Synthesis, Characterization, and Polymerization of Sulfonamide Based Bifunctional Monomers

Transcription

1 Synthesis, Chrteriztion, nd Polymeriztion of Sulfonmide Bsed Bifuntionl Monomers A thesis submitted in prtil fulfillment of the requirements for the degree of Mster of Siene By BRADY HALL B.S., The University of Southern Mississippi, Wright Stte University

2 WRIGHT STATE UNIVERSITY GRADUATE SCHOOL July 26, 2016 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Brdy Hll ENTITLED Synthesis, Chrteriztion, nd Polymeriztion of Sulfonmide Bsed Bifuntionl Monomers BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Mster of Siene. Eri Fossum, Ph.D. Thesis Advisor Committee on Finl Exmintion Dvid Grossie, Ph.D. Chir, Deprtment of Chemistry Eri Fossum, Ph.D. Willim A. Feld, Ph.D. Kenneth Turnbull, Ph.D. Robert E. W. Fyffe, Ph.D. Vie President for Reserh nd Den of the Grdute Shool

3 ABSTRACT Hll, Brdy. M.S., Deprtment of Chemistry, Wright Stte University, Synthesis, Chrteriztion, nd Polymeriztion of Sulfonmide Bsed Bifuntionl Monomers. A series of bifuntionl monomers bsed on N,N-dillylbenzenesulfonmides with vrying groups on the benzene moiety were investigted. The min gol of this projet ws to polymerize these monomers using rdil nd yli diene metthesis (ADMET) polymeriztion methods to polymerize through the llyl groups, nd nuleophili romti substitution (S N Ar) to polymerize through the fluorine groups on the phenyl ring. Using phenyl substituted benzenesulfonyl hloride derivtives s strting mteril, series of N,N-dillylbenzenesulfonmide derivtives were prepred. The ADMET nd rdil ylopolymeriztions were monitored by 1 H NMR spetrosopy, observing the dispperne of signls for the llyl groups in both, nd the pperne of brod liphti signls in the rdil ylopolymers. The polymers formed vi S N Ar retions were followed by DEPT C NMR spetrosopy. Additionlly, GPC, DSC, nd TGA were used to hrterize the polymers, whih indited suessful ylopolymeriztion, ADMET, nd S N Ar retions. iii

4 TABLE OF CONTENTS 1. INTRODUCTION Rdil Polymeriztion Free Rdil Polymeriztion (FRP) Atom Trnsfer Rdil Polymeriztion (ATRP) Inititors for Constnt Ativtor Regenertion (ICAR) ATRP Reversible Addition-Frgmenttion Chin Trnsfer (RAFT) Polymeriztion Ayli Diene Metthesis (ADMET) Polymeriztion Cylopolymeriztion Nuleophili Aromti Substitution (S N Ar) Polyondenstion Bifuntionl Monomers Introdution of Funtionlity Current Reserh EXPERIMENTAL Mterils Instrumenttion Generl Proedure for the Synthesis of N,N-dillylbenzenesulfonmide (DABSA) Derivtives Generl Proedure for the Synthesis of N,N-diotylbenzenesulfonmide (DOtBSA) Derivtives Rdil Polymeriztion FRP of DABSA Derivtives ATRP of DABSA Derivtives iv

5 ICAR ATRP of DABSA Derivtives Reversible Addition-Frgmenttion Chin Trnsfer (RAFT) Polymeriztion of DABSA-2,4-DF ADMET Polymeriztion of DABSA Derivtives S N Ar Copolymeriztion of 2/b nd 1d/e using 4,4 -dihydroxydiphenyl ether Chrteriztion Size Exlusion Chromtogrphy (SEC) Differentil Snning Clorimetry (DSC) Thermogrvimetri Anlysis (TGA) RESULTS AND DISCUSSION Monomer Synthesis Synthesis of N,N-dillylbenzenesulfonmide (DABSA) Derivtives Synthesis of N,N-diotylbenzenesulfonmide Derivtives Sprtn Clultions Free Rdil Polymers ATRP nd ICAR ATRP Polymers RAFT of DABSA-2,4-DF ADMET Polymers S N Ar Copolymers S N Ar Copolymeriztion of 1d nd 2 using 4,4 -dihydroxydiphenyl ether Polymer Moleulr Weights nd Therml Properties v

6 4. CONCLUSIONS FUTURE WORK REFERENCES vi

7 LIST OF FIGURES Figure 1. Di- nd tri-thiorbonylthio RAFT gents Figure 2. Commerilly vilble PAES Figure 3. Exmples of bifuntionl monomers Figure MHz 1 H NMR spetrum (CDCl 3 ) of Figure MHz NMR spetr (CDCl 3 ) of the romti region of 1-e Figure MHz DEPT 135 (top) nd 13 C NMR (bottom) spetrl overly (CDCl 3 ) of DABSA Figure MHz 13 C NMR spetrl overly (CDCl 3 ) of DABSA derivtives Figure 8. 1 H NMR spetrl overly (CDCl 3 ) of 2 (top) nd 2b (bottom) Figure MHz DEPT 135 (top) nd 13 C (bottom) NMR spetrl overly (CDCl 3 ) of Figure MHz DEPT 135 (top) nd 13 C NMR (bottom) spetrl overly (CDCl 3 ) of 2b Figure 11. Eletron density mpping of strting mterils Figure MHz 1 H NMR spetrl overly (CDCl 3 ) of AIBN initited p1-e Figure MHz 1 H NMR spetrl overly (CDCl 3 ) of BPO initited p1, d, nd e.43 Figure MHz 1 H NMR spetr of 1d (top) nd p2d (bottom) Figure MHz 1 H NMR spetrl overly (CDCl 3 ) of 1 (top) nd p3 (bottom).. 48 Figure MHz 1 H NMR spetrl overly (CDCl 3 ) of ADMET polymers p3-e Figure MHz 13 C NMR spetr (CDCl 3 ) of 1 (top) nd p3 (bottom) Figure MHz 13 C NMR spetrl overly (CDCl 3 ) of ADMET polymers p3-e. 51 vii

8 Figure MHz 1 H NMR (CDCl 3 ) spetrl overly of p4 (top) nd p4b (bottom) Figure MHz DEPT C NMR (CDCl 3 ) spetrl overly of 1d (top) nd p4 (bottom) Figure MHz DEPT C NMR (CDCl 3 ) spetrl overly of 1e (top) nd p4b (bottom) Figure 22. DSC results of AIBN initited DABSA derivtives Figure 23. TGA results of AIBN initited DABSA derivtives Figure 24. DSC results of BPO initited DABSA derivtives Figure 25. TGA results of BPO initited DABSA derivtives Figure 26. DSC results of ADMET polymers Figure 27. TGA results of 1 nd p Figure 28. TGA results of ADMET Polymers Figure 29. DSC results of S N Ar opolymers Figure 30. TGA results of S N Ar opolymers viii

9 LIST OF SCHEMES Sheme 1. Rdil formtion in the rdil inititors AIBN nd BPO Sheme 2. Hed nd til ddition Sheme 3. Mehnism of the free rdil polymeriztion of styrene Sheme 4. Generl mehnism of ATRP Sheme 5. Generlly epted mehnism for RAFT polymeriztion Sheme 6. Mehnism of ADMET polymeriztion Sheme 7. Cyliztion of quternry mines Sheme 8. Degrdtive hin trnsfer Sheme 9. Generl mehnism for S N Ar Sheme 10. Outline of S N Ar polyondenstion Sheme 11. Synthesis of PAEs vi met-tivted S N Ar polyondenstion retions Sheme 12. Introduing funtionlity vi pre nd post polymeriztion modifition Sheme 13. Pre (top) nd post (bottom) polymeriztion modifition of DABSA-4-Br. 14 Sheme 14. Pre (top) nd post (bottom) polymeriztion modifition of DABSA-3,5-DF Sheme 15. Syntheti route for DABSA derivtives Sheme 16. Syntheti route for DOtBSA derivtives Sheme 17. Generl outline of the FRP of DABSA derivtives Sheme 18. ATRP of 1-e Sheme 19. ICAR ATRP of 1-e Sheme 20. RAFT polymeriztion of 1d Sheme 21. ADMET polymeriztion of monomers 1-e ix

10 Sheme 22. S N Ar opolymeriztion of 2/b nd 1d/e to form p4/b x

11 LIST OF TABLES Tble 1. Literture vlues for dillylmine derivtives Tble 2. Clulted eletrostti hrges of dillylmine derivtives Tble 3. Differenes in hemil shift nd moleulr weights of free rdil polymers. 56 Tble 4. Therml dt for free rdil polymers Tble 5. Moleulr weight of RAFT polymer p2d Tble 6. Moleulr weights nd therml properties of ADMET polymers Tble 7. Moleulr weights nd therml properties of S N Ar polymers xi

12 ACKNOWLEDGEMENTS I would first like to express my grtitude to my dvisor, Dr. Eri Fossum for his guidne nd enourgement during my sojourn in his group. His ptiene nd genility hs inspired me s hemist, nd most importntly s person. I will be forever grteful to him for giving me this opportunity. I would lso like to thnk my ommittee members Dr. Willim Feld nd Dr. Kenneth Turnbull for their suggestions nd ssistne towrd this thesis. Additionlly, I would like to thnk Luke Meyer for his invluble ssistne, s well s the pst nd present members of the Fossum reserh group, nd the fulty nd stff members of the Wright Stte University Deprtment of Chemistry. This work is bsed upon work supported by the Ntionl Siene Foundtion under CHE xii

13 DEDICATION I would like to dedite this work to my prents, Jodie nd Steve Srtin, nd Kenneth nd Meliss Hll, s well s my grndprents, Helen nd Gene Spene. Their ontinued love nd support hs pushed me to strive for my best. I would lso like to dedite this work to my prtner, Kty Gines, who hs stood beside me during this demnding time in my life. I n t figure out if it s n end, or the beginning, but I know you ll will be right there with me. Thnk you. xiii

14 1. INTRODUCTION 1.1. Rdil Polymeriztion Free Rdil Polymeriztion (FRP) Rdils re hemil speies tht possess n unpired eletron in n outer shell, sometimes lled free spin, whih gives rise to the term free rdil. Free rdil polymeriztion (FRP) is type of hin growth polymeriztion, mening tht high moleulr weight polymer is formed erly in the retion. FRP is most ommonly onduted on ompounds with rbon-rbon double bond using rdil inititor, suh s 2,2 -zobis(2-methylpropionitrile) (AIBN) or benzoyl peroxide (BPO). The rdils re formed through either therml or photohemil deomposition (see Sheme 1), nd dd to monomer moleule by opening the π-bond to form new rdil enter. This proess is repeted mny times s more monomer moleules re dded to the propgting rdil enter. AIBN BPO Sheme 1. Rdil formtion in the rdil inititors AIBN nd BPO. Substitution t rdil enter lmost lwys inreses stbility by reduing the bond dissoition energy, nd s suh rdil stbility typilly inreses from 1

15 methyl<primry<seondry<tertiry. Normlly this results in the ddition of rdil to the less highly substituted end of symmetrilly substituted ompounds (i.e. they predominntly result in til ddition, s shown in Sheme 2). Due to the high onentrtion of rdil speies in the system, the growing polymer hin is terminted by the destrution of the retive enter through hydrogen bstrtion or some type of oupling, s illustrted in Sheme 3. Til Addition Sheme 2. Hed nd til ddition. Rdil Formtion Hed Addition Initition Propgtion Trnsfer Termintion Sheme 3. Mehnism of the free rdil polymeriztion of styrene. 2

