Thiol-Michael Addition Polymerization Reactions

186 Pages·2017·22.15 MB·English

University of Colorado, Boulder
CU Scholar
Chemistry & Biochemistry Graduate Theses &
Chemistry & Biochemistry
Dissertations
Summer 7-14-2014
Thiol-Michael Addition Polymerization Reactions
Shunsuke Chatani
University of Colorado Boulder, [email protected]
Follow this and additional works at:https://scholar.colorado.edu/chem_gradetds
Part of thePolymer Chemistry Commons
Recommended Citation
Chatani, Shunsuke, "Thiol-Michael Addition Polymerization Reactions" (2014).Chemistry & Biochemistry Graduate Theses &
Dissertations. 12.
https://scholar.colorado.edu/chem_gradetds/12
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THIOL-MICHAEL ADDITION POLYMERIZATION REACTIONS

by
SHUNSUKE CHATANI
B.S., Kyoto University, 2003
M.S., Kyoto University, 2005

A thesis submitted to the
Faculty of the Graduate School of the
University of Colorado in partial fulfillment
of the requirement for the degree of
Doctor of Philosophy
Department of Chemistry and Biochemistry
2014
!
This!thesis!entitled:!
Thiol-Michael!Addition!Polymerization!Reactions!
written!by!Shunsuke!Chatani!
has!been!approved!for!the!Department!of!Chemistry!and!Biochemistry!
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Christopher!N.!Bowman,!Ph.!D.!
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Wei!Zhang,!Ph.!D.!
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Date! ! ! !
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The!final!copy!of!this!thesis!has!been!examined!by!the!signatories,!and!we!
find!that!both!the!content!and!the!form!meet!acceptable!presentation!standards!
of!scholarly!work!in!the!above!mentioned!discipline.!
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Abstract(
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Chatani,!Shunsuke!
(Ph.D.,!Chemistry!and!Biochemistry)!
Thiol-Michael!Addition!Polymerization!Reactions!
Thesis!directed!by!Professor!Christopher!Bowman!
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! This!thesis!is!focused!on!understanding!and!implementation!of!the!thiol-Michael!
addition! reaction! for! controlling! polymer! structures! and! properties.! The! thiol-Michael!
addition!‘click’!reaction!has!numerous!advantageous!characteristics!for!polymerization!
reactions,!such!as!having!a!high!reaction!rate!and!yield!under!mild!reaction!conditions!
without!the!formation!of!byproducts,!starting!from!a!large!selection!of!easily!accessible!
monomers.!Firstly,!control!of!the!onset!of!the!thiol-Michael!addition!reaction!was!achieved!
by! development! of! two! different! initiator! systems,! i.e.,! a! latent! initiator! (nucleophilic!
initiator! and! acid! inhibitor)! and! a! photoinitiator! (sensitizer,! base-tetraphenylborate!
complex!and!radical!inhibitor).!Both!initiator!systems!provided!excellent!control!of!the!
onset!of!the!reaction!and!provided!facile!methods!to!form!crosslinked!polymer!networks.!
Secondly,! selectivities! of! various! functional! groups! toward! the! thiol-Michael! addition!
reaction! were! assessed,! and! it! was! demonstrated! that! multiple! functional! group!
combinations!present!over!99%!selectivity!of!one!functional!group!over!the!other.!This!
concept!of!kinetically!selective!thiol-Michael!addition!reactions!are!implemented!to!control!
polymer!structural!evolution,!and!eventually!led!to!dendrimer!synthesis!and!multiphase!
network! polymer! formation.! In! dendrimer! synthesis,! a! 5th! generation! dendrimer! or!
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dendritic-linear!polymer!conjugate!were!synthesized!in!less!than!a!half!day,!and!in!the!case!
of! dendritic-linear! polymer! conjugate,! the! reactions! were! all! in! one-pot! with! just! one!
purification!step!for!the!whole!procedure.!Multiphase!network!polymer!formation!was!
