University of Massachusetts Amherst ScholarWorks@UMass Amherst Doctoral Dissertations 1896 - February 2014 1-1-1993 Surface chemical transformations of poly(ether ether ketone) ; Adsorption/migration of selectively-functionalized polystyrenes from a polystyrene matrix/ Nicole L. Franchina University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/dissertations_1 Recommended Citation Franchina, Nicole L., "Surface chemical transformations of poly(ether ether ketone) ; Adsorption/migration of selectively- functionalized polystyrenes from a polystyrene matrix/" (1993). Doctoral Dissertations 1896 - February 2014. 805. https://scholarworks.umass.edu/dissertations_1/805 This Open Access Dissertation is brought to you for free and open access by ScholarWorks@UMass Amherst. It has been accepted for inclusion in Doctoral Dissertations 1896 - February 2014 by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. I. SURFACE CHEMICAL TRANSFORMATIONS OF POLY(ETHER ETHER KETONE) II. ADSORPTION/MIGRATION OF SELECTIVELY- FUNCTIONALIZED POLYSTYRENES FROM A POLYSTYRENE MATRIX A Dissertation Presented by NICOLE L. FRANCHINA Submitted to the Graduate School of the University of Massachusetts in partial fulfillment of the degree requirements for the degree of DOCTOR OF PHILOSOPHY February 1993 Polymer Science and Engineering © Copyright by Nicole L. Franchina 1993 All Rights Reserved I. SURFACE CHEMICAL TRANSFORMATIONS OF POLY(ETHER ETHER KETONE) n. ADSORPTION/MIGRATION OF SELECTIVELY- FUNCTIONALIZED POLYSTYRENES FROM A POLYSTYRENE MATRIX A Dissertation Presented by NICOLE L. FRANCHINA Approved as to style and content by: David A. Tirrell, Member Paul M. Lahti, Member William J. MacKnight, Department Head Polymer Science and Engineering To my parents Maureen and Joseph Franchina ACKNOWLEDGMENTS Several people have had an impact on my life in graduate school and many of them deserve special mention. In particular, I want to express gratitude to my advisor Dr. Tom McCarthy for his help and guidance. Somehow Tom always has had faith in me, even from the beginning when I hardly trusted myself; this has helped immensely to build my self- confidence. Drs. Lahti and Tirrell deserve my gratitude, as well, for the help and time they have given me in the last year. Special thanks to Tom and DT for helping me get a job. I would like to thank the current members of the McCarthy group (Tim, Molly, Katrina Anthony, Bob, Eric, Damo and Juha-Matti) for their friendship and especially for their tolerance of my "nic"- pickiness. It is hard to believe that those guys still like me after all the jumping up and down I have done in the last five years. Many thanks to Jack Hirsch for his friendship and diligence in keeping the XPS (rather, my xps) working well. Most of all, I would like to express deep gratitude to my husband, Dr. Brant Kolb. Brant is undoubtedly one of the best scientists I will ever meet, capable of extraordinary things. I greatly appreciate the countless hours he has spent helping me to understand and develop my own science, as well as the immeasurable joy and happiness he has brought to my life. I also want to thank my parents for their love and total support throughout my tenure in grad school. (What other parents would have trouble sleeping the night before a cume??) Thanks to Justine and Greg for their support, as well, and of course to Casta, Angus, Sammy and Charlie, my favorites. V ABSTRACT I. SURFACE CHEMICAL TRANSFORMATIONS OF POLY(ETHER ETHER KETONE) II. ADSORPTION/MIGRATION OF SELECTIVELY- FUNCTIONALIZED POLYSTYRENES FROM A POLYSTYRENE MATRIX FEBRUARY 1993 NICOLE L. FRANCHINA, A.B., PRINCETON UNIVERSITY Ph.D., UNIVERSITY OF MASSACHUSETTS Directed by: Professor Thomas J. McCarthy Several carbonyl-selective reactions were carried out with semicrystaUine poly(ether ether ketone) (PEEK) film to assess the reactivity of the diaryl ketones at the fihn-solution interface. Surface analyses with X-ray photoelectron spectroscopy (XPS), attenuated total reflectance infrared spectroscopy (ATR IR) and contact angle measurement indicate that a thin layer of reagent-induced functionality results from these derivatizations in roughly 50% reaction yield. Data obtained indicate that derivatized surfaces can be functionaUzed further. Several PEEK-alcohol surfaces were prepared containing primary, secondary and tertiary alcohols, and the secondary and tertiary species were chain extended by reaction with hthium diisopropylamide and ethylene oxide. Primary alcohol groups were introduced by reacting PEEK with acetaldehyde lithiopropyl ethyl acetal and subsequent deprotection. Secondary alcohols were produced by reducing PEEK with Red-Al® reagent, and tertiary hydroxyls result from