16 Owing to the high rte of termintion in FRP, nrrow distribution of moleulr weights nnot be hieved, nd the dispersity (Đ) is greter thn In order to ddress this issue, methods of limiting the onentrtion of tive rdil speies were investigted. Vrious types of ontrolled rdil polymeriztion (CRP) tehniques were developed, ll of whih owe their suess to the persistent rdil effet; type of selfregultion of the two types of rdil speies (propgting nd persistent) by some sort of mediting omplex Atom Trnsfer Rdil Polymeriztion (ATRP) Atom Trnsfer Rdil Polymeriztion (ATRP), first reported in 1995 from the lbortories of Swmoto, 3 Mtyjszewski, 4 nd Pere, 5 ws the first true CRP tehnique. Previous ttempts inlude iniferter nd nitroxide-medited rdil polymeriztion (NMP) methods, both of whih hve only limited suess in filitting rdil polymeriztions. Both iniferter nd NMP hve limited seletion of monomers from whih to hoose, nd iniferter polymeriztion further suffers from brod Đ nd limited blok opolymer formtion. ATRP does not hve these issues, nd n be tilored for speifi retions by modifying one of the regents involved: the hlogented inititor, trnsition metl ompound, or nitrogen bsed lignd. In ATRP, trnsition metl ompound in its lower oxidtive stte (e.g. opper (I) bromide) is used to medite reversible redox proess nd estblish equilibrium between propgting nd persistent rdils. 1 This reversible proess results in ontrol of the rdil speies by detivting the rdil enter, using low rdil onentrtion nd minimizing termintion of the growing polymer hin. The suess of n ATRP is ontingent on fst nd quntittive initition of the monomers so tht ll of the 3

17 propgting speies grow simultneously; resulting in nrrow Đ. ATRP is trditionlly onduted on vinyl monomers, with rtios of monomer:tlyst:inititor in the rnge of 100:1:1 to 100:1:10 nd n been onduted in bulk, solution, or vrious heterogeneous medi inluding suspension, dispersion nd queous emulsion. 6 Sheme 4. Generl mehnism of ATRP Inititors for Constnt Ativtor Regenertion (ICAR) ATRP While ATRP is very verstile polymeriztion method, it is not pplible for every type of sitution. Inititors for onstnt tivtor regenertion (ICAR) ATRP is one tehnique tht hs been developed to ddress these limittions. Unlike ATRP, ICAR ATRP utilizes trnsition metl ompound in higher oxidtive stte, (e.g. opper (II) hlide) s well s trditionl rdil inititor (e.g. AIBN or BPO). The inititor genertes rdils tht ret with the trnsition metl omplex to ontinuously regenerte its lower oxidtive stte, preventing it from being onsumed in termintion retions. This llows for use of the tlyst t onentrtions between ppm, nd is benefiil in situtions where removl or reyling of the tlyst is not possible. 8 4

18 Reversible Addition-Frgmenttion Chin Trnsfer (RAFT) Polymeriztion Another prominent type of CRP is reversible ddition-frgmenttion hin trnsfer (RAFT) polymeriztion, whih ws developed in 1996 by tem t Commonwelth Sientifi nd Industril Reserh Orgnistion (CSIRO). 9 In RAFT polymeriztion, the propgting nd persistent rdil equilibrium is medited by di- or trithiorbonylthio RAFT gent. Retive double bond Leving group Wek single bond Ativting Group Figure 1. Di- nd tri-thiorbonylthio RAFT gents. RAFT owes its suess to sequene of ddition-frgmenttion equilibri, shown in Sheme 5. Erly in the polymeriztion, the propgting rdil dds to the thiorbonylthio ompound, whih results in frgmenttion of the intermedite rdil speies (Step II). This yields polymeri thiorbonylthio ompound (P m ) s well s new rdil speies, whih n further ret with more monomer forming new propgting rdil speies (P n ). A rpid equilibrium is estblished between the tive propgting rdils (P m nd P n ) tht provide n equl probbility for ll hins to grow, llowing for the formtion of polymers with nrrow Đ. 10 5

19 Sheme 5. Generlly epted mehnism for RAFT polymeriztion Ayli Diene Metthesis (ADMET) Polymeriztion Ayli diene metthesis (ADMET) polymeriztion is type of step-growth, ondenstion polymeriztion, nd ws developed in 1991 by Dr. Ken Wgener t the University of Florid. In ADMET polymeriztion, trnsition metl tlyst is used to polymerize terminl dienes to polyenes. Polymer formtion is driven by the libertion of ethylene gs, with the double bonds formed either in is- or trns-onfigurtion, depending on the monomer nd tlyst struture. 6

20 Sheme 6. Mehnism of ADMET polymeriztion Cylopolymeriztion Alternting intr-intermoleulr polymeriztion, more ommonly known s ylopolymeriztion, is type of polymeriztion in whih yli speies re formed from the intrmoleulr yliztion of monomers ontining unonjugted dienes. This type of polymeriztion ws first introdued by Butler nd oworkers, who demonstrted tht the rdil polymeriztion of N,N-dillyl-N,N-dimethylmmonium hloride (DADMAC) yielded soluble, unrosslinked polymers with little to no unsturtion. 11 Though Butler believed tht he hd formed six-membered (endo ylized) speies, Hwthorn et l. demonstrted tht the route through whih the polymer ws formed yielded fivemembered (exo ylized) speies due to more fvorble orbitl overlp in the trnsition stte, 12 s shown in Sheme 7. 7

21 endo Butler, 1956 exo Hwthorne, 1976 Sheme 7. Cyliztion of quternry mines. Although dillyl quternry mmonium slts ylopolymerize to reltively high effiieny, dillyl tertiry mines do not redily ylopolymerize, 13 in prt due to degrdtive hin trnsfer, hin-breking retion involving the bstrtion of hydrogen or some other tom or speies, i.e. inititor, monomer, or polymer. 14 This dereses the size of the propgting polymer speies, nd results in brnhed polymer system when hin trnsfer to polymer ours. However, Zubov et l. suggested tht strong eletron withdrwing substituent on dillyl tertiry mines indues strong prtil positive hrge on the nitrogen tom, deresing the effets of degrdtive hin trnsfer. 15 Trnsfer to Inititor Trnsfer to Monomer Trnsfer to Polymer Sheme 8. Degrdtive hin trnsfer. Due to the strong eletron withdrwing nture of the sulfone group, prtil positive hrge is indued on the nitrogen in dillyl tertiry sulfonmides, whih should 8

22 inrese their bility to polymerize. Indeed, J. H. Hodgkin et l. suessfully rdilly polymerized tertiry dillyl sulfonmides with methyl nd phenyl substituents in bulk. 16 It hs lso been shown tht the smller the differene in hemil shifts of the terminl nd penultimte lkene rbons or hydrogens, the greter the yliztion effiieny nd greter the moleulr weight of the resulting polymer, 17 nd is inditive of greter prtil positive hrge on the nitrogen. Tble 1. Literture vlues for dillylmine derivtives. % Conversion to Polymer R 1 R 2 -H - Tre 16 -H -H CH CH 3 -CH CN SO 2 C 6 H SO 2 C 6 H 4 Cl Nuleophili Aromti Substitution (S N Ar) Polyondenstion Poly(rylene ether sulfone)s (PAES) re lss of morphous engineering thermoplstis, nd n be prepred by either eletrophili romti substitution, 22 or nuleophili romti substitution (S N Ar) polyondenstion. 23 Tody, the S N Ar route of polyondenstion is most ommonly utilized for the ommeril prodution of these thermoplstis, nd few of the ommerilly vilble PAES re shown in Figure 2. The mehnism of S N Ar involves the tivtion of n ryl hlide by n eletronwithdrwing group (EWG), typilly loted in the pr-position, s shown in Sheme 9. 9

23 UDEL (Union Crbide) T g = 190 C RADEL (Union Crbide) T g = 220 C VICTREX (ICI) T g = 230 C PES (ICI) T g = 250 C Figure 2. Commerilly vilble PAES. The first step in S N Ar mehnism is lrgely thought to be reversible nd the rte-determining step: nuleophili ttk t the ipso rbon resulting in Meisenheimer omplex, resonne stbilized nioni intermedite speies. The seond step involves the loss of the hlide group, resulting in the benzene regining its romtiity. ASTREL (3M Corp) T g = 285 C Sheme 9. Generl mehnism for S N Ar. 10

24 Sheme 10. Outline of S N Ar polyondenstion. Although S N Ar retions re usully rried out with ryl hlides tivted by n EWG in the ortho- or pr- position, Kiti et l. demonstrted tht S N Ar n lso tke ple t the met position reltive to the EWG. 24 Sine then, our group hs introdued vriety of tivting groups for the synthesis of PAEs vi met tivted S N Ar retions, s shown in Sheme 11. In these systems, the tivting group resides pendent to the polymer bkbone, llowing for the introdution of vrious funtionl groups without diretly modifying the bkbone of the polymer. Sheme 11. Synthesis of PAEs vi met-tivted S N Ar polyondenstion retions. Sulfonmides hve been desribed s strong eletron withdrwing groups for the tivtion of ryl hlides for S N Ar retions when positioned ortho nd pr, 28 s well s met, to the hlide. 27,29 As site for the introdution of vriety of funtionl groups pendent to the polymer hin, sulfonmides re n ttrtive option. This feture n be exploited to tilor the properties of the polymer for speifi pplition. 11

25 1.5. Bifuntionl Monomers Bifuntionl monomers re ompounds tht hve two distint types of funtionlity with mutully exlusive retivity. Tht is to sy, polymeriztion of one type of funtionl group does not ffet the other. Current methods of polymerizing bifuntionl monomers mke use of nioni, tioni, nd rdil polymeriztion methods, exmples of whih re shown in Figure 3. Hgiswr Jing Alkn Frey Sumerlin Figure 3. Exmples of bifuntionl monomers Introdution of Funtionlity In order to meet speifi pplition need, it is useful tool to tilor the physil nd hemil properties of polymer through introdution of funtionl groups to the system. This n be hieved in one of two wys: by either introduing funtionlity t the monomer stge (pre), or by introduing funtionlity fter the polymeriztion hs been ompleted (post). A generl sheme for the introdution of funtionl groups is shown in Sheme

26 Sheme 12. Introduing funtionlity vi pre nd post polymeriztion modifition Current Reserh In this projet, the sulfonmide moiety ws exploited in order to form bifuntionl monomers tht were pble of undergoing S N Ar polyondenstion, s well s metthesis nd vrious forms of rdil polymeriztions. A series of N,N-dillylbenzenesulfonmide bsed monomers were prepred in one-step proess modified from the literture, s shown in Sheme 15. These monomers re ble to be utilized for both pre-nd post polymeriztion funtionliztion, nd provide strightforwrd wy of tuning the physil properties of polymer by hnging the rtio of the seleted monomer. In order to tke dvntge of both systems (pre or post polymeriztion modifition), s well s the bifuntionlity of these monomers, the type of modifition, s well s the type of polymeriztion (rdil, ADMET, or S N Ar) n be vried to produe wide vriety of polymers. For post-polymeriztion funtionliztion of polymer formed by either rdil or ADMET polymeriztion, n intive funtionl group, suh s bromine, n be introdued t the monomer level then onverted by postpolymeriztion modifition (Sheme 13). Conversely, polymers formed vi S N Ar n be 13

