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Bio-Based Reactive Diluents and Thiol-Ene

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Bio-Based Reactive Diluents and Thiol-Ene BIO-BASED REACTIVE DILUENTS AND THIOL-ENE PHOTOPOLYMERIZATION FOR ENVIRONMENTALLY BENIGN COATINGS A Dissertation Presented to The Graduate Faculty of the University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Kosin Wutticharoenwong December, 2007 BIO-BASED REACTIVE DILUENTS AND THIOL-ENE PHOTOPOLYMERIZATION FOR ENVIRONMENTALLY BENIGN COATINGS Kosin Wutticharoenwong Dissertation Approved: Accepted: _____________________________ _____________________________ Advisor Department Chair Dr. Mark D. Soucek Dr. Sadhan C. Jana _____________________________ _____________________________ Committee Member Dean of the College Dr. Kevin Cavicchi Dr. Stephen Cheng _____________________________ _____________________________ Committee Member Dean of the Graduate School Dr. Kyonsuku Min Cakmak Dr. George R. Newkome _____________________________ _____________________________ Committee Member Date Dr. George Chase _____________________________ Committee Member Dr. Wiley J. Youngs ii ABSTRACT Tung oil was used as diene for modification via a Diels-Alder reaction with acrylate dienophiles. Tung oil was modified with three different acrylate molecules: 3- methacryloxypropyl trimethoxysilane (MAS), 2,2,2-trifluoroethyl methacrylate (TFM) and triallyl ether acrylate (TAEA) at atmospheric pressure. The modified tung oils were characterized using 1H NMR, 13C NMR, and FT-IR. The molecular weight and distribution were characterized using GPC, and MALDI-TOF. The effects of new acrylate modified tung oils on the properties of alkyd-based coatings film were investigated including hardness, solvent resistance, flexibility, gloss, impact resistance, contact angle, tensile, and thermo-mechanical properties. The viscosity can be reduced to the application viscosity of the alkyd by the reactive diluents. Drying time study showed that drying time can be altered by types and level of diluent added. All the results revealed that modified tung oils can be used as volatile organic compound (VOC) compliant in alkyd systems. Synthetic methods were developed to prepare thiols and mercaptopropionate thiols for thiol-ene photopolymerization. New thiols were characterized by 1H NMR, 13C NMR, Fourier transform infrared spectroscopy (FT-IR), and elemental analysis (C, H, S, O). Photopolymerization kinetics of the thiols with representative alkenes were investigated by time resolved Fourier transform infrared spectroscopy (FT-IR) with and iii without photoinitiator. It was proposed that steric hinderance of thiol structures lower the initial reaction rate of photopolymerization. An experiment was planned according to ternary mixture design to investigate the influence the three thiols on the thermo- mechanical and coatings properties of thiol-ene photopolymerizable materials. It was found that the steric and rigidity of the double cycloaliphatic structure of thiol enhanced the tensile strength, tensile modulus, glass transition temperature (Tg) and pencil hardness with loss of crosslink density of the film. The result suggested that steric and rigidity of thiols structures played an important role in both kinetics and material properties on thiol- ene photopolymerization. A thiol colloid oligomer was prepared vas sol-gel method from mercaptopropyl- trimethoxysilane (MPTS). Thiol colloid oligomer was also characterized using 1H NMR, 29Si NMR, FT-IR, GPC, and MALDI-TOF mass spectroscopy. Thiol colloid oligomer was attempted to photopolymerize with triallyl ether modified tung oil (TAETO) as a bio-based alkene via thiol-ene photopolymerization. However, kinetics results via time- resolved FT-IR indicated that MPTS colloid oligomer did not affect the initial reaction rate and final conversion of MPTS/TAETO system due to the immiscibility between TAETO and MPTS oligomer. iv DEDICATION To my parents and my sisters for their exceptional love and support v ACKNOWLEDGEMENTS I would like to express my special thank to my advisor, Dr. Mark D. Soucek, for his guidance, support, and motivation throughout my doctoral work. I would like to also thank to my committee members, Dr. Kevin Cavicchi, Dr. Kyonsuku Min Cakmak, Dr. George Chase, and Dr. Wiley J. Youngs for their contributions. I would like to thank Dr. Jun Hu for allowing me to use the time-resolved FT-IR equipment in Department of Chemistry. I would like to also thank Mr. Jay Hawkins, Mr. Chris Harding from Waterlox Coatings Inc. for their financial support and allowing me to have a chance to work with tung oil, Mr. Steven Johnson from Advanced coatings international for my internship experiences. I would like to thank to the faculty and stuff in the Department of Polymer Engineering and my colleagues in Soucek’s research groups for their help and support. Finally, I would like to express my sincere gratitude to my parents Chamroen and Rattana Wutticharoenwong. Without their unconditional love and support, this work would not have been possible. vi TABLE OF CONTENTS Page LIST OF TABLES……………………………………………………………..........