ANTICORROSION UV CURABLE ALKYDS a Thesis Presented to The
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ANTICORROSION UV CURABLE ALKYDS A Thesis Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Master of Science Rongcheng Xu December, 2017 ANTICORROSION UV CURABLE ALKYDS Rongcheng Xu Thesis Approved: Accepted: ______________________________ _____________________________ Advisor Department Chair Dr. Mark Soucek Dr. Sadhan Jana ______________________________ ______________________________ Faculty Reader Dean of the College Dr. Xiong Gong Dr. Eric Amis ______________________________ ______________________________ Faculty Reader Executive Dean of Graduate School Dr. Younjin Min Dr. Chand Midha ______________________________ _____________________________ Date:_________________________ ii ACKNOWLEDGEMENTS I would like to sincerely thank the amazing people who have helped and supported me throughout my graduate research. I would like to sincerely thank Professor Mark Soucek, for his guidance, support, training, and advice during my time at the University of Akron. I had the pleasure of being trained by excellent mentors and group members, especially Dr. Qianhe Wang, Dr. Lei Meng, and Dr. Ryan Salata. I’d also like to thank Anisa Cobaj, Brittany Pellegrene, and Dr. Sayyed Abed for their experimental support. Especially, I want to thank my classmates Cheng Zhang and Haoran Wang for their precious help and encouragement. Most importantly, I want to thank my parents for their unconditional love and everything they have done for me. In addition, I want to thank my girlfriend Yidan Zhang for her support all the way and hope her a happy PhD life in Cornell University. iii ABSTRACT Alkyds are essentially oil modified polyesters derived from oils, dibasic acids and polyols. Being bio-renewable, versatile and low-cost made alkyds one of the most consumed coating material in the world. The slow autoxidative drying of a conventional alkyd formulation has limited the potential application for alkyds. Silicone additives are usually used in the hybrid coating formulations to get better anticorrosion property via sol-gel structure. In the meantime, high crosslink density from UV curing and sol-gel structure can give the coating films great resistance properties compared to conventional alkyds, especially anticorrosion property. This thesis is focused on the development of anticorrosion UV curable alkyd coating systems with fasting curing speed and competitive coating properties. Two UV-curable alkyd resins were synthesized by functionalizing conventional medium linseed oil alkyd with acrylate and methacrylate functional groups. Two compatible silicone additives were prepolymerized as VTMS colloid and TEOS oligomer. The chemical structures were characterized using 1H NMR, MALDI mass spectrometry, and FTIR. UV curing kinetics of UV curable alkyd systems with 0- 20 wt% silicone additives were investigated with real-time FTIR and photo DSC. General coating properties were characterized including pendulum hardness, pencil hardness, impact resistance, cross hatch adhesion, pull off adhesion, and MEK double rub. To improve the enhance of anticorrosion property of modified UV curable coatings, salt spray test was used to evaluate the hybrid coatings. iv Table of contents Acknowledgement ........................................................................................................................ iii Abstract ......................................................................................................................................... iv List of Figures ..............................................................................................................................viii List of Tables ................................................................................................................................ xi CHAPTER I. Introduction .............................................................................................................................. 1 II. Background .............................................................................................................................. 3 2.1 Seed Oils ..................................................................................................................... 4 2.2 Linseed Oil .................................................................................................................. 7 2.3 Autoxidation and driers............................................................................................... 8 2.4 History of Alkyds ........................................................................................................ 10 2.5 Alkyds Resins ............................................................................................................. 11 2.6 UV Curing Coating System ........................................................................................ 16 2.7 Anticorrosion Organic Coating System ...................................................................... 18 2.7.1 Definition of corrosion ................................................................................. 18 2.7.2 Mechanism of corrosion .............................................................................. 18 2.7.3 Anticorrosive Organic Coatings .................................................................. 19 v 2.7.4 Sol-gel Process ............................................................................................. 21 2.7.5 Organic/ Inorganic hybrid coatings ............................................................ 23 III. Synthesis and kinetic study of Anticorrosion UV curable alkyd ............................................ 25 3.1 Abstract ....................................................................................................................... 25 3.2 Experimental ............................................................................................................... 26 3.2.1 Materials ...................................................................................................... 26 3.2.2 Instrumentation ............................................................................................ 26 3.2.3 Synthesis of Medium Linseed Oil................................................................ 27 3.3.4 Synthesis of Acrylated Medium Linseed Oil ............................................... 27 3.3.5 Synthesis of Methacrylates Medium Linseed Oil ........................................ 28 3.3.6 Synthesis of Vinyltrimethoxysilane Colloid ................................................ 30 3.3.7 Formulation of Anticorrosion UV Curable Alkyd ....................................... 31 3.3.8 Realtime FTIR ............................................................................................. 33 3.3.9 Photo DSC ................................................................................................... 33 3.3 Results and Discussion ............................................................................................... 34 3.3.1 1H NMR....................................................................................................... 35 3.3.2 Fourier Transform Infrared Spectra ............................................................. 36 3.3.3 MALDI-MS ................................................................................................. 39 vi 3.3.4 Realtime FTIR ............................................................................................. 42 3.3.5 Photo DSC ................................................................................................... 46 3.4 Conclusion .................................................................................................................. 51 IV. Study of Anticorrosion UV curable alkyd coating properties ................................................ 53 4.1Abstract ....................................................................................................................... 53 4.2 Experimental ............................................................................................................... 54 4.2.1 Materials ...................................................................................................... 54 4.2.2 Synthesis of Acrylated Medium Linseed Oil Alkyd .................................... 54 4.2.3 Formulation of Anticorrosion UV Curable Alkyd Resin ............................. 55 4.2.4 Pencil Hardness and Pendulum Hardness Tests .......................................... 56 4.2.5 Cross hatch Adhesion and Pull off Adhesion Tests ..................................... 57 4.2.6 Impact Resistance Test ................................................................................ 60 4.3.7 MEK Double Rubs Test ............................................................................... 60 4,3.8 Salts Spray Test............................................................................................ 61 4.3 Results and Discussion ............................................................................................... 63 4.4 Conclusion .................................................................................................................. 71 V. Summary .................................................................................................................................. 72 Reference ...................................................................................................................................... 74 vii List of Figures Figure 2-1 The