University of Massachusetts Amherst ScholarWorks@UMass Amherst Open Access Dissertations 9-2009 Synthesis and Study of Hybrid Organic – Inorganic Polyhedral Oligomeric Silsesquioxanes (poss) Based Polymers Gunjan A, Gadodia University of Massachusetts Amherst, [email protected] Follow this and additional works at: https://scholarworks.umass.edu/open_access_dissertations Part of the Polymer Science Commons Recommended Citation Gadodia, Gunjan A,, "Synthesis and Study of Hybrid Organic – Inorganic Polyhedral Oligomeric Silsesquioxanes (poss) Based Polymers" (2009). Open Access Dissertations. 97. https://doi.org/10.7275/x6zc-t890 https://scholarworks.umass.edu/open_access_dissertations/97 This Open Access Dissertation is brought to you for free and open access by ScholarWorks@UMass Amherst. It has been accepted for inclusion in Open Access Dissertations by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. SYNTHESIS AND STUDY OF HYBRID ORGANIC – INORGANIC POLYHEDRAL OLIGOMERIC SILSESQUIOXANES (POSS) BASED POLYMERS A Dissertation Presented By GUNJAN A. GADODIA Submitted to the Graduate School of the University of Massachusetts Amherst in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY September 2009 Department of Polymer Science and Engineering © Copyright by Gunjan A. Gadodia 2009 All Rights Reserved SYNTHESIS AND STUDY OF HYBRID ORGANIC – INORGANIC POLYHEDRAL OLIGOMERIC SILSESQUIOXANES (POSS) BASED POLYMERS A Dissertation Presented By GUNJAN A. GADODIA Approved as to style and content by: ____________________________________ E. Bryan Coughlin, Chair ____________________________________ Alfred J. Crosby, Member ____________________________________ Anthony D. Dinsmore, Member ________________________________ Shaw Ling Hsu, Department Head Polymer Science and Engineering DEDICATION To my beloved family ACKNOWLEDGEMENTS I would like to express my sincerest gratitude to my advisor and mentor Prof E. Bryan Coughlin. The journey towards my PhD would not have been possible without this constant support and encouragement. I would also like to thank him for his patience and freedom he gave me to try new and different things. Working with him, I have become a more optimist person, and a better communicator. I would also like to thank Prof. Al Crosby and Prof Anthony Dinsmore for serving on my committee. I have learned a great deal through their insightful comments and constructive criticism. I would like to acknowledge a number of collaborators with whom I have worked Prof. Sam Gido, Eric Anderson, Wim De Jeu, Ling Yang, Jiayu Wang and Prof. Tom Russell. I have learnt a lot working with them. I would especially like to thank Prof. Sam Gido, even though he was not on my committee he has always been available for discussions. Further, I would like to thank all the faculty members of Polymer Science and Engineering Department. I would also like to thank Dr. Stephen Eyles, Dr. Greg Dabkowski, Dr. Weiguo Hu, Dr. Sekar Dhanasekaran and Jack Hirsh for keeping the facilities up and running, and helping me to run my experiments. I also need to thank the administrative staff especially Erin and Vivien for their fantastic job. I would like to thank the sixth floor students, and the many other students with whom I have worked or interacted. It’s truly a great experience working in the Polymer Science and Engineering department at University of Massachusetts Amherst. It has been wonderful working in the Coughlin group and I would like to thank all present and past Coughlin group members. Push helped me in my first year to settle in v the group. I have learnt a lot from Nui and Brad, my fellow hybrid group members. It has been fun working around Ranga, Rich, Chris, Liz, Katie, Tsung Han, Bon-Choel, Makoto and Tarik. I have found friends for life in Ying, Shilpi, Gregoire, Yoan and Sergio. Ying has been fantastic friend for last the past 5 years, we started together and she has been very helpful to me. Hopefully in the future we will stay in touch with each other. Shilpi has also been a great friend for more than just research, we have discussed India, politics, life etc. Gregoire has been a great friend and a mentor. When I started, I had no synthetic skills and knowledge, he really helped me get started. We have been good friend since then and hopefully we will stay in touch. I think I have spent most time of my graduate life working around Yoan and Sergio. It has been a great cultural experience working with them. I am sure I will miss all of them once I go back to India. There is a huge Indian Mafia at UMASS and they make a foreign country, 10,000 miles away from India, feel like home. My roommates and friends, present and past, Nilanjan, Gautam, Abhishek, Srikant, Neha, Swetha, Raja, Mayur, Suresh