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Reactions of Modified Silica Gel Surfaces with Organometallic Compounds: Enhancing Olefin Op Lymerization Catalysts" (1998)

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Reactions of Modified Silica Gel Surfaces with Organometallic Compounds: Enhancing Olefin Op Lymerization Catalysts Eastern Illinois University The Keep Masters Theses Student Theses & Publications 1998 Reactions of Modified iS lica Gel Surfaces with Organometallic Compounds: Enhancing Olefin Polymerization Catalysts Richard E. Diebel III Eastern Illinois University This research is a product of the graduate program in Chemistry at Eastern Illinois University. Find out more about the program. Recommended Citation Diebel, Richard E. III, "Reactions of Modified Silica Gel Surfaces with Organometallic Compounds: Enhancing Olefin oP lymerization Catalysts" (1998). Masters Theses. 1740. https://thekeep.eiu.edu/theses/1740 This is brought to you for free and open access by the Student Theses & Publications at The Keep. It has been accepted for inclusion in Masters Theses by an authorized administrator of The Keep. For more information, please contact [email protected]. THESIS REPRODUCTION CERTIFICATE TO: Graduate Degree Candidates (who have written formal theses) SUBJECT: Permission to Reproduce Theses The University Library is receiving a number of request from other institutions asking permission to reproduce dissertations for inclusion in their library holdings. Although no copyright laws are involved, we feel that professional courtesy demands that permission be obtained from the author before we allow these to be copied . PLEASE SIGN ONE OF THE FOLLOWING STATEMENTS: Booth Library of Eastern Illinois University has my permission to lend my thesis to a reputable college or university or the purpose of copying it for inclusion in that institution's library or research holdings. - Author's Signature Date I respectfully request Booth Library of Eastern Illinois University NOT allow my thesis to be reproduced because: Author's Signature Date lhesis4.form Reactions of Modified Silica gel Surfaces with Organometallic Compounds: Enhancing Olefin (TITLE) Polymerization Catalysts BY Richard E. Diebel III THESIS SUBMITIED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science in Chemistry IN THE GRADUATE SCHOOL, EASTERN ILUNOIS UNIVERSITY CHARLESTON. ILLINOIS 1998 YEAR I HEREBY RECOMMEND THIS THESIS BE ACCEPTED AS FULFILLING THIS PART OF THE GRADUATE DEGREE CITED ABOVE DATE ADVISER 12/<{(q f DATE 19iPARTMENT HEAD Reactions of Modified Silica Gel Surfaces with Organometallic Compounds: Enhancing Olefin Polymerization Catalysts By: Richard E. Diebel III Advisor: Dr. Jonathan P. Blitz Date Submitted: Sept. 14, 1998 Approved by the thesis committee: Dr. J~nathan P. Blit~ Date F I Dr. Carol A. Deag¥ne Date Dr. Mark E. McGuire Date rlat Reactions of Modified Silica Gel Surfaces with Organometallic Compounds: Enhancing Olefin Polymerization Catalysts Richard E. Diebel III ABSTRACT Pretreated silica gels with distinct silica surfaces containing either isolated silanols, vicinal silanols, siloxanes, or some combinations of the three, were reacted with several organometallic compounds to determine how each compound reacted with the different silica surface species. The organometallic compounds used were trimethylaluminum, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, dibutylmagnesium, and bis-cyclopentadienyl dimethyl zirconium. These reacted silica gels were analyzed usmg diffuse reflectance infrared Fourier transform spectroscopy and ICP-AES elemental analysis. CH/Metal ratios were calculated using specific peaks in the IR spectra to elucidate the surface bonded species. Elemental analysis was used to determine how much metal was bonded to each silica gel surface. Elemental analysis showed that under the conditions studied all of the compounds had reactivities with respect to the four silica gel surfaces following the order of bare silica > 600°C silica > HMDS silica > 600°C/HMDS silica. All of the compounds, with the exception of dimethylzirconocene (which only reacts appreciably with isolated silanols), react with both isolated and vicinal silanols, and appear to react significantly with the siloxane groups. Based on CH/Metal ratios, all compounds are believed to react with isolated silanols forming singly bonded surface structures. Most of the compounds also appear to form bridged surface species after reaction with vicinal silanols. EADC, however, is believed to react with each silanol in a hydrogen bonded silanol pair, yielding two dichloroaluminum surface groups. Most of the compounds also seem to react appreciably with siloxanes, resulting in siloxane bond cleavage. The theoretical CH/Metal ratios for each compound were calculated to follow the order of 600°C/HMDS silica > 600°C silica > bare silica > HMDS silica. There were some differences between the