27 post funtionlized by reting the pendent llyl groups with n pproprite ompound, e.g. thiol ompound (Sheme 14). Sheme 13. Pre (top) nd post (bottom) polymeriztion modifition of DABSA-4-Br. Sheme 14. Pre (top) nd post (bottom) polymeriztion modifition of DABSA-3,5-DF. 14

28 2. EXPERIMENTAL 2.1. Mterils Diethyl ether nd toluene were purhsed from Fisher Sientifi nd used s reeived. 4-Fluorobenzenesulfonyl hloride, 2,4-difluorobenzenesulfonyl hloride nd 3,5-diflurobenzenesulfonyl hloride were purhsed from Okwood Chemils nd used s reeived. 2,2 -Azobis(2-methylpropionitrile) (AIBN), benzenesulfonyl hloride, 4- bromobenzenesulfonyl hloride, benzoyl peroxide (BPO), hloroform-d (CDCl 3 ), opper (I) bromide (CuBr), opper (II) bromide (CuBr 2 ), dillylmine, diotylmine, ethyl-2- bromopropionte (EBrP), Hoveyd-Grubbs 2 nd genertion tlyst (HG2G), hydrohlori id (HCl), N,N,N,N,N -pentmethyldiethylenetrimine (PMDETA), triethylmine (TEA), tris[2-(dimethylmino)ethyl]mine (Me 6 TREN), nd ynomethyl methyl(phenyl) rbmodithiote (CMMPCDT), were purhsed from Sigm-Aldrih nd used s reeived. 4,4 -dihydroxydiphenyl ether ws purhsed from TCI Chemils nd rerystllized from toluene nd dried under vuum prior to use. Clium hydride (CH 2 ) nd potssium rbonte (K 2 CO 3 ) were purhsed from Sigm-Aldrih nd dried in n oven t 130 C before use. Dihloromethne (DCM) nd xylenes were purhsed from Fisher Sientifi; N-methyl-2-pyrrolidone (NMP) ws purhsed from Sigm- Aldrih, ll were dried over CH 2 nd distilled prior to use. 15

29 2.2. Instrumenttion Differentil Snning Clorimetry (DSC) nd Thermogrvimetri Anlysis (TGA) nlyses were rried out on TA Instruments DSC Q200 (under nitrogen) nd TGA Q500 (under nitrogen or ir), respetively t heting rte of 10 C/min. Gs hromtogrphy-mss spetrosopy (GC/MS) nlyses were performed using n Agilent Tehnologies 7820A Series GC System, nd n Agilent Tehnologies 5975 Mss Seletive Detetor/Qudrupole system. 1 H nd 13 C Nuler Mgneti Resonne (NMR) spetr were quired using Bruker AVANCE 300 MHz instrument operting t 300 nd 75.5 MHz, respetively. Smples were dissolved in CDCl 3 t onentrtion of (~30 mg /0.7 ml). Gel permetion hromtogrphy (GPC) nlysis ws performed using instrumenttion onsisting of Visotek Model 270 dul detetor (visometer nd light sttering) nd Visotek Model VE3580 refrtive index detetor. Two Polymer Lbortories 5 µm PLgel Mixed-C olumns (heted to 35 C) were used with THF/5% (v/v) eti id s the eluent nd GPC mx VE-2001 with pump operting t 1.0 ml/minute. Cyliztion effiienies (CE) were determined by integrting the double bond proton peks reltive to the bkbone proton peks in the 1 H NMR spetrum. Weight verge moleulr weights, M w, nd Dispersity (Đ) vlues were determined using OmniSe softwre (librted with polystyrene stndrds). Melting points were determined on MEL-TEMP pprtus, or DSC nd re unorreted. Elementl nlyses were obtined from Midwest Mirolbs, In., Indinpolis, IN. The energy of monomers 1-e ws lulted in vuum using the Sprtn 10 omputtionl softwre pkge (Wvefuntion, In., Irvin, CA). The geometries were initilly optimized using the semiempiril method RM1, nd then further optimized using density funtionl theory t 16

30 the B3LYP/6-31+G ** level. The energy of eh of the monomers ws reorded nd expressed s reltive energy with respet to the most stble speies of tht hrge Generl Proedure for the Synthesis of N,N-dillylbenzenesulfonmide (DABSA) Derivtives The generl proedure for the synthesis of N,N-dillylbenzenesulfonmide (DABSA) derivtives will be illustrted using N,N-dillylbenzenesulfonmide. To solution of benzenesulfonyl hloride (4.00 g, 22.6 mmol) in 70 ml of dihloromethne, ws dded triethylmine (TEA, 3.95 ml, 28.3 mmol, 25% exess). The solution ws llowed to stir for five minutes, t whih point dillylmine (3.62 ml, mmol, 25% exess) ws dded nd the resulting mixture stirred for pproximtely three hours, during whih time mild exothermi retion ourred. Anlysis of n liquot by GC/MS showed quntittive onversion of the strting mteril to the desired produt (if the GC/MS did not show quntittive onversion, TEA ws dded dropwise until TEA- HCl preipitted in the retion mixture). The orgni phse ws extrted with 2 x 250 ml 10% HCl, 2 x 250 ml old, distilled wter, 1 x 100 ml 5% HCl, nd 1 x 100 ml old, distilled wter, nd then dried over MgSO 4 nd filtered. The solvent ws removed vi rotry evportion to fford 4.83 g (90%) of N,N-dillylbenzenesulfonmide (DABSA, 1) s light yellow liquid (M.P. < -85 C by DSC), 1 H-NMR (CDCl 3, δ): 3.84 (d, 4H, N-CH 2 -), 5.13 (m, 2H, is C=CH 2 ), 5.18 (m, 2H, trns C=CH 2 ), 5.62 (m, 2H, -CH=), 7.56 (m, 3H, Ar-H), 7.84 (m, 2H, Ar-H) ppm; DEPT C NMR (CDCl 3, δ): 49.3 (s, N-CH 2 -), (s, =CH 2 ), (s, Ar-H), (s, Ar-H), (s, -CH=), (s, Ar-H) ppm. 13 C NMR (CDCl 3, δ): 49.3 (s, -CH 2 -), (s, =CH 2 ), (s, Ar-H), (s, Ar-H), (s, Ar-H), (s, -CH=), (s, Ar-SO 2 ) ppm. 17

31 Elementl Anlysis: Cl. Anl. for C 12 H 15 NO 2 S: C, 60.3; H, 6.37; Found: C, 60.8; H, Syntheses of the remining N,N-dillylbenzenesulfonmides were rried out in similr fshion, with the exeption of N,N-dillyl-3,5-difluorobenzenesulfonmide whih ws preipitted from ethnol/wter to fford white solid. N,N-dillyl-4-bromobenzenesulfonmide (DABSA-4-Br, 1b, 96%): M.P. = -62 C by DSC; 1 H-NMR (CDCl 3, δ): 3.76 (d, 4H, N-CH 2 -), 5.10 (m, 2H, is C=CH 2 ), 5.13 (m, 2H, trns C=CH 2 ), 5.56 (m, 2H, -CH=), 7.63 (m, 4H, Ar-H) ppm; DEPT C NMR (CDCl 3, δ): 49.3 (s, N-CH 2 -), (s, =CH 2 ), (s, Ar-H), (s, Ar-H), (s, -CH=) ppm. 13 C NMR (CDCl 3, δ): 49.3 (s, -CH 2 -), (s, =CH 2 ), (s, Ar-Br), (s, Ar-H), (s, Ar-H), (s, -CH=), (s, Ar-SO 2 ) ppm. Elementl Anlysis: Cl. Anl. for C 12 H 14 NO 2 SBr: C, 45.5; H, 4.46; Found: C, 45.7; H, N,N-dillyl-4-fluorobenzensulfonmide (DABSA-4-F, 1, 86%): M.P. < -85 C by DSC; 1 H-NMR (CDCl 3, δ): 3.79 (d, 4H, N-CH 2 -), 5.10 (m, 2H, is C=CH 2 ), 5.15 (m, 2H, trns C=CH 2 ), 5.58 (m, 2H, -CH=), 7.16 (m, 2H, Ar-H), 7.82 (m, 2H, Ar-H) ppm; DEPT C NMR (CDCl 3, δ): 49.3 (s, N-CH 2 -) (d, Ar-H), (s, =CH 2 ), (d, Ar-H), (s, -CH=) ppm. 13 C NMR (CDCl 3, δ): 49.3 (s, -CH 2 -), (s, Ar-H), (s, =CH 2 ), (d, Ar-H), (s, -CH=), (s, Ar-SO 2 ), (d, Ar-F) ppm. Elementl Anlysis: Cl. Anl. for C 12 H 14 NO 2 SF: C, 56.5; H, 5.53; Found: C, 56.5; H, N,N-dillyl-2,4-diflurobenzenesulfonmide (DABSA-2,4-DF, 1d, 94%): M.P. < - 85 C by DSC; 1 H-NMR (CDCl 3, δ): 3.92 (d, 4H, N-CH 2 -), 5.15 (m, 2H, is C=CH 2 ), 18

32 5.19 (m, 2H, trns C=CH 2 ), 5.64 (m, 2H, -CH=), 6.95 (m, 2H, Ar-H), 7.94 (m, 1H, Ar-H) ppm; DEPT C NMR (CDCl 3, δ): 49.1 (s, N-CH 2 -), (t, Ar-H), (dd, Ar- H), (s, =CH 2 ), (s, -CH=), (d, Ar-H) ppm. 13 C NMR (CDCl 3, δ): 49.1 (d, -CH 2 -), (t, Ar-H), (d, Ar-H), (s, =CH 2 ), (m, Ar-SO 2 ), (s, -CH=), (d, Ar-H) (dd, Ar-F), (dd, Ar-F) ppm. Elementl Anlysis: Cl. Anl. for C 12 H 13 NO 2 SF 2 : C, 52.7; H, 4.79; Found: C, 52.3; H, N,N-dillyl-3,5-diflurobenzenesulfonmide (DABSA-3,5-DF, 1e, 93%): M.P. = C; 1 H-NMR (CDCl 3, δ): 3.86 (d, 4H, N-CH 2 -), 5.18 (m, 2H, is C=CH 2 ), 5.22 (dq, 2H, trns C=CH2), 5.64 (m, 2H, -CH=C), 7.03 (tt, 1H, Ar-H), 7.37 (m, 2H, Ar-H); DEPT C NMR (CDCl 3, δ): 49.4 (s, N-CH 2 -), (t, Ar-H), (dd, Ar-H), (s, =CH 2 ), (s, -CH=) ppm. 13 C NMR (CDCl 3, δ): 49.4 (s, -CH 2 -), (t, Ar-H), (dd, Ar-H), (s, =CH 2 ), (s, -CH=), (t, Ar-SO 2 ) (dd, Ar-H) ppm. Elementl Anlysis: Cl. Anl. for C 13 H 14 NO 2 SF 2 : C, 52.74; H, 4.79; Found: C, 52.8; H, Generl Proedure for the Synthesis of N,N-diotylbenzenesulfonmide (DOtBSA) Derivtives The generl proedure for the synthesis of N,N-diotylbenzenesulfonmide derivtives will be illustrted using N,N-diotyl-2,4-difluorobenzenesulfonmide (2). To solution of 2,4-difluorobenzenesulfonyl hloride (4.00 g, 22.6 mmol) in 70 ml of dihloromethne, ws dded triethylmine (TEA, 3.95 ml, 28.3 mmol, 25% exess). The solution ws llowed to stir for five minutes, t whih point diotylmine (3.62 ml, mmol, 25% exess) ws dded nd the resulting mixture stirred for pproximtely three hours, during whih time mild exothermi retion ourred. 19