reaction with methylLthium. In general, the alcohol surfaces were reactive toward electrophiles. XPS and contact angle measurement were used to follow surface reconstruction in heat-treated samples containing specific concentrations of surface-active polystyrenes (SAP) in a polystyrene matrix (Mn = 10 K). The objective was to determine how certain molecular and environmental parameters influence surface reconstruction. The SAPs were prepared with three different architectures: the first (SAP:E-1) (Mn = 1, 5, 10, 40 and 100 K) contained a single perfluoroalkyl endgroup, the second (SAP:E-2) (Mn = 10 K) contained two fluorinated endgroups and the third contained a single perfluoroalkyl group in the middle of the chain (SAP:M- 1) (Mn = 10 K). SAP:E-1 samples were annealed at different temperatures (180, 150, 110 °C and room temperature) for varied lengths of time (24, 48, 72, 96, 120 h and two weeks) to determine optimum annealing conditions to maximize surface fluorine enrichment (as detected by XPS). Comparison of these data indicate the effect of increasing polystyrene tail length on surface-activity of perfluoroalkyl groups. Optimum anneaUng conditions were used for heat treatment of SAP:E-2 and SAP:M-1 samples and comparisons were made on the basis of differences in architecture. TABLE OF CONTENTS page ACKNOWLEDGMENTS v ABSTRACT vi LIST OF TABLES xii LIST OF FIGURES xvii LIST OF SCHEMES xx CHAPTER I. SURFACE CHEMICAL TRANSFORMATIONS OF POLY(ETHER ETHER KETONE): INTRODUCTION 1 Polymer Surface Modification 2 Structure-Property Relationships 3 Surface Modification of Poly(ether ether ketone) 6 Properties of PEEK 6 Objective 8 Polymer Surface Analytical Techniques 9 X-Ray Photoelectron Spectroscopy 10 Contact Angle 13 References 15 II. EXPERIMENTAL 20 Materials 20 Materials Handling 22 Methods 22 Ketone Derivatizations 23 Reaction of PEEK with 2,4-Dinitrophenyl- hydrazine 23 Reaction of PEEK with Hydroxylamine 24 Reaction of PEEK-Oxime with Benzenesulfonyl Isocyanate 24 Oxidation of PEEK with KCIO3/H2SO4/H2O 25 viii Reaction of PEEK-(0H)C02H with ThaUous Ethoxide 25 Reaction of PEEK with Methylenetriphenyl- phosphorane 25 Bromination of PEEK~C=CH2 .......26 Reaction of PEEK with Dimsyl Sodium 26 Reaction of PEEK with Trimethylsilyl Cyanide 26 PEEK-Alcohol Surfaces 27 Reduction of PEEK with Sodium Bis(2-methoxy- ethoxy)aluminum Hydride 27 Reaction of PEEK with Methyllithium 28 Reaction of PEEK~0H2° and PEEK~0H3° with Ethylene Oxide 29 Preparation of Acetaldehyde Lithiopropyl Ethyl Acetal 29 Preparation of PEEK~C(OH)PrOP 29 Hydrolysis of PEEK~C(OH)PrOP 30 Reactions with PEEK-Alcohol Surfaces 30 Reaction of PEEK~OH with Trichloroacetyl Chloride 30 Reaction of PEEK~OH with Isocyanates 32 Reaction of PEEK~OH with Thionyl Chloride 32 Failed Reactions with PEEK 33 Attempted Synthesis of PEEK~C(NH2)CN 33 Attempted Synthesis of PEEK-COCHa 33 Attempted Synthesis of PEEK-CCh 34 Attempted Friedel Crafts Acylations 34 References 35 HI. RESULTS AND DISCUSSION 36 Solvent Resistance 36 Characterization of PEEK 37 Ketone Transformations 42 PEEK-Hydrazone Synthesis 42 PEEK-Oxime Synthesis 44 Oxidation of PEEK 46 Wittig Reaction 50 ix Reaction of PEEK with Dimsyl Sodium 52 Cyanosilyiation of PEEK 52 Comments about Derivatized PEEK Samples 53 Preparation of PEEK-Alcohol Surfaces 57 Reduction of PEEK 57 Reaction of PEEK with Methyllithium 60 Reaction of PEEK~0H2° and PEEK~0H3° with LDA and Ethylene Oxide 61 Reaction of PEEK with Acetaldehyde Lithiopropyl Ethyl Acetal 62 Reactions with PEEK-Alcohol Surfaces 64 Reaction of PEEK-OH with Trichloroacetyl Chloride (TCAC) 64 Reaction of PEEK-OH with Trichloroacetyl Isocyanate (TCAI) 67 Reaction of PEEK-OH with Thionyl Chloride 72 Failed Reactions with PEEK 75 Failed Attempt at PEEK~C(NH2)CN 75 Failed Attempt at PEEK-COCHi 76 Failed Attempt at PEEK-CCh 76 Failed Attempt at Friedel Crafts Acylations 77 Conclusion 78 References 89 IV. ADSORPTION/MIGRATION OF SELECTIVELY- FUNCTIONALIZED POLYSTYRENES FROM A POLYSTYRENE MATRIX: INTRODUCTION 91 Reconstruction of Polymers 92 Environmental Influences 93 Surface Adsorption/Migration of Low Energy Component 94 Surface Tension 96 Bulk Order 97 Segregation to Interfaces 100 Surface Activity in Fluorinated Polymers 101 Theory and Predictions for Surface-Active Molecules 102 X Objective 105 Properties of Polystyrene 107 Perfluoroalkyl Groups 108 Surface Analyses 109 References 110 V. EXPERIMENTAL 114 Materials 114 Materials Handling 115 Reaction Methods 116 Polymers 116 Polymer Mixtures and Solutions 116 Sample Preparation 117 Heat Treatment of Samples 118 Methods of Analysis 121 Synthesis of Polystyrene and SAP:E-1 Polymers 122 Polystyrene (PS-H) 123 2-Polystyryl(ethanol) (PS-OH) 124 Perfluorodecanoyl