and many others have been like a family. Deepak and Ajay have been special friends and I have enjoyed conversations with them and learnt a lot from them. Keyur and Vishal my high school friends have been great support in US. My friends Shreenath, Gopal and Pushkar in India have also been very supportive. Finally I would like to dedicate this thesis to my parents, sister Neha and girlfriend Janavi. It was only because of them that I have managed to do a Ph.D. Without their incessant love, support and patience this journey would not have been possible. It has been very difficult living away from them for 5 years and I look forward to my life with them. Thank you all! vi ABSTRACT SYNTHESIS AND STUDY OF HYBRID ORGANIC-INORGANIC POLYHEDRAL OLIGOMERIC SILSESQUIOXANE (POSS) BASED POLYMERS SEPTEMBER 2009 GUNJAN A. GADODIA, B.TECH., UNIVERISTY OF MUMBAI, INDIA M.S., UNIVERISTY OF MASSACHUSETTS, AMHERST Ph.D., UNIVERISTY OF MASSACHUSETTS, AMHERST Directed by: Professor E. Bryan Coughlin Hybrid organic-inorganic materials represent a new class of materials having scientific and technological potential. In this thesis, Polyhedral Oligomeric Silsesquioxanes (POSS) are used as an inorganic building block which has been tethered to an organic polymer. POSS are silica precusors, having a well defined silsesquioxane cental core surrounded by an organic periphery which makes them compatible with monomers and possibly polymers. The objectives of this study are to (1) study the basic structures of POSS homopolymers, (2) to incorporate POSS building blocks by a bottom- up approach into polymer chains and study the resulting morphologies, and (3) to study the thin film behavior of POSS block copolymers. PMA and styryl POSS homopolymers of different peripheries were synthesized by ATRP and mass spectrometry studies were carried out by MALDI-TOF and ESI. PMA POSS chains undergo a number of fragmentations while styrly POSS chains have a vii relatively robust backbone. Poly(ethylene-butylene-b-MAPOSS), AB type copolymers and poly(MAPOSS-b-styrene-b-MAPOSS), ABA type copolymers were synthesized by a combination of anionic and ATRP polymerization. Spheres, inverse cylinders, lamellar and crystalline lamellar morphologies were observed for the poly(ethylene-butylene-b- MAPOSS) copolymers. In the poly(MAPOSS-b-styrene-b-MAPOSS) copolymers, cylindrical, lamellar and perforated lamellar morphologies were obtained. Beyond the interaction parameter (χ), total degree of polymerization (N) and volume fraction (f), the conformational asymmetry (ε) also plays an important role in determining the morphology of these block copolymer. Crystallization of the POSS phase and better thermal properties were observed in the both block copolymers. Thin film studies of poly(MAPOSS-b-styrene-b-MAPOSS) copolymers showed that the microdomains can be oriented either parallel or perpendicular to the substrate depending upon the film thickness, morphology and relative volume fractions of the connecting blocks. By removal of the organic phase, ordered mesoporous low dielectric constant silica films were obtained. These hybrid block copolymers are a potential candidate for nanopatterning applications. viii TABLE OF CONTENTS ACKNOWLEDGEMENTS.................................................................................................v ABSTRACT...................................................................................................................... vii LIST OF TABLES............................................................................................................ xii LIST OF FIGURES ......................................................................................................... xiv LIST OF SCHEMES..........................................................................................................xx LIST OF ABBREVIATIONS AND SYMBOLS ............................................................ xxi CHAPTER 1. INTRODUCTION ...................................................................................................1 1.1 Hybrid Organic – Inorganic Materials...............................................................1 1.2 Self – Assembly of Block Copolymers..............................................................5 1.3 Hybrid Organic - Inorganic Polymers Based on Polyhedral Oligomeric Silsesquioxanes (POSS).....................................................................................7 1.3.1 Synthesis and Properties of Polyhedral Oligomeric Silsesquioxanes (POSS)...............................................................................7 1.3.2 POSS as Fillers .................................................................................12