvent to Synthesize High Molecular Weight PMMA 22 2.2.4 Copper Based Catalyst ....................................................................... 22 2.2.5 Nitrogen Based Ligand ........................................................................ 25 2.3 Experimental Section ................................................................................. 27 2.3.1 Materials .............................................................................................. 27 vii 2.3.2 ARGET ATRP of MMA in PEG (600) with PMDETA as Reducing Agent and Ligand ................................................................................................... 28 2.3.3 Characterization of PMMA .................................................................. 28 2.4 Results and Discussion ............................................................................. 29 2.4.1 Scheme of Reactants .......................................................................... 29 2.4.2 Effect of Solvents ................................................................................ 32 2.4.3 Effect of Catalyst ................................................................................. 41 2.4.4 Effect of Ligand ................................................................................... 45 2.5 Conclusions ............................................................................................... 49 III. SYNTHESIS OF PMMA-PS BY ARGET ATRP.............................................. 51 3.1 Introduction ................................................................................................ 51 3.1.1 Fractional Precipitation ........................................................................ 52 3.2 Experimental Section ................................................................................. 57 3.2.1 Materials .............................................................................................. 57 3.2.2 Fractional Precipitation ........................................................................ 57 3.2.3 Chain Extension of PMMA Macroinitiator with Styrene ....................... 57 3.2.4 Characterization of PMMA-PS ............................................................ 58 3.3 Results and Discussion ............................................................................. 58 3.3.1 Fraction Precipitation of PMMA ........................................................... 58 3.3.2 Effect of Styrene Amount .................................................................... 60 3.3.2 Effect of PMMA Macroinitiator Molecular Weight ................................ 64 viii 3.4 Conclusions ............................................................................................... 66 CONCLUSIONS .................................................................................................. 68 REFRENCES ...................................................................................................... 70 ix LIST OF FIGURES Figure Page 1.1 Scheme of high-pressure AGET ATRP method ..................................... 14 2.1 X-ray structure of CuCl2 and CuBr2 ........................................................ 24 2.2 UV-visible spectra of Cu (II) Br2 with (A) TMEDA, (B) PMDETA ............ 26 2.3 Solubility test of CuBr2 in (A) acetonitrile, (B) PEG-600, and (C) anisole .............................................................................................................. 34 2.4 Molecular weight evolution affected by PEG molecular weight .............. 37 2.5 Kinetic plots affected by PEG molecular weight ..................................... 38 2.6 Molecular weight dispersity (Đ) affected by PEG molecular weight ....... 39 2.7 Molecular weight evolution affected by catalyst ..................................... 42 2.8 Kinetic plots affected by catalyst ............................................................ 43 2.9 Molecular weight dispersity (Đ) affected by catalyst .............................. 44 2.10 Molecular weight evolution affected by ligand ...................................... 46 2.11 Kinetic plots affected by ligand ............................................................. 47 2.12 Molecular weight dispersity (Đ) affected by ligand ............................... 48 3.1 Process of fractional precipitation .......................................................... 54 3.2 GPC traces of PMMA
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