demonstrated!by!sequential,!selective!thiol-Michael!addition!reactions!of!multicomponent!
monomer! mixtures,! and! it! was! shown! that! the! material! exhibits! two! distinct! glass!
transition!temperatures!(10!and!55!°C).!!Thus,!triple!shape!memory!behavior!was!achieved!
with! a! stable! intermediate! shape.! Lastly,! spatiotemporal! control! of! both! the! thiol-ene!
reaction! and! thiol-Michael! addition! reaction! were! utilized! to! form! a! material! with!
patterned! functionalities! and! material! properties,! starting! from! a! mixture! of!
multifunctional!thiols!and!an!excess!of!multifunctional!acrylates.!This!approach!is!based!on!
the!difference!in!the!thiol-vinyl!reaction!mechanisms!between!the!radical!pathway!and!the!
anionic!pathway,!in!which!the!former!consumes!more!acrylates!via!homopolymerization!
and!the!latter!consumes!both!thiols!and!acrylates!in!a!stoichiometric!ratio.!!
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This thesis is dedicated to my wife, Asami and our son, Hiroto.! !
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Acknowledgements(
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I!would!like!to!thank!Prof.!Christopher!Bowman!for!his!guidance,!encouragement!and!
support!over!the!years.!Your!passion!for!research!has!always!been!motivated!me.!I!can!say!
without!doubt!that!to!be!a!member!of!your!research!team!was!one!of!the!best!decisions!I!
have!made.!!
I!would!like!to!acknowledge!my!committee!members!Profs.!Wei!Zhang,!David!Walba,!
Zhongping!Tan!and!Charles!Musgrave.!I!would!like!to!thank!Prof.!Jeffrey!Stansbury!for!his!
helpful!suggestions!to!my!research.!!
I!would!like!to!thank!Bowman!group!and!Stansbury!group!members!for!their!support!and!
for!the!wonderful!time!I!spent!in!and!out!the!lab.!I!would!like!to!thank!Dr.!Devatha!Nair,!Dr.!
Tao!Gong,!Dr.!Maciej!Podgórski,!Dr.!Neil!Cramer,!Dr.!Parag!Shah,!Dr.!Richard!Sheridan,!Dr.!
Diana!Leung,!Dr.!Raveesh!Shenoy,!Dr.!Megan!Cole,!Dr.!Kenneth!Koehler,!Dr.!JianCheng!Liu,!
Dr.!Haiyan!Peng,!Dr.!Sankha!Pattanayak,!Dr.!Austin!Baranek,!Dr.!Mauro!Claudino,!Dr.!Brady!
Worrell,!James!Wydra,!Weixian!Xi,!Abeer!Alzahrani,!Gayla!Berg,!Ethan!Gillett,!Christopher!
Fenoli,!Chen!Wang,!Matthew!McBride,!Alexandar!Flores,!Xinpeng!Zhang,!Eftalda!Becka,!
Danielle!Konetski,!Han!Byul!Song!and!Nancy!Sowan!for!their!insights!and!discussions,!and!
also!for!the!pleasant!and!joyful!time!in!the!group.!I!would!like!to!thank!undergraduate!
students!Brittany!Earle!and!Anna!Murphy!for!working!with!me.!
I!would!like!to!thank!Mitsubishi!Rayon!for!giving!me!the!great!opportunity!to!study!in!
University!of!Colorado!and!also!for!the!financial!support!for!my!PhD!course.!I!would!like!to!
acknowledge! National! Science! Foundation,! National! Institutes! of! Health! and! the!
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Industry/University!Cooperative!Research!Center!for!Fundamentals!and!Applications!of!
Photopolymerizations!for!providing!funding!for!the!research.!
I!would!like!to!thank!my!BS!and!MS!degree!advisor!Prof.!Yukio!Yamamoto!for!teaching!me!
the!basis!of!my!career!as!a!chemist.!
I!would!like!to!thank!my!family!for!their!love!and!support.!My!wife,!Asami!has!always!
supported!me!with!love!and!patience.!I!could!not!have!accomplished!my!PhD!without!your!
support.!Our!son,!Hiroto!has!brought!a!joy!to!our!lives!with!his!cheerful!character.!The!
times!I!spent!with!my!family!gave!me!the!energy!to!work.!I!would!like!to!thank!my!parents,!
Masaaki!and!Tatsumi!Chatani,!my!sisters,!Satoko!and!Tomoko!Chatani,!my!grandmother,!
Mitsu! Chatani,! my! mother-in-law,! Izumi! Nakamura! and! my! brother-in-law,! Shinichiro!
Nakamura!for!their!love!and!support.!
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TABLE OF CONTENTS

