ABSTRACT WANG, GUAN. Synthesis and Application of Bleach Activators Containing Various Cationic Groups and PET Fabric Decolorization using Fenton’s Reagent. (Under the direction of Dr. David Hinks.) CBAs are quaternary ammonium salts (QAS) that are extensively used in various applications. Although most of the QAS are generally believed to be nontoxic to humans, they will harm aquatic life both animals and plants. CBAs are applied in textile bleaching process and the wastewater after bleaching contains chemicals including bleach activators. Even though wastewater contains CBAs will be treated in a wastewater treatment plant, the treated water still contain these chemicals. The study of acute toxicity and genotoxicity of CBAs to aquatic organisms was conducted in this study. Eight new bleach activators and two bench mark cationic bleach activators were investigated. New invented cationic bleach activator 3- PBBC is 86 times less toxic in the Daphnia sp. Immobilization Test, 18 times less toxic in Algae Toxicity assay and 10 times less mutagenic in the Salmonella/microsome microsuspension assay in comparison with the benchmark product (TBBC). This confirmed that replacing the cationic group in CBAs using low toxicity ammines can reduce the toxicity of CBAs to aquatic organisms. An effective low temperature and neutral pH bleaching system was developed using CBAs. A comparison life-cycle assessment for conventional and innovational bleaching system was conducted in this study. Their relative environmental performance was analyzed and compared. Based on data from industry, pre-published research, lab-scale experiments and the Ecoinvent database, the life-cycle-inventory (LCI) for both innovative and conventional bleaching process was developed. Seven impact categories from TRACI, USETox and IPCC 2007 were selected to evaluate the impact based on the results of the LCI. The innovative bleaching process has lower environmental impacts than conventional method. It consumes less electricity, steam, water, and process time by modifying the conventional bleaching process. Polyester (polyethylene terephthalate; PET) fibers now exceed cotton as the largest volume textile substrate in commerce, owing to their economy, strength, and versatility. Unlike cotton, PET fibers are not readily biodegradable, leading to their persistent if placed in a landfill environment following their useful lifetime. The modern-day corporate commitment to product stewardship has led to considerable interest in the recycle/reuse of textiles derived from synthetic fibers such as PET. It is generally recognized that the key step in the recycling process is color removal. Fenton’s chemistry was used in the present investigation as an approach to decolorizing PET fabrics containing a variety dye structural types, providing an indication of the versatility of this method. A full factorial design of experiments was used to establish the amount of FeSO4 and H2O2 needed to optimize fabric decolorization. In this study, an optimized method consisting of FeSO4 (0.18 mM), H2O2 (1235 mM), and water: acetone (1:1), at 120 oC, for 15 min was found suitable for color removal from most PET fabrics. Due to the technique barrier, the used PET garment cannot be recycled as simple as used PET bottles. By developing the method which can be used to remove the dye in the used PET garments, it is possible to recycle used PET garments for PET fiber production. In this study, a life-cycle assessment was used to compare the environmental impacts of fiber production using post-consumer PET fabric and virgin PET fiber production. After analysis, using post- consumer PET fabric to produce fiber will release 5.45% to 44.61% less impacts to the environment compared to virgin PET production. Only emissions, which cause ozone depletion, released by recycled fiber production through chemical recycling process are more than the emissions released by virgin PET production. In order to reduce the environmental impacts of the post-consumer PET fabric to fiber production, the optimizations of PET fabric decolorization process, recycling process and chemical production are necessary. A decolorization process using less chemical and at lower temperature should be developed in the future. A more environmental friendly process for hydrogen peroxide production should be used. © Copyright 2015 Guan Wang All Rights Reserved Synthesis and Application of Bleach Activators Containing Various Cationic Groups and PET Fabric Decolorization using Fenton’s Reagent by Guan Wang A dissertation submitted to the Graduate Faculty of North Carolina State University in partial fulfillment of the requirements for the Degree of Doctor of Philosophy Fiber and Polymer Science Raleigh, North Carolina 2015 APPROVED BY: _______________________________ _______________________________ Dr. David Hinks Dr. Harold S. Freeman Committee Chair _______________________________ _______________________________ Dr. Peter J. Hauser Dr. Joseph F. DeCarolis DEDICATION To Tong Yao ii BIOGRAPHY Guan Wang, the only son of Sifeng Wang and Ying Wang, was born on January 4th, 1989 in Zhejiang, China. He graduated from Huzhou High school in June, 2007, and received a Bachelor of Engineering degree in Textile Engineering from Donghua University, Shanghai, China in June 2011. In undergraduate study, he conducted research on 3D-weaving ramie polypropylene enforced composite under the guidance of Dr. Yiping Qiu. He was one of the Donghua “3+X” program students who took three years to complete the B.S. degree and then entered the Master of Science in Textile Chemistry in the College of Textiles at North Carolina State University in August, 2010. After he got Master of Science degree in Textile Chemistry in May, 2012, Guan continue his education and studied for his Doctor of Philosophy degree in Fiber and Polymer Science under the direction of Dr. David Hinks. On June 29, 2015, Guan married Tong Yao in Xi’an, China. Tong is now pursuing her Ph.D degree in Fiber and Polymer Science in the College of Textiles at North Carolina State University. iii ACKNOWLEDGMENTS Firstly, I would like to express my sincere gratitude to my advisor Dr. David Hinks for the continuous support of my Ph.D study and related research, for his patience, motivation, and immense knowledge. His guidance helped me in all the time of research and writing of this dissertation. This dissertation could not be written to its fullest without Dr. Harold S. Freeman, who challenged and encouraged me throughout my time spent studying under him. He would have never accepted anything less than my best efforts, and for that, I thank him. Besides, I would like to thank the rest of my dissertation committee: Dr. Peter J. Hauser and Dr. Joseph F. DeCarolis, for their insightful comments and encouragement, but also for the hard question which incented me to widen my research from various perspectives. Also I thank my friends. Thank you so much for your time, your support, your well wishes and friendship. Last but not the least, I would like to thank my family: my wife Tong Yao and my parents for supporting me spiritually throughout writing this dissertation and my life in general. iv TABLE OF CONTENTS LIST OF TABLES ................................................................................................................. ix LIST OF FIGURES ............................................................................................................... xi LIST OF SCHEMES ............................................................................................................. xi Chapter 1 Introduction........................................................................................................... 1 1.1 Dissertation Outline ...................................................................................................... 1 1.2 Research Objectives ...................................................................................................... 2 Chapter 2 Literature Review ................................................................................................. 3 2.1 Natural color contents in cotton .................................................................................... 3 2.2 Peroxide-based bleaching ............................................................................................. 4 2.3 Bleach activators ........................................................................................................... 6 2.3.1 Cationic Bleach Activators ................................................................................. 9 2.3.2 Synthesis of cationic bleach activators process ................................................ 14 2.3.3 Environmental properties of cationic compounds ............................................ 15 2.4 Structure analysis ........................................................................................................ 19 2.4.1 Time-of-flight mass spectrometry ..................................................................... 19 2.4.2 High-performance liquid chromatography ....................................................... 19 2.4.3 NMR spectroscopy............................................................................................ 20 2.5 Whiteness Measurement ............................................................................................. 21 2.6 Whiteness .................................................................................................................... 21 2.7