…xii LIST OF FIGURES……………………………………………………………......…..xiii CHAPTER I. INTRODUCTION……………………………………………………………………..1 II. LITERATURES REVIEW: BIO-BASED REACTIVE DILUENTS………………...5 2.1 Historical………………………………………………………….…….……5 2.2 Solvents………………………………………………………………………7 2.3 Drying oils…………………………………………………………….……14 2.4 Diels-Alder Reactions………………………………………………………18 2.5 Sol-gel Chemistry…………………………………....................……….….22 2.6 Fluorinated polymers….................................................................................23 2.7 Alkyds resins………………………………………………………………..24 2.8 High Solid Coatings……………………………………………….………..26 2.9 Previous Studies of Reactive Diluents……………………………...………28 III. SYNTHESIS AND CHARACTERIZATION OF ACRYLIC MODIFIED TUNG OILS……………………………………………………………………………….....30 3.1 Abstract……………………………………………………………..............30 3.2 Introduction………………………………………………....................……30 vii 3.3 Materials…………………………………………....................................…34 3.4 Instruments and Characterization…..............................................................34 3.5 Synthesis of acrylic modified tung oils…......................................................35 3.6 Result and discussion……………………………………………….....……38 3.7 Conclusions………………………………………………………….......….53 IV. EVALUATION OF MODIFIED TUNG OIL AS A REACTIVE DILUENT ON COATINGS PROPERTIES IN ALKYD SYSTEMS…………….............................54 4.1 Abstract…………………………………………………..........................…54 4.2 Introduction………………………………………....................................…56 4.3 Materials…....................................................................................................58 4.4 Synthesis of long-oil alkyd resin....................................................................59 4.5 Coating Formulation and Film preparation…................................................61 4.6 Instruments and Characterization…..............................................................61 4.7 Result and Discussion………………………………………………............62 4.8 Conclusions……………………………………………………………........70 V. THERMO-MECHANICAL PROPERTIES OF ALKYD/ACRYLIC MODIFIED TUNG OIL COATINGS………………………………………………………..........71 5.1 Abstract………………………………………………………………..........71 5.2 Introduction…………………………………………………………............72 5.3 Materials........................................................................................................74 5.4 Synthesis of long-oil alkyd resin…………………………............................75 5.5 Coating Formulation and Film preparation…………………........................76 5.6 Instruments and Characterization…………………………..........................77 viii 5.7 Result and discussion……………………………………………….............78 5.8 Conclusions…………………………………………………………............87 VI. LITERATURES REVIEW: THIOL-ENE PHOTOPOLYMERIZATION…….......89 6.1 Historical…………………………………………………………………....89 6.2 Polymerization mechanism of thiol-ene systems……………………….......91 6.3 Application of thiol-ene photopolymerization………………………….......98 6.4 Experimental design………………………………………………….........101 VII. SYNTHESIS AND CHARACTERIZATION OF THIOLS…………………......105 7.1 Abstract………………………………………………………………........105 7.2 Introduction…………………………………………………………..........105 7.3 Materials…………………………………………………..........................107 7.4 Instrument and Characterizations…………………………………………109 7.5 Synthesis of thiols…………………………………………………………109 7.6 Result and discussion……………………………………………………...113 7.7 Conclusions………………………………………………………………..123 VIII. REACTION KINETICS OF THIOLS FOR THIOL-ENE PHOTOPOLYMERIZATION…………………………………………………....125 8.1 Abstract………………………………………………………………........125 8.2 Introduction…………………………………………………………..........126 8.3 Materials…..................................................................................................128 8.4 Instrument and Characterizations…............................................................128 8.5 Evaluation of photopolymerization………………………………………..129 8.6 Result and discussion………………………………………………….......131 ix 8.7 Conclusions……………………………………………………………......149 IX. EVALUATION OF NEW 3-MERCAPTOPROPIONATE THIOLS FOR THIOL- ENE PHOTOPOLYMERIZATION COATINGS USING EXPERIMENTAL DESIGN…………………………………………………………………….............151 9.1 Abstract…………………………………………………………………....151 9.2 Introduction……………………………………………………………......152 9.3 Materials…..................................................................................................154 9.4 Instrumentation and testing protocol….......................................................154 9.5 Formulations and Film Formation.......................................................…....155
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