33 Anlysis of n liquot by GC/MS showed quntittive onversion of the strting mteril to the desired produt (if the GC/MS did not show quntittive onversion, TEA ws dded dropwise until TEA-HCl preipitted in the retion mixture). The orgni phse ws extrted with 2 x 250 ml 10% HCl, 2 x 250 ml old, distilled wter, 1 x 100 ml 5% HCl, nd 1 x 100 ml old, distilled wter, nd then dried over MgSO 4 nd filtered. One the solvent ws removed vi rotry evportion, pproximtely 25 ml of hexnes ws dded nd the solution stirred for two hours. The diotylmine preipitte ws filtered off, nd the solvent removed vi rotry evportion to fford 4.83 g (70%) of N,N-diotyl-2,4-difluorobenzenesulfonmide (DOtBSA-2,4-DF, 2) s light yellow liquid. 1 H-NMR (CDCl 3, δ): 0.89 (t, 6H, -CH 3 ), 1.28, (m, 20H, -CH 2 -), 1.51 (m, 4H, - CH 2 -), 3.23 (t, 4H, N-CH 2 -), 6.96 (m, 2H, Ar-H), 7.93 (m, 1H, Ar-H) ppm. DEPT C NMR (CDCl 3, δ): 13.9 (s, -CH 3 ), 22.5 (s, -CH 2 -), 26.5 (s, -CH 2 -), 28.4 (s, -CH 2 -), 29.1 (s, -CH 2 -), 29.1 (s, -CH 2 -), 31.7 (s, -CH 2 -), 49.5 (d, N-CH 2 ), (t, Ar-H), (dd, Ar- H), (dd, Ar-H) ppm. 13 C NMR (CDCl 3, δ): 13.9 (s, -CH 3 ), 22.5 (s, -CH 2 -) 26.5 (s, - CH 2 -), 28.4 (s, -CH 2 -), 29.1 (s, -CH 2 -), 29.1 (s, -CH 2 -), 31.7 (s, -CH 2 ), 49.5 (d, N-CH 2 -), (t, Ar-H), (dd, Ar-H), (dd, Ar-SO 2 -), (dd, Ar-H), (dd, Ar- F), (dd, Ar-F) ppm. Elementl Anlysis: Cl. Anl. for C 22 H 33 NO 2 SF 2 : C, 63.3; H, 8.93; Found: C, 62.3; H, N,N-diotyl-3,5-difluoronbenzenesulfonmide (DOtBSA-3,5-DF, 2b, 70%): 1 H- NMR (CDCl 3, δ): 0.90 (t, 6H, -CH 3 ), 1.27 (m, 20H, -CH 2 -), 1.53 (m, 4H, -CH 2 -), 3.15 (t, 4H, N-CH 2 -), 7.01 (tt, 1H, Ar-H), 7.35 (m, 1H, Ar-H) ppm. DEPT C NMR (CDCl 3, δ): 14.0 (s, -CH 3 ), 22.6 (s, -CH 2 ), 26.7 (s, -CH 2 -), 28.6 (s, -CH 2 -), 29.1 (s, -CH 2 -), 31.7 (s, -CH 2 -), 48.2 (s, N-CH 2 -), (t, Ar-H), (dd, Ar-H) ppm. 13 C NMR (CDCl 3, δ): 20

34 14.0 (s, -CH 3 ), 22.6 (s, -CH 2 ), 26.7 (s, -CH 2 -), 28.6 (s, -CH 2 -), 29.1 (s, -CH 2 -), 31.7 (s, - CH 2 -), 48.2 (s, N-CH 2 -), (t, Ar-H), (dd, Ar-H), (t, Ar-SO 2 ), (dd, Ar-F) ppm. Elementl Anlysis: Cl. Anl. for C 22 H 33 NO 2 SF 2 : C, 63.9; H, 8.04; Found: C, 63.1; H, Rdil Polymeriztion FRP of DABSA Derivtives The generl proedure for the free rdil polymeriztion (FRP) of N,Ndillylbenzenesulfonmide (DABSA) derivtives will be illustrted using DABSA, with AIBN s the inititing speies. To 25 ml Shlenk tube equipped with mgneti stir br ws dded DABSA (0.183 g, 7.75 mmol) nd AIBN (0.191 g, 1.16 mmol, 15%). After purging with nitrogen for 25 minutes, the tube ws lowered into n oil bth heted to 70 C nd llowed to ret for 24 hours, fter whih point highly visous, drk yellow oil ws observed. The polymer ws preipitted from diethyl ether to fford g (51%) of p1 s white solid. 1 H NMR (CDCl 3, δ): 2.06 (m, 243H, Bkbone H), 3.83 (d, 4H, N-CH 2 -), 5.15 (m, 4H, =CH 2 ), 5.61 (m, 2H, -CH=), 7.57 (s, 65H, Ar-H), 7.82 (s, 45H, Ar-H) ppm. p1 (BPO, 49%) 1 H NMR (CDCl 3, δ): 1.97 (m, 503 H, Bkbone-H), 3.83 (d, 4H, N-CH 2 -), 5.15 (m, 4H, =CH 2 ), 5.61 (m, 2H, -CH=), 7.56 (s, 149H, Ar-H), 7.82 (s, 99H, Ar-H) ppm. The FRP of the remining DABSA derivtives were rried out in n nlogous fshion p1b (AIBN, 84%) 1 H NMR (CDCl 3, δ): 2.08 (m, 330H, Bkbone-H), 3.83 (d, 4H, N-CH 2 -), 5.17 (m, 2H, =CH 2 ), 5.59 (m, 4H, -CH=), 7.70 (m, 122H, Ar-H) ppm. 21

35 p1 (AIBN, 63%) 1 H NMR (CDCl 3, δ): 2.05 (m, 285H, Bkbone-H), 3.83 (d, 4H, N-CH 2 -), 5.16 (m, 4H, =CH 2 ), 5.62 (m, 2H, -CH=), 7.23 (m, 50H, Ar-H), 7.85 (m, 50H, Ar-H) ppm. p1d (AIBN, 67%) 1 H NMR (CDCl 3, δ): 2.19 (m, 869H, Bkbone-H), 3.91 (d, 4H, N-CH 2 -), 5.17 (m, 4H, =CH 2 ), 5.63 (m, 2H, -CH=), 7.03 (s, 145H, Ar-H), 7.91 (s, 75H, Ar-H) ppm. p1d (BPO, 58%) 1 H NMR (CDCl 3, δ): 2.15 (m, 923H, Bkbone-H), 3.92 (d, 4H, N-CH 2 -), 5.17 (m, 4H, =CH 2 ), 5.63 (m, 2H, -CH=), 7.01 (s, 164H, Ar-H), 7.91 (s, 85H, Ar-H) ppm. p1e (AIBN, 90%) 1 H NMR (CDCl 3, δ): 2.10 (m, 490H, Bkbone-H), 3.86 (d, 4H, N-CH 2 -), 5.20 (m, 4H, =CH 2 ), 5.63 (m, 2H, -CH=), 7.09 (s, 42H, Ar-H), 7.36 (s, 92H, Ar-H) ppm. p1e (BPO, 56%) 1 H NMR (CDCl 3, δ): 2.12 (m, 509H, Bkbone-H), 3.86 (d, 4H, N-CH 2 -), 5.19 (m, 4H, =CH 2 ), 5.64 (m, 2H, -CH=), 7.08 (s, 50H, Ar-H), 7.36 (s, 108, Ar- H) ppm ATRP of DABSA Derivtives The generl proedure for tom trnsfer rdil polymeriztion (ATRP) will be illustrted using DABSA nd tris[2-(dimethylmino)ethyl]mine (Me 6 TREN) s the lignd. To 25 ml Shlenk tube under nitrogen tmosphere ws dded DABSA (0.712 gm, 3.00 mmol), nd CuBr (4.30 mg, mmol, 1%), ethyl-2-bromopropionte (EBrP, 5.43 mg, mmol, 1%), nd Me 6 TREN (5.96 µl, mmol, 1%) in 2.00 ml of dry xylenes. After sprging the solution with nitrogen for 30 minutes, the flsk 22

36 ws lowered into n oil bth heted to 100 C, nd llowed to ret for 48 hours. Anlysis vi 1 H NMR spetrosopy indited no onversion to polymer ICAR ATRP of DABSA Derivtives The generl proedure for inititors for onstnt tivtor regenertion (ICAR) ATRP will be illustrted using DABSA, Me 6 TREN s the lignd, nd AIBN s the soure of rdils tht ret with the trnsition metl omplex to ontinuously regenerte its lower oxidtive stte. To 25 ml Shlenk tube under nitrogen tmosphere ws dded DABSA (0.712 g, 3.00 mmol), nd CuBr 2 ( mg, 1.50x10-4 mmol, 0.005%), EBrP (2.72 mg, mmol, 1%), nd Me 6 TREN ( µl, 1.50x10-4 mmol, 0.005%) in 2.00 ml of dry xylenes. After sprging the solution with nitrogen for 30 minutes, the flsk ws lowered into n oil bth heted to 100 C, nd llowed to ret for 48 hours. Anlysis vi 1 H NMR spetrosopy indited no onversion to polymer Reversible Addition-Frgmenttion Chin Trnsfer (RAFT) Polymeriztion of DABSA-2,4-DF To 25 ml Shlenk tube under nitrogen tmosphere ws dded DABSA-2,4- DF (0.728 g, 2.67 mmol), ynomethyl methyl(phenyl) rbmodithiote (CMMPCDT, mg, mmol, 5%) nd AIBN (21.88 mg, mmol, 5%) in 1mL of dry xylenes. After sprging the solution with nitrogen for 30 minutes, the flsk ws lowered into n oil bth heted to 80 C for 7 dys, fter whih point the polymer ws preipitted from diethyl ether to fford g (12%) of p2d s yellow solid. 23

37 2.6. ADMET Polymeriztion of DABSA Derivtives The generl proedure of yli diene metthesis (ADMET) polymeriztion will be illustrted using DABSA. To solution of DABSA (0.133 g, 0.56 mmol) in 0.56 ml of xylenes, ws dded Hoveyd-Grubbs 2 nd Genertion tlyst (11.4 mg, mmol, 3.25%). The solution ws sprged with nitrogen for 25 minutes, then lowered into n oil bth heted to 70 C nd llowed to ret under vuum for 24 hours. The polymer ws preipitted from diethyl ether nd dried under vuum to fford g (52%) of p3 s grey solid. The polymer ws hrterized by 1 H-NMR spetrosopy, GPC nlysis, TGA, nd DSC (Mn = 14,915 g/mol, T m = 115 C, T d-5% = 146 C), 1 H NMR (CDCl 3, δ): 4.15 (s, 4H, N-CH 2 ), 5.67 (s, 2H, -CH=), 7.58 (m, 3H, Ar-H), 7.86 (m, 2H, Ar-H) ppm; 13 C NMR (CDCl 3, δ): 54.9 (s, N-CH 2 ), (s, -CH=), (s, Ar-H), (s, Ar-H), (s, Ar-H), (s, Ar-H) ppm. The ADMET Polymeriztion of the remining DABSA derivtives ws rried out in n nlogous fshion. p3b (54%): M n = 8,690 g/mol, T m = 136 C, T d-5% = 167 C; 1 H-NMR (CDCl 3, δ): 4.14 (s, 4H, N-CH 2 -), 5.69 (s, 2H, -CH=), 7.70 (m, 4H, Ar-H) ppm. 13 C NMR (CDCl 3, δ): 54.9 (s, N-CH 2 -), (s, -CH=), (s, Ar-Br), (s, Ar-H), (s, Ar-H), (s, Ar-SO 2 -) ppm. p3 (50%): M n = 17,075 g/mol T m = 90 C, T d-5% = 159 C; 1 H-NMR (CDCl 3, δ): 4.13 (s, 4H, N-CH 2 -), 5.68 (s, 2H, -CH=), 7.22 (t, 2H, Ar-H), 7.86 (m, 2H, Ar-H) ppm. 13 C (CDCl 3, δ): 54.9 (s, N-CH 2 -), (d, Ar-H), (s, -CH=), (d, Ar-H), (s, Ar-SO 2 ), (d, Ar-F) ppm. 24

38 p3d (49%): M n = 5,550 g/mol T m = 65.5 C, T d-5% = 146 C; 1 H-NMR (CDCl 3, δ): 4.24 (s, 4H, N-CH 2 -), 5.75 (s, 2H, -CH=), 6.99 (m, 3H, Ar-H), 7.96 (m, 1H, Ar-H) ppm. 13 C (CDCl 3, δ): 54.5 (s, N-CH 2 -), (t, Ar-H), (dd, Ar-H), (m, Ar- SO 2 ), (s, -CH=), (dd, Ar-H), (dd, Ar-F), (dd, Ar-F). p3e (58%): M n = 10,210 g/mol, T m = 109 C, T d-5% = 125 C; 1 H-NMR (CDCl 3, δ): 4.17 (s, 4H, N-CH 2 ), 5.72 (s, 2H, -CH=), 7.06 (tt, 1H, Ar-H), 7.39 (m, 2H, Ar-H) ppm; 13 C (CDCl 3, δ): 55.0 (s, N-CH 2 -), (t, Ar-H), (dd, Ar-H), (s, - CH=), (t, Ar-SO 2 -), (dd, Ar-F) ppm S N Ar Copolymeriztion of 2/b nd 1d/e using 4,4 -dihydroxydiphenyl ether The generl proedure for nuleophili romti substitution (S N Ar) opolymeriztion will be illustrted using 2,4-DFDOtBSA (2), nd DABSA-2,4-DF (1d). To solution of 2 (0.595 g, 1.43 mmol, 95%), 1d ( g, mmol, 5%), nd 4,4 -dihydroxydiphenyl ether (0.303 g, 1.5 mmol) in 4.69 ml of NMP, ws dded K 2 CO 3 (0.311 g, 2.25 mmol) nd the solution sprged for 25 minutes then lowered into n oil bth heted to 135 C nd llowed to ret for 72 hours. The polymer ws preipitted from wter nd dried under vuum to fford g (58.6%) of 95/5- poly(2,4-dotbsa-o-2,4-dabsa) (p4, M n = 3,660 g/mol, T g = 14.5 C, T d-5% = 354 C), 1 H-NMR (CDCl 3, δ): 0.87 (m, 6H, -CH 3 ), 1.24 (s, 20H, -CH 2 -), 1.53 (m, 4H, -CH 2 -), 3.27 (m, 4H, N-CH 2 -), 3.96 (m, 4H, N-CH 2 -), 5.17 (d, m, 4H, =CH 2 ), 5.69, (m, 2H, - CH=), 6.54 (m, 2H, Ar-H), 7.02 (m, 4H, Ar-H), 7.28 (s, 2H, Ar-H), 7.92 (d, 2H, Ar-H) ppm; DEPT C NMR (CDCl 3, δ): (s, Ar-H), (s, Ar-H), (s, Ar-H), (d, Ar-H), (s, -CH=) ppm. 25

39 S N Ar opolymeriztion of 1e/2b ws rried out in n nlogous fshion. p4b (54.3%): M n = 3,050 g/mol; T g = 6.34 C; T d-5% = 329 C; 1 H NMR (CDCl 3, δ): 0.89 (m, 6H, -CH 3 ), 1.27 (s, 20H, -CH 2 -), 1.52 (m, 4H, -CH 2 -), 3.15 (m, 4H, N-CH 2 -), 3.79 (m, 4H, N-CH 2 -), 5.16 (m, 4H, =CH 2 ), 5.64 (m, 2H, -CH=), 6.79 (m, 2H, Ar-H), 7.11 (m, 4H, Ar-H), 7.37 (d, 4H, Ar-H) ppm; DEPT C NMR (CDCl 3, δ): (s, Ar-H), (s, Ar-H), (s, Ar-H), (s, -CH=) ppm Chrteriztion Size Exlusion Chromtogrphy (SEC) Size exlusion hromtogrphy (SEC) ws used to determine moleulr weight nd moleulr weight distributions of polymers in THF/5% eti id. Number verge moleulr weights (M n ) nd dispersity (Đ) were determined using the refrtive index (RI) signl, the weight verge moleulr weight (M w ) were determined vi the light sttering signl. Clibrtion ws done using polystyrene stndrds Differentil Snning Clorimetry (DSC) The therml trnsition tempertures of the mterils were determined using TA Instruments Q200 Differentil Snning Clorimeter. The melting point of the monomers were determined by heting 5 mg of smple, in T zero luminum pn, t 10 C/min from -185 to 50 C. A typil method of determining the therml trnsition tempertures of polymers inluded heting 5 mg of smple, in T zero luminum pn, t 10 C/min from 40 to 150 C nd ooling t 10 C/min to 0 C in two yles under nitrogen tmosphere. The glss trnsition temperture (T g ) ws determined t the midpoint of the tngent of the seond heting yle. The first heting yle ws utilized to erse the therml history of 26

40 the polymers, nd the melting temperture (T m ) ws determined t the endothermi pek of the seond heting yle Thermogrvimetri Anlysis (TGA) The therml stbility of the polymers ws investigted using TA Instruments Q500 Thermogrvimetri Anlyzer. The nlysis involved heting smple of 5 mg t rte of 10 C/min from 40 to 800 C under nitrogen tmosphere. The weight loss ws reorded s funtion of temperture, nd the therml stbility ws reported s 5% weight loss (T d-5% ). 27

41 3. RESULTS AND DISCUSSION 3.1. Monomer Synthesis A series of bifuntionl monomers bsed on N,N-dillylbenzenesulfonmide (DABSA) with vrying groups present on the benzene moiety, ws investigted. Using the pproprite benzenesulfonyl hloride (BSC) derivtive s strting mteril, five monomers were prepred vi nuleophili substitution, s shown in Sheme 15. For eh of the retions, ommerilly vilble triethyl mine (TEA) nd dillylmine were llowed to ret with the BSC derivtive in DCM for pproximtely three hours, t whih point GC/MS nlysis indited omplete onversion of the strting mterils to the desired produt. DABSA 1 DABSA-4-Br 1b DABSA-4-F 1 DABSA-2,4-DF 1d Sheme 15. Syntheti route for DABSA derivtives. DABSA-3,5-DF 1e 28

42 Synthesis of N,N-dillylbenzenesulfonmide (DABSA) Derivtives Using benzenesulfonyl hloride s strting mteril, N,Ndillylbenzenesulfonmide (DABSA), 1, ws prepred by nuleophili substitution. Commerilly vilble benzenesulfonyl hloride ws llowed to ret t room temperture with triethyl mine for fifteen minutes, t whih point dillylmine ws dded nd llowed to ret for 3 hours, during whih time n exothermi retion ourred. GC/MS nlysis of n liquot onfirmed tht the strting mterils were onverted to the desired produt. After wshing with HCl/wter, nd removing the DCM vi rotry evportion, the produt ws isolted to fford 1 s yellow oil in 90 % yield. The struture ws onfirmed by 1 H nd 13 C NMR spetrosopy, GC/MS, nd elementl nlysis. The 1 H nd 13 C NMR spetr of 1 re presented in Figure 4 nd Figure 6, respetively. Integrtion of the 1 H NMR spetrum onfirmed the orret number of hydrogens in the monomer. There re six unique peks tht pper in the 1 H NMR spetrum of 1 (Figure 4). The most upfield proton ppers s doublet t 3.84 ppm ( 3 J H-H = 6.28 Hz) due to oupling with n djent hydrogen tom. Both the is- ( ) nd trns- () protons pper s multiplets from nd ppm, respetively. Protons nd n be distinguished by the differene in shielding; is more shielded by the CH 2 thn is, resulting in being more upfield. Protons b nd d pper s series of multiplets from nd from ppm, respetively. Protons e nd f pper s omplex series of overlpping multiplets from ppm. 29

43 d ' b e/f d e f * b ' * Figure MHz 1 H NMR spetrum (CDCl 3 ) of 1. Syntheses of the remining N,N-dillylbenzenesulfonmide derivtives were rried out in n nlogous fshion, nd the mjor differenes between the 1 H nd 13 C NMR spetr re the speifi signls in the romti region, rising from the benzenesulfonyl hloride derivtive used for the synthesis (see Figure 5 nd Figure 7). Protons - nd rbons - pper in essentilly the sme positions in monomers 1-e. N,N-dillyl-4-bromobenzenesulfonmide (1b) ws prepred in 96% yield s yellow oil, nd in the 1 H NMR spetrum protons d nd e pper s series of brod, overlpping multiplets from ppm. N,N-dillyl-4-fluorobenzenesulfonmide (1) ws prepred in 86% yield s yellow oil; protons d nd e pper s series of brod multiplets from nd ppm, respetively. N,N-dillyl-2,4- difluorobenzenesulfonmide (1d) ws prepred in 94% yield s yellow oil; proton d ppers s multiplet from ppm, nd protons e nd f pper s series of brod, overlpping multiplets from ppm. N,N-dillyl-3,5-30

44 difluorobenzenesulfonmide (1e) ws prepred in 93% yield s white powder; proton d ppers s series of brod multiplets from ppm respetively, while proton e ppers s triplet of triplets t 7.03 ppm due to oupling with two ortho-fluorines with equl oupling onstnts ( 3 J H-F = 8.47 Hz) nd two met-hydrogens with equl oupling onstnts ( 4 J H-H = 2.32 Hz). d e f d e/f * 1 d e d e d d/e * * e 1b 1 d e f d * e/f 1d d e d * e 1e Figure MHz NMR spetr (CDCl 3 ) of the romti region of 1-e. In the 13 C NMR spetrum of 1 (Figure 6), rbons, b,, d, e, f, nd g pper s singlets t 119.0, 132.5, 49.3, 140.4, 127.1, 129.1, nd ppm, respetively. Crbons b nd g pper t ppm, nd the two peks n be distinguished by the shielding ssoited with g. Crbon g experienes greter pull of eletrons from the pr-sulfone thn rbon b does from the ipso-ch 2 -N, resulting in g being slightly more upfield. 31

45 f b/g e b g d b/g f e e f b d g * b g Figure MHz DEPT 135 (top) nd 13 C NMR (bottom) spetrl overly (CDCl 3 ) of DABSA. The 13 C NMR spetr of 1-1e re presented in Figure 7. In the 13 C NMR spetrum of 1b, rbons d, e, nd g pper s singlets t 139.5, 128.7, nd ppm, respetively. Both rbons b nd f pper t ppm, nd the two peks n be distinguished by the shielding ssoited with f. Crbon f experienes greter pull of eletrons from the pr-sulfone thn rbon b does from the ipso-ch 2 -N, resulting in f being slightly more upfield. In the 13 C NMR spetrum of 1, rbons d t ( 4 J C-F = 3.29 Hz), e t ppm ( 3 J C-F = 9.30 Hz), f t ppm ( 2 J C-F = 22.5 Hz), nd g t ppm ( 1 J C-F = 254 Hz) ll pper s doublets. In the 13 C NMR spetrum of 1d, rbon d ppers s multiplet from ppm, rbon h ppers s triplet t ppm ( 2 J C-F = 25.7 Hz) due to splitting with two ortho fluorines. Crbon f ppers s doublet of doublets t ppm ( 2 J C-F = 3.81 Hz, 4 J C-F = 21.6 Hz) due to splitting with ortho- nd pr-fluorines. Crbon e ppers s doublet of doublets t ppm ( 3 J C-F 32

46 = 2.2 Hz, 3 J C-F = 10.2 Hz) due to splitting with two non-equivlent met-fluorines. Crbons g t ppm ( 1 J C-F = 13.5 Hz, 3 J C-F = 259 Hz) nd i t ppm ( 1 J C-F = 14.4 Hz, 3 J C-F = 260 Hz) both pper s doublets of doublets due to oupling with two nonequivlent fluorine toms. In the 13 C NMR spetrum of 1e, rbons d ppm ( 3 J C-F = 8.15 Hz), nd g t ppm ( 2 J C-F = 25.1 Hz) both pper s triplets t due to splitting with two equivlent fluorine toms. Crbons e t ppm ( 2 J C-F = 9.39 Hz, 4 J C-F = 18.3 Hz) nd f t ppm ( 1 J C-F = 11.6 Hz, 3 J C-F = 255 Hz) both pper s doublet of doublets due to splitting with two non-equivlent fluorine toms. b/g f d b f d e e g b e f e f d d g g * * 1 1b g b d e f e f d g * 1 g i e b d f h e f d i h g * 1d f d b e g e d f g * 1e Figure MHz 13 C NMR spetrl overly (CDCl 3 ) of DABSA derivtives Synthesis of N,N-diotylbenzenesulfonmide Derivtives Using 2,4-difluorobenzenesulfonyl hloride s strting mteril, N,N-diotyl- 2,4-difluorobenzenesulfonmide (DOtBSA-2,4-DF, 2) ws prepred by nuleophili substitution, s illustrted in Sheme 16. Commerilly vilble 2,4- difluorobenzenesulfonyl hloride ws llowed to ret t room temperture with triethyl 33

47 mine (TEA) for fifteen minutes, t whih point diotylmine ws dded nd llowed to ret for 3 hours, during whih time n exothermi retion ourred. GC/MS nlysis of n liquot onfirmed tht the strting mterils hd been onverted to the desired produt. After wshing with HCl/wter, hexnes, nd removing the DCM vi rotry evportion, the produt ws isolted to fford 2 s yellow oil in 86 % yield. DOtBSA- 2,4-DF DOtBSA- 3,5-DF Sheme 16. Syntheti route for DOtBSA derivtives. The struture ws onfirmed by 1 H, DEPT 135, nd 13 C NMR spetrosopy, GC/MS, nd elementl nlysis. Integrtion of the 1 H NMR spetrum onfirmed the struture of the monomer. The 1 H NMR spetrum (Figure 8) ontins six unique peks. The most upfield proton,, ppers s triplet t 0.89 ppm ( 3 J H-H = 6.81 Hz) due to oupling with two djent hydrogens with equivlent oupling onstnts. Protons -g pper s brod multiplet from ppm due to oupling with djent hydrogens. Protons b nd i pper s brod multiplets from ppm nd ppm, respetively. Protons i nd j pper s series of brod, overlpping multiplets from ppm. Synthesis of N,N-diotyl-3,5-difluorobenzenesulfonmide (DOtBSA-3,5-DF, 2b) ws rried out in n nlogous fshion, nd the mjor differenes between the 1 H nd 34

48 13 C NMR spetr re the speifi signls in the romti region, rising from the monomer used. Protons -h nd rbons -h pper in essentilly the sme positions in both of the monomers. Monomer 2b ws prepred in 76% yield s yellow oil; proton i ppers s multiplet from ppm, nd proton j ppers s triplet of triplets t 7.01 ppm due to oupling with two ortho-fluorines with equl oupling onstnts ( 3 J H-F = 8.50 Hz) nd two met-hydrogens with equl oupling onstnts ( 4 J H-H = 2.31 Hz) * b d e f g i j h k -g i j/k h b i b d f h e g i j j h b -g Figure 8. 1 H NMR spetrl overly (CDCl 3 ) of 2 (top) nd 2b (bottom). The DEPT 135 nd 13 C NMR spetr of 2 (Figure 9) ontin 10 nd 14 peks, respetively. Crbons t 13.9 ppm, b t 22.5 ppm, g t 26.5 ppm, f t 28.4 ppm, nd t 31.7 ppm pper s singlets. Protons d nd e pper s singlets t 29.1 ppm, with proton e shifted slightly more upfield due to shielding from the nitrogen. Crbon h ppers s doublet t 47.5 ppm (J C,F = 2.27 Hz) due to through-spe oupling with the fluorine ortho- to the sulfonmide. Crbon m ppers s triplet t ppm ( 2 J C-F = 25.8) due 35

49 to oupling with two similr fluorine toms. Crbons k t ppm ( 2 J C-F = 3.74 Hz, 4 J C- F = 21.6 Hz), i t ppm ( 2 J C-F = 3.90 Hz, 4 J C-F = 15.2 Hz), j t ppm ( 3 J C-F = 2.29 Hz, 3 J C-F = 10.2 Hz), n t ppm ( 1 J C-F = 12.5 Hz, 3 J C-F = 257 Hz), nd l t ppm ( 1 J C-F = 11.3 Hz, 3 J C-F = 256 Hz) eh pper s doublet of doublets due to oupling with two non-equivlent fluorine toms. h g l i j n h m k b d d e e f g h j i k l n m f g f b Figure MHz DEPT 135 (top) nd 13 C (bottom) NMR spetrl overly (CDCl 3 ) of 2. The DEPT 135 nd 13 C NMR spetr of 2b (Figure 10) ontin nine nd twelve unique peks, respetively. Crbons t 14.0 ppm, b t 22.6 ppm, t 31.7 ppm, d nd e t 29.1 ppm, f t 28.6 ppm, g t 26.7 ppm, nd h t 48.2 ppm pper s singlets. Crbons i t ppm ( 3 J C-F = 7.99 Hz) nd l t ppm ( 2 J C-F = 25.1 Hz) pper s triplets due to splitting with pr- nd ortho- fluorine, respetively. Crbons j t ppm ( 2 J C-F = 9.26 Hz, 4 J C-F = 18.2 Hz) nd k t ppm ( 1 J C-F = 11.6 Hz, 3 J C-F = 254 Hz) pper s doublets of doublets due to splitting with two non-equivlent fluorine toms. 36

50 j l h j i k l b d e f g j k h h i l f g d/e g f b b Figure MHz DEPT 135 (top) nd 13 C NMR (bottom) spetrl overly (CDCl 3 ) of 2b Sprtn Clultions The energy of monomers 1-e ws lulted in vuum using the Sprtn 10 omputtionl softwre pkge (Wvefuntion, In., Irvin, CA). The geometries were initilly optimized using the semiempiril method RM1, nd then further optimized using density funtionl theory t the B3LYP/6-31+G ** level. The energy of eh of the monomers ws reorded nd expressed s reltive energy with respet to the most stble speies of tht hrge. As shown in Tble 2, by inorporting the benzenesulfonmide moiety, the eletrostti hrge on the nitrogen beomes signifintly more positive; whih, s previously stted, redues the rte of degrdtive hin trnsfer, nd indites tht higher moleulr weight polymer n be formed. 37

51 DAA DABSA DABSA- 4-Br DABSA- 4-F Figure 11. Eletron density mpping of strting mterils. DABSA- 2,4-DF DABSA- 3,5-DF Tble 2. Clulted eletrostti hrges of dillylmine derivtives. Eletrostti Compound Chrge on Nitrogen Atom Dillylmine DABSA (1) DABSA-4-Br (1b) DABSA-4-F (1) DABSA-2,4-DF (1d) DABSA-3,5-DF (1e) The most negtive hrge on the nitrogen ws on dillylmine, while the most positive hrge on the nitrogen tom ws lulted on DABSA. The monomers ontining hlides (1b-e) hve slightly more negtive hrge thn does DABSA, whih 38

52 n be explined through eletron donting effets. Both fluorine nd bromine withdrw eletron density through indutive effets, but strongly donte ortho- nd pr- through resonne effets. The met-fluorines in DABSA-3,5-DF re eletron withdrwing through indutive effets on the rbon ipso- to the sulfonmide, resulting in derese in eletron density t tht position. However, the ontribution through resonne is muh greter thn the indutive effets, the two fluorine groups donte eletron density to the ortho- nd pr- positions through resonne, resulting in benzene ring tht is more eletron rih thn it is in monomers 1-d. As shown in Tble 3, these lultions lso orrelte with the differene in hemil shift of the llyl groups in the 13 C NMR spetr of the monomers Free Rdil Polymers Polymers p1-e were prepred vi the free rdil polymeriztion (FRP) of monomers 1-e, s outlined in Sheme 17. For eh of the retions, ommerilly vilble 2,2 -zobis(2-methylpropionitrile) (AIBN) or benzoyl peroxide (BPO) ws llowed to ret with the DABSA derivtive for pproximtely twenty-four hours. AIBN ws seleted s the inititor for FRP beuse the resulting polymers typilly hd higher yield nd greter therml stbility thn those prepred with BPO, s shown in Tble 4. 39

53 p1 1 1b 1 1d 1e Sheme 17. Generl outline of the FRP of DABSA derivtives. The polymers were preipitted from diethyl ether, entrifuged, wshed gin with diethyl ether, nd isolted s off-white solids by the removl of diethyl ether by denttion nd vuum. The strutures were onfirmed by 1 H NMR Spetrosopy, SEC, TGA, nd DSC, while the yliztion effiienies (CE) were determined by integrting the double bond proton peks reltive to the bkbone proton peks in the 1 H NMR spetrum (Figure 12) AIBN Initited Polymeriztion of DABSA Derivtives AIBN initited p1 ws prepred in 51% yield, with yliztion effiieny of 97.5%. Protons nd b pper s series of brod multiplets from ppm nd ppm, respetively (see Figure 12). Proton ppers s doublet t 3.83 ppm ( 3 J H-H = 5.90 Hz) due to oupling with n djent hydrogen tom. The derese in intensity of protons - indites suessful polymeriztion of 1, while the residul llyl peks indited tht 100% yliztion did not our. Protons n, nd o/p pper s brod singlets from nd ppm, respetively, nd protons d-m pper s brod series of multiplets from ppm, both of whih re typil in FRP. 40

54 AIBN initited FRP of the remining N,N-dillylbenzenesulfonmide derivtives were rried out in n nlogous fshion, nd the mjor differenes between the 1 H spetr (Figure 12) re the speifi signls in the romti region, rising from monomer used, with protons -m pper in essentilly the sme positions in eh of the polymers. AIBN initited p1b ws prepred in n 84% yield, with yliztion effiieny of 98.2%; protons n nd o pper s brod singlets from , whih is typil in FRP. AIBN initited p1 ws prepred in 63% yield, with yliztion effiieny of 97.9%; protons n nd o pper s brod singlets from nd ppm, respetively, whih is typil in FRP. AIBN initited p1d ws prepred in 67% yield, with yliztion effiieny of 99.3%; protons n nd o/p pper s brod multiplets from nd ppm, respetively, whih is typil in FRP. AIBN initited p1e ws prepred in 90% yield, with yliztion effiieny of 98.8%; protons n nd o pper s brod singlets from nd ppm, respetively, whih is typil in FRP. 41

55 n o/p n o p b l m k j i h g e f d b d-m p1 n/o n * o n o n o b b d-m d-m p1b p1 n * o/p n o p b d-m p1d n o n o b d-m p1e Figure MHz 1 H NMR spetrl overly (CDCl 3 ) of AIBN initited p1-e BPO Initited Polymeriztion of DABSA Derivtives Benzoyl peroxide (BPO) initited p1 ws prepred in 49% yield, with yliztion effiieny of 98.8%. Protons nd b pper s series of brod multiplets from ppm nd ppm, respetively (see Figure 13). Proton ppers s doublet t 3.83 ppm ( 3 J H-H = 5.90 ppm) due to oupling with n djent hydrogen. Protons n nd o/p pper s brod singlets from nd ppm, respetively, nd protons d-m pper s brod series of multiplets from ppm, both of whih re typil in FRP. The dditionl peks present in the romti region re ttributed to the phenyl ring in BPO. BPO initited FRP of the remining N,N-dillylbenzenesulfonmide derivtives were rried out in n nlogous fshion, nd the mjor differenes between the 1 H spetr (Figure 13) re the speifi signls in the romti region, rising from monomer 42

56 used, with protons -m ppering in essentilly the sme positions in eh of the polymers. BPO initited p1d ws prepred in 58% yield, with yliztion effiieny of 99.3%; protons n nd o/p pper s brod singlets from nd ppm, respetively, whih is typil in FRP. BPO initited p1e ws prepred in 56% yield, with yliztion effiieny of 98.8%; protons n nd o pper s brod singlets from nd ppm, respetively, whih is typil in FRP. n g o/p e f m l k j i h d * n o b * p b * d-m p1 n * o/p n * o p d-m p1d b n * o n o b d-m p1e * Figure MHz 1 H NMR spetrl overly (CDCl 3 ) of BPO initited p1, d, nd e ATRP nd ICAR ATRP Polymers ATRP of DABSA Derivtives The tom trnsfer rdil polymeriztion (ATRP) of 1-e ws onduted s outlined in Sheme 18. For eh of the retions, ommerilly vilble N,N,N,N,N - pentmethyldiethylenetrimine (PMDETA) or tris[2-(dimethylmino)ethyl]mine (Me 6 TREN) in xylenes ws dded to Shlenk tube ontining CuBr, ethyl-2-43

57 bromopropionte (EBrP), nd the pproprite DABSA derivtive, nd llowed to ret t 100 C for 48 hours. After 48 hours, the polymer ws nlyzed vi 1 H NMR nlysis, whih showed no onversion of monomer to polymer. ATRP owes its suess to the trnsition metl tlyst, in this se CuBr, nd nitrogen bsed lignd omplex. Beuse the monomers used re lso nitrogen bsed, they my be ting s n lterntive lignd for the opper enter, resulting in the ATRP being unsuessful. 1 b Sheme 18. ATRP of 1-e. d e ICAR ATRP of DABSA Derivtives The ICAR ATRP of 1-e ws onduted s outlined in Sheme 19. For eh of the retions, ommerilly vilble PMDETA or Me 6 TREN in xylenes ws dded to Shlenk tube ontining CuBr, EBrP, AIBN, nd the pproprite DABSA derivtive, nd llowed to ret t 100 C for 48 hours. After 48 hours, the polymer ws nlyzed vi 1 H NMR nlysis, whih showed no onversion of monomer to polymer. For resons tht were previously mentioned, ICAR ATRP ws unsuessful in polymerizing the monomers tht were used. 44

58 1 b Sheme 19. ICAR ATRP of 1-e RAFT of DABSA-2,4-DF d e The reversible ddition-frgmenttion hin trnsfer (RAFT) polymeriztion of DABSA-2,4-DF (1d) ws onduted s outlined in Sheme 20. For eh of the retions, ommerilly vilble ynomethyl methyl(phenyl) rbmodithiote (CMMPCDT) in xylenes ws dded to Shlenk tube ontining AIBN nd 1d nd llowed to ret t 100 C for 48 hours. After 48 hours, the polymer ws nlyzed vi 1 H NMR nlysis, whih showed little onversion of monomer to polymer. The retion ws llowed to ontinue for 7 dys, t whih point the polymer ws preipitted from diethyl ether to fford g (2%) of p2d. The polymer ws one gin nlyzed vi 1 H NMR spetrosopy nd GPC. Sheme 20. RAFT polymeriztion of 1d. 45

59 The 1 H NMR spetrum of RAFT polymeriztion of 1d is shown in Figure 14. The spetrum indites suessful polymeriztion of 1d, with yliztion effiieny of 94.5%. The derese in intensity of protons - indites the polymeriztion of 1d, while the residul llyl peks indite tht 100% yliztion did not our. Protons d nd e/f pper s brod singlets from ppm nd , respetively. Protons ', b', nd ' pper s brod series of multiplets from ppm. The brodening in the romti nd liphti region re both stereotypil in ylopolymeriztion. The dditionl peks present in the romti region re ttributed to the phenyl ring in CMMPCDT. b d e/f d e f b o n m l k j i h g d e f b g-o d e/f b Figure MHz 1 H NMR spetr of 1d (top) nd p2d (bottom) ADMET Polymers Polymers p3-e were prepred vi the yli diene metthesis (ADMET) polymeriztion of monomers 1-e, s outlined in Sheme 21. For eh of the retions, ommerilly vilble Hoveyd-Grubbs 2 nd genertion tlyst ws llowed to ret 46

60 with the pproprite DABSA derivtive t 70 ºC for pproximtely 48 hours. The retion ws rried out under redued pressure in order to remove the ethylene tht builds up in the retion, whih n result in the formtion of lower moleulr weight polymers (Sheme 6). The polymers were preipitted from diethyl ether, entrifuged, wshed gin with diethyl ether, nd isolted by the removl of diethyl ether vi denttion nd vuum to fford n off-white solid. The strutures were onfirmed by 1 H nd 13 C NMR spetrosopy, nd integrtion of the 1 H NMR spetrum onfirmed the orret number of hydrogens in the polymer. 1 p3 b d e Sheme 21. ADMET polymeriztion of monomers 1-e. Polymer p3 ws prepred in 52% yield. The 1 H NMR spetrum ontins six unique peks (see Figure 15). Both protons b (5.67 ppm) nd (4.15 ppm) pper s singlets. Peks nd b in the monomer 1 H NMR spetrum re onsolidted into single pek in the polymer 1 H NMR spetrum (b ), inditing the loss of ethylene, nd the suessful formtion of polymer. The lk of splitting in b nd indites tht the llyl groups hve been onverted to lkenes, nd ould be inditive of onformtionlly loked polymer struture (i.e. rbon-rbon double bond in the bkbone is either in isor trns- onformtion). As in the monomer spetrum, proton d ppers s multiplet 47

61 from , nd protons e nd f pper s series of brod, overlpping multiplets from ppm, inditing tht the phenyl ring ws unffeted by the polymeriztion. d e/f b * d b e f * ' b' ' d' e'/f' f' d' e' b' * Figure MHz 1 H NMR spetrl overly (CDCl 3 ) of 1 (top) nd p3 (bottom). ADMET polymeriztions of the remining N,N-dillylbenzenesulfonmide derivtives were rried out in n nlogous fshion, nd the mjor differenes between the 1 H spetr (see Figure 16) re the speifi signls in the romti region, rising from monomer used, with protons b nd ppering in essentilly the sme positions in eh of the polymers. Polymer p3b ws prepred in 54% yield; protons d nd e pper s series of brod, overlpping multiplets from ppm. Polymer p3 ws prepred in 50% yield; proton d nd e pper s series of brod multiplets from ppm nd ppm, respetively. Polymer p3d ws prepred in 40% yield; proton d ppers s series of brod multiplets from ppm, nd protons e /f pper s 48

62 series of brod, overlpping multiplets from ppm. Polymer p3e ws prepred in 58% yield; proton d ppers s series of brod multiplets from ppm, nd proton e ppers s triplet of triplets t 7.06 ppm due to oupling with two equivlent ortho-fluorine toms ( 2 J H-F = 2.34 Hz) nd two equivlent met-hydrogen toms ( 3 J H-H = 8.50 Hz). d' e'/f' * d' e' f' b' ' b' ' d'/e' d' * e' d' e' d' e' b' b' ' ' d' * e'/f' d' e' f' b' ' d' * e' d' e' b' ' Figure MHz 1 H NMR spetrl overly (CDCl 3 ) of ADMET polymers p3-e. The 13 C NMR spetrum of p3 (Figure 17) ontins six unique peks. Peks nd b in the monomer spetrum re onsolidted into single pek in the polymer spetrum (b ), inditing the loss of ethylene, nd the suessful formtion of polymer. Crbons b nd pper s singlets t nd 54.9 ppm, respetively. Crbons d t ppm, e t ppm, f t 129.1, nd g t lso pper s singlets, s they do in the 13 C NMR spetrum of 1, inditing tht the phenyl ring ws unffeted by the polymeriztion. 49

63 b b f e d e f d g g ' b' d' e' g' f' f' e' b' ' g' d' Figure MHz 13 C NMR spetr (CDCl 3 ) of 1 (top) nd p3 (bottom). The mjor differenes between the 13 C spetr (see Figure 18) re the speifi signls in the romti region, rising from monomer used, with rbons b nd ppering in essentilly the sme positions in eh of the polymers. In the 13 C NMR spetrum of p3b, rbons d, e, nd f pper s singlets t 136.4, 128.8, nd ppm, respetively. In the 13 C NMR spetrum of p3, rbon d ppers s singlet t ppm, rbon e ppers s doublet t ppm ( 3 J C-F = 9.28 Hz) due to oupling with met-fluorine tom, rbon f ppers s doublet t ppm ( 2 J C-F = 22.5 Hz) due to oupling with n ortho-fluorine tom, nd rbon g ppers s doublet t ppm ( 1 J C-F = 255 Hz) due to oupling with n ipso-fluorine tom. In the 13 C NMR spetrum of p3d, rbon d ppers s multiplet from ppm, nd rbons e t ppm ( 3 J C-F = 2.24, 3 J C-F = 10.3 Hz), f t ppm ( 2 J C-F = 3.81 Hz, 4 J C-F = 21.8 Hz), g t ppm ( 1 J C-F =11.4 Hz, 3 J C-F = 166 Hz) nd rbon i t ppm ( 1 J C-F = 12.7 Hz, 3 J C-F = 258 Hz) pper s doublets of doublets 50