theoretical and experimental ratio orders but, in most cases they were comparable. ii ACKNOWLEDGEMENTS I would like to give heartfelt thanks to my lovely wife Michelle, for her endless love and support. She made it all worthwhile as well as possible. Special thanks also to my morn, dad, and brother. They instilled in me the values and tools necessary to succeed in life. May everyone be so lucky. Special thanks also to my mentor and friend, Dr. Jon Blitz, for sharing his knowledge and advice and putting up with my endless questions. His guidance during my research made me a better chemist. I would also like to express gratitude to the students and chemistry department faculty of Eastern Illinois University. They are the reason I chose EIU to pursue a chemistry degree. It was one of my better decisions and time well spent. Finally, I would like to thank the Petrochemical Research Fund and Equistar Inc. (special thanks to Craig Meverden) for their help in supporting this research. iii TABLE OF CONTENTS Abstract ................................................ ............................ i Acknowledgements ........................................................... .iii Table of Contents .............................. ... ... ... ... .................... iv List of Tables ................................................................... vi List of Figures ............................................................ ..... vii Chapter I: Introduction and Background ................................ 1 1.1 Introduction ............................................................. 1 1.2 The Silica Gel Surface ............................................... 1 1.3 Pretreatment of Silica Gels ........................... .............. 3 1.4 Infrared Analysis of the Silica Surface ......................... 5 1.5 Diffuse Reflectance Technique .................................... 6 1.6 Polymerization Catalysts .. .. .. .. ......... ... .................... 8 1.6. l Ziegler-Natta Catalysts ................................... 9 1.6.2 Metallocene Catalysts ................................... 10 Chapter II: Experimental Section .............................. ......... 12 2.1 Materials ............................................................... 12 2.2 Instrumentation ....................................................... 13 2.3 Synthesis ............ ................................................... 14 Chapter III: Results and Discussion .................................... 16 3.1 Dibutylmagnesium ................................................... 16 3 .1.1 CH/Mg Ratios for D ibutylmagnesium ................ 18 iv 3 .1.2 The Siloxane Reaction ..................... .............. 22 3 .2 Organoaluminum Compounds ..................................... 23 3.2.1 Trimethylaluminum ....................................... 25 3.2.2 TEAL, DEAC, and EADC ........................... .... 27 3.2.3 CH/Al Ratios for TEAL, DEAC, and EADC ....... 29 3 .2.4 Surface Species of the TMA/ Silica Reaction ...... 36 3 .3 Metallocene Dichlorides ................................. .. ....... 38 3.4 Dimethylzirconocene ...... ...... .................................... 38 Chapter IV: Conclusions ...... ............................................ .41 References ...................................................................... 43 v LIST OF TABLES Table 1 ...... .................. ... ...... ... .... ... ... ... .... Reaction Specifications Table 2 ...... ...... .................. .. .. .. .......... ........... Elemental Analysis Table 3 ..................... ............ ......... ... .... .. ...... .. ... CH/Metal Ratios Table 4 ... .................. .......... ... Elemental Analysis for Metallocenes vi LIST OF FIGURES Figure 1 ...... ... ............ ............................... Silica Surface Structures Figure 2 .................................................... Modified Silica Surfaces Figure 3 .................................... .. ... Dehydration vs. Dehydroxylation Figure 4 ...................................................................... Bare Silica Figure 5 ...... .............................................................. 600°C Silica Figure 6 ....................................... ............................ HMDS Silica Figure 7 .......................................................... 600°C/HMDS Silica Figure 8 ................................................. DBM Modified Bare Silica Figure 9 ............................................... DBM Modified 600°C Silica Figure 10 ............................................. DBM Modified HMDS Silica Figure 11. .................................. DBM Modified 600°C/HMDS Silica Figure 12 ................... ................... Titanium Tetrachloride Reactions Figure 13 ...................... ................ ...... Dibutylmagnesium Reactions Figure 14 .................................. TMA (Hexane)
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