CHAPTER PAGE

1. INTRODUCTION AND BACKGROUND ......................................... 1

1.1. Click Chemistry in Polymer Science ................................................ 1
1.2. Orthogonality ..................................................................................... 2
1.3. Thiol-X Reactions .............................................................................. 3
1.3.1. Radical Mediated Thiol-Ene and Thiol-Yne Reactions .............. 4
1.3.2. Thiol-Michael Addition Reaction ................................................. 5
1.3.3. Thiol-Isocyanate Reaction ......................................................... 10
1.4. Photochemical Processes in Polymer Science ................................ 11
1.5. Applications and Implementations of Thiol-X Reactions .............. 12
1.5.1. Dendrimers and Dendritic Polymer Architectures .................. 13
1.5.2. Network Polymers ...................................................................... 14
1.5.3. Surface Functionalization and Post-Polymerization
Modification ................................................................................ 15
1.6. References ........................................................................................ 15

2. OBJECTIVES ...................................................................................... 22

2.1. References ........................................................................................ 26

3. TEMPORAL CONTROL OF THIOL-CLICK CHEMISTRY ........ 27

3.1. Introduction ..................................................................................... 28
3.2. Experimental ................................................................................... 30
3.2.1. Materials .................................................................................... 30
3.2.2. Methods ...................................................................................... 31
3.3. Results and Discussion ................................................................... 33
3.4. Conclusions ...................................................................................... 49
3.5. Acknowledgements .......................................................................... 49
3.6. References ........................................................................................ 49

4. VISIBLE-LIGHT INITIATED THIOL-MICHAEL ADDITION
PHOTOPOLYMERIZATION REACTIONS ................................... 52

4.1. Introduction ..................................................................................... 53
4.2. Experimental ................................................................................... 54
4.2.1. Materials .................................................................................... 54
4.2.2. Methods ...................................................................................... 55
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4.3. Results and Discussion ................................................................... 56
4.4. Conclusions ...................................................................................... 65
4.5. Acknowledgements .......................................................................... 65
4.6. References ........................................................................................ 66

5. RELATIVE REACTIVITY AND SELECTIVITY OF VINYL
SULFONES AND ACRYLATES TOWARDS THE THIOL-
MICHAEL ADDITION REACTION AND POLYMERIZATION 68

5.1. Introduction ..................................................................................... 68
5.2. Experimental ................................................................................... 72
5.2.1. Materials .................................................................................... 72
5.2.2. Methods ...................................................................................... 73
5.3. Results and Discussion ................................................................... 74
5.4. Conclusions ...................................................................................... 88
5.5. Acknowledgements .......................................................................... 89
5.6. References ........................................................................................ 89

6. FACILE AND EFFICIENT SYNTHESIS OF DENDRIMERS
AND ONE-POT PREPARATION OF DENDRITIC-LINEAR
POLYMER CONJUGATES VIA SINGLE CHEMISTRY:
UTILIZATION OF SELECTIVE THIOL-MICHAEL ADDITION
REACTIONS ........................................................................................ 92

6.1. Introduction ..................................................................................... 93
6.2. Experimental ................................................................................... 95
6.2.1. Materials .................................................................................... 95
6.2.2. Synthesis .................................................................................... 96
6.2.3. Methods ...................................................................................... 99
6.3. Results and Discussion ................................................................. 100
6.4. Conclusions .................................................................................... 114
6.5. Acknowledgements ........................................................................ 115
6.6. References ...................................................................................... 115

7. TRIPLE SHAPE MEMORY MATERIALS INCORPORATING
TWO DISTINCT POLYMER NETWORKS FORMED BY
SELECTIVE THIOL-MICHAEL ADDITION REACTIONS ...... 117

7.1. Introduction ................................................................................... 118
7.2. Experimental ................................................................................. 121
7.2.1. Materials .................................................................................. 121
7.2.2. Methods .................................................................................... 121
7.3. Results and Discussion ................................................................. 123
7.4. Conclusions .................................................................................... 134
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