64 due to oupling with two non-equivlent fluorine toms nd rbon h ppers s triplet t ppm ( 2 J C-F =25.7 Hz) due to oupling with two equivlent fluorine toms. In the 13 C NMR spetrum of p3e, rbons d t ppm ( 3 J C-F = 7.79 Hz) nd g t ppm ( 2 J C-F = 25.1 Hz) pper s triplets due to oupling with two equivlent fluorine toms, nd rbons e t ppm ( 2 J C-F = 9.36 Hz, 4 J C-F = 18.2 Hz) nd f t ppm ( 1 J C-F =11.64 Hz, 3 J C-F = 255 Hz) pper s doublets of doublets due to oupling with two non-equivlent fluorine toms. e' d' f' g' e' f' g' d' d' d' f' g' e' f' e' g' b' b' ' b' ' ' g' g' i' e' f' g' e' f' d' g' d' i' h' d' e' e' b' b' d' f' f' h' ' ' f' e' f' g' d' d' b' e' g' ' Figure MHz 13 C NMR spetrl overly (CDCl 3 ) of ADMET polymers p3-e S N Ar Copolymers Copolymers p4 nd p4b were prepred vi the S N Ar opolymeriztion of 1d/2 or 1e/2b in 95/5 rtio using 4,4 -dihydroxydiphenyl ether, s shown in Sheme 22. The regents were heted to 135 C in order to prevent rosslinking of the llyl groups. After 72 hours, DEPT C NMR spetrosopy showed no residul strting mteril, s indited by the bsene of the triplet present in the strting mteril. The struture of the 51

65 polymers were onfirmed by 1 H nd DEPT C NMR spetrosopy, nd the polymers were hrterized by GPC, TGA, nd DSC nlyses. 2 1d p4 2b 1e p4b Sheme 22. S N Ar opolymeriztion of 2/b nd 1d/e to form p4/b S N Ar Copolymeriztion of 1d nd 2 using 4,4 -dihydroxydiphenyl ether The 1 H NMR spetrum of p4 (Figure 19) ontins eleven distint peks. Protons nd b from , from ppm, i from ppm, j from ppm, l from ppm, nd p from ppm pper s series of brod multiplets. Protons d, e, f, g, nd h pper s singlet t 1.24 ppm, s does proton o t 7.28 ppm. Protons k t 5.17 ppm ( 3 J H-H = Hz), m t 3.96 ppm ( 3 J H-H = 6.01 Hz), nd n t 7.92 ppm ( 3 J H-H = 8.40 Hz) pper s doublets due to oupling with n djent proton. Due to oupling with both the ipso- proton, s well s n djent proton, proton k hs lrger oupling onstnt thn either m or n. Protons -l pper in essentilly the sme positions in p4b, with the mjor differenes being in the romti region. Protons nd b from , n from ppm, nd o from ppm pper s multiplets. 52

66 k m l /b n o p b j h i f g d e j o p n l m k i d-h o l k o /b n m b j h i f g d e n m l k j i * d-h Figure MHz 1 H NMR (CDCl 3 ) spetrl overly of p4 (top) nd p4b (bottom). In the DEPT C NMR spetrum of p4 (Figure 20), rbons, b,, nd d pper s singlets t 132.9, 120.2, nd ppm, respetively. Crbons e nd f ppers s doublet t ppm ( 2 J C-O = 8.15 Hz) beuse of the differene in hemil shift ssoited with oupling with n ortho- nd pr- sulfonmide. In the DEPT C spetrum of p4b (Figure 21), rbons, b,, nd d/e pper s singlets t 136.0, 110.0, 110.7, nd ppm, respetively. 53

67 54 Figure MHz DEPT C NMR (CDCl 3 ) spetrl overly of 1d (top) nd p4 (bottom). Figure MHz DEPT C NMR (CDCl 3 ) spetrl overly of 1e (top) nd p4b (bottom). b d b d b d e b d e/f f b b b d b d/e e

68 3.4. Polymer Moleulr Weights nd Therml Properties The polymers were further nlyzed using gel permetion hromtogrphy (GPC), differentil snning lorimetry (DSC), nd thermogrvimetri nlysis (TGA). Chrteriztion dt, inluding number nd weight verge moleulr weight (M n nd M w, respetively), dispersity (Đ), yliztion effiieny (CE), glss trnsition temperture (T g ), melting temperture (T m ), nd the 5% weight loss (T d-5% ) re summrized in Tbles 3-7. GPC ws used to determine moleulr weight nd moleulr weight distributions of polymers soluble in THF/5% eti id. The Đ nd M w were determined using the refrtive index (RI) nd light-sttering detetors. For the free rdil polymers, the M w ws found to be from 1,421 to 5,079 g/mol, with Đ vlues rnging from In both the AIBN nd BPO initited polymers, N,N-dillyl-3,5-difluorobenzenesulfonmide (1e) fforded the highest M w polymers, wheres N,N-dillylbenzenesulfonmide (1) fforded the lowest. By ompring the lulted eletrostti hrge nd differenes in hemil shift between the terminl nd penultimte llyl rbons, the differene in moleulr weight n be explined. Although the lulted hrge on the nitrogen is more negtive for 1e thn it is on 1-d, the tul hemil shifts explin the differene in moleulr weight. As previously stted, Mthis et l. showed tht the smller the differene in hemil shift in the llyl groups, the lower the propensity for hin trnsfer vi hydrogen bstrtion from the llyl position, resulting in n inrese in moleulr weight of the resulting polymer. 55

69 Tble 3. Differenes in hemil shift nd moleulr weights of free rdil polymers. Δδ (ppm) Eletrostti Chrge p p1b p p1d p1e M w Inititor M n Yield CE Đ (g/mol) (g/mol) (%) (%) AIBN 700 1, BPO 1,128 2, AIBN 820 2, BPO AIBN 994 2, BPO AIBN 1,497 3, BPO 1,209 2, AIBN 1,325 4, BPO 1,630 5, The therml stbility of the polymers, reported s 5% deomposition temperture (T d-5% ) under nitrogen ws investigted using thermogrvimetri nlysis (TGA), while the glss trnsition tempertures (T g ) were determined using differentil snning lorimetry (DSC). Overlys of the therml nlyses of AIBN nd BPO initited polymers re shown in Figures The glss trnsition tempertures (T g ) rnged from 86 C for BPO initited DABSA (see Figure 22) to 114 C for AIBN initited DABSA-4-Br (see Figure 24). The higher T g n be ttributed to more rigid polymer bkbone. The free rdil polymers showed moderte therml stbility bove 290 C for AIBN initited polymers (see Figure 23), nd 262 C for BPO initited polymers (see Figure 25) under nitrogen tmosphere. For AIBN initited polymers, the T d-5% for the first degrdtion step rnged from 290 C for p1 to 305 C for p1d, while the BPO initited polymers rnged from 262 C for p1 to 302 C for p1d. 56

70 Tble 4. Therml dt for free rdil polymers. p1 p1b p1 p1d p1e T g T d-5% Inititor ( C) ( C) AIBN BPO AIBN BPO - - AIBN BPO - - AIBN BPO AIBN BPO Figure 22. DSC results of AIBN initited DABSA derivtives. 57

71 Figure 23. TGA results of AIBN initited DABSA derivtives. Figure 24. DSC results of BPO initited DABSA derivtives. 58

72 Figure 25. TGA results of BPO initited DABSA derivtives. For the RAFT polymer of DABSA-2,4-DF, the M w ws found to be 1,154 g/mol, with dispersity of The low moleulr weight my be ttributed to the seletion of RAFT trnsfer gent (RTA), by seleting n lterntive RTA suh s 2- (dodeylthiorbonothioylthio)-2-methylpropioni id, whih is well suited for the RAFT polymeriztion of rylmides. Tble 5. Moleulr weight of RAFT polymer p2d. DABSA- 2,4-DF M n (g/mol) M w (g/mol) Đ 786 1, For the ADMET polymers, the M w ws found to be from 10,150 to 30,229 g/mol, with Đ vlues rnging from N,N-dillylbenzenesulfonmide (1) fforded the highest M w polymers, wheres N,N-dillyl-2,4-difluorobenzenesulfonmide (1d) fforded the lowest. Due to the ortho- nd pr- fluorine toms in monomer 1d, the struture is 59

73 symmetri. This ould limit the bility of the tlyst to onvert monomer to polymer, resulting in the derese in moleulr weight. Tble 6. Moleulr weights nd therml properties of ADMET polymers. M n M w T Đ m T d-5% (g/mol) (g/mol) ( C) ( C) DABSA 14,915 30, DABSA- 4-Br 8,692 14, DABSA- 4-F 17,075 28, DABSA- 2,4-DF 5,547 10, DABSA- 3,5-DF 10,210 13, Melting tempertures (T m ) were determined using differentil snning lorimetry (DSC), nd re shown in (Figure 26). The melting temperture (T m ) of the ADMET polymers rnged from 65.5 C for p3d to 136 C p3b. The lower T m ssoited with p3d is, s previously stted, due to steri effets ssoited with monomer 1d. The ADMET polymers showed low therml stbility bove 125 C for under nitrogen tmosphere. The T d-5% for the first degrdtion step rnged from 125 C for 1e to 171 C for 1d. As shown in Figure 27, the differene in degrdtion temperture between 1 nd p3 is miniml (152 nd 157 C, respetively), whih n be explined through the struture of the polymer. The similrity of the polymer struture to tht of the monomer (see Sheme 21) results in the degrdtion of the polymer being only slightly higher thn the monomer. The TGA thermogrm of ADMET polymers under nitrogen tmosphere is shown in Figure

74 Figure 26. DSC results of ADMET polymers. Figure 27. TGA results of 1 nd p3. 61

75 Figure 28. TGA results of ADMET Polymers. As shown in Tble 7, the M w of the S N Ar opolymers were 7,440 g/mol for p4b nd 9,530 g/mol for p4, with Đ vlues rnging from Tble 7. Moleulr weights nd therml properties of S N Ar polymers. Polymer Monomer M Rtio n M w T Đ g T d-5% Components (g/mol) (g/mol) ( C) ( C) p4 2:1d 95:5 3,660 9, p4b 2b:1e 95:5 3,050 7, Glss trnsition tempertures (T g ) were determined using differentil snning lorimetry (DSC) nd overlys of S N Ar opolymers re shown in Figure 29. The glss trnsition tempertures (T g ) were 70.3 C for p4b nd 96.3 C for p4. The higher T g n be ttributed to more rigid polymer bkbone, resulting from the inorportion of greter mount of monomer into the polymer. 62

76 Figure 29. DSC results of S N Ar opolymers. The S N Ar opolymers showed moderte therml stbility bove 329 C under nitrogen tmosphere. The T d-5% for the first degrdtion step rnged from 329 C for p4b to 354 C for p4. The TGA thermogrm of S N Ar opolymers under nitrogen tmosphere is shown in Figure

77 Figure 30. TGA results of S N Ar opolymers. 64