Appendix A SYNTHESIS AND CHARACTERIZATION OF SIDE-GROUP LIQUID CRYSTAL POLYMERS

Transcription

1 191 Appenix A SYNTHESIS AND CHARACTERIZATIN F SIDE-GRUP LIQUID CRYSTAL PLYMERS Appenix A A.1 Appenix A.2 Tles A.3 Shemes...23 A.4 Figures...25 A.5 Referenes...23 A.1 Appenix All regents were purhse n use s reeive from Alrih, unless otherwise note. A.1.1 Strtegy for Synthesis of e-group Liqui Crystl Polymers Polymer-nlogous synthesis is use to tth liqui rystlline sie-groups to existing polymer kones. A lirry of polyutiene (PB) homopolymers (Figure A.1-Figure A.3) n PB-ontining lok opolymers (Figure A.4-Figure A.12) ws otine from vrious soures. The PB portion of every polymer ontins high perentge (> 8 mol %) of 1,2-ition monomers. A ynoiphenyl-se mesogen is synthesize seprtely n tthe in one step to the pennt vinyl groups of 1,2-PB, yieling sie-group liqui rystl polymer (SGLCP). A.1.2 Synthesis of Cynoiphenyl-Bse Mesogeni e Groups A ynoiphenyl-se mesogen is synthesize y Mitsunou retion [1, 2] etween 4- yno-4 -hyroxyiphenyl (CHB) n 3-uten-1-ol (4H) (Sheme A.1). CHB (1.3 g, 6.2

2 192 mmol, purhse n use s reeive from TCI Ameri) n 1.1 equivlents eh of 4H (.6 ml, 6.8 mmol) n triphenylphosphine (TPP) (1.8 g, 6.8 mmol) re issolve together in 5 ml nhyrous tetrhyrofurn (THF). The solution is hille in n ie wter th followe y the ropwise ition of 1.1 equivlents of iisopropyl zoiroxylte (DIAD) (1.3 ml, 6.8 mmol). The retion flsk is then remove from the ie wter th n the retion proees t room temperture until thin-lyer hromtogrphy no longer revels the presene of CHB (pproximtely 3-5 hours). Upon ompletion, the THF is evporte n the prout, 4-yno-4 -(3-utenoxy)-iphenyl (CBV4), is issolve in ihloromethne (DCM) n purifie on sili gel olumn using 5% ethyl ette in hexne s the moile phse. CBV4 is further purifie y rerystlliztion from hexne, hieving 77% yiel overll (1.2 g, 4.7 mmol). The phenoli Mitsunou retion (Sheme A.1) is the preferre sheme for synthesizing CBV4 euse reltively high yiel is hieve in single retion. However, n lternte [3, 4] sheme is Willimson ether synthesis (Sheme A.2). 4H (1. ml, 12 mmol) is first onverte to 3-utenyl-1-tosylte (4Ts) y retion with two equivlents of p- toluenesulfonyl hlorie (tosyl hlorie, TsCl) (44 g, 23 mmol) in 15 ml DCM long [5, 6] with one equivlent of pyriine (9.4 ml, 12 mmol). Regents re mixe t C then the retion flsk is remove to room temperture n the retion proees for pproximtely ten hours. The prout, 4Ts, is purifie y liqui-liqui extrtion. After ing n exess of pyriine (1 ml), the DCM solution is wshe with 4 ml of queous hyrohlori i (5% HCl). 4Ts remining in the queous lyer is extrte with DCM then the omine orgni lyers re wshe one more with 5% HCl. The orgni lyer is rie with nhyrous soium sulfte n the DCM evporte to reover the prout (83% yiel, 22 g, 96 mmol). Willimson ether synthesis yiels the finl prout, CBV4. A seventy perent exess of 4Ts (22 g, 96 mmol) is e to solution of CHB (11 g, 57 mmol) in 5 ml of N,N-imethylformmie (DMF). A seventy perent exess of nhyrous potssium ronte is e (13 g, 96 mmol) n the mixture hete t 9 C for eight hours. Upon ompletion, the potssium tosylte yprout is preipitte with n exess of DCM n remove y filtrtion. After evporting the mjority of the solvent the remining CBV4 is purifie on sili gel olumn using ten perent ethyl

3 193 ette in hexne, then rerystllize from hexne for n overll yiel of 43% (6.1 g, 25 mmol). A siloxne linking group is tthe to the ynoiphenyl mesogen, CBV4, y hyrosilyltion (Sheme A.3). A tenfol exess of 1,1,3,3-tetrmethylisiloxne (TMDS) (18 ml, 99 mmol) is issolve together with CBV4 (2.5 g, 9.9 mmol) in 2 ml nhyrous toluene. A rop of pltinum tlyst (PC72 pltinum ivinyl omplex in xylene, Unite Chemil Tehnologies, Bristol, PA) is e n the mixture is stirre t room temperture for 16 hours uner inert gs. Upon ompletion, the solvent n exess TMDS re evporte t 8 C uner vuum n the prout, 4-yno-4 -(5-(1,1,3,3,- tetrmethylisiloxne)utoxy)iphenyl (CB4), is purifie y olumn hromtogrphy. An nhyrous hromtogrphy olumn is prepre in orer to prevent the egrtion of CB4 y retion with wter. The olumn is fille with sili gel rie in 15 C oven n then repetely flme with propne torh while ry, inert gs flows through the sili. The olumn is then fille with nhyrous hexne n mixe to rete slurry of sili gel in hexne. ne the sili gel settles, the CB4 is loe onto the olumn n elute with n nhyrous mixture of 1% ethyl ette in hexne. Anhyrous olumn hromtogrphy is sometimes repete to reover ler, liqui prout (75% yiel, 2.1 g, 7.4 mmol). A.1.3 Atthing e Groups to Polymer The ynoiphenyl-se mesogen with tthe siloxne linking group (CB4) is suitle for tthment to the pennt vinyl groups of 1,2-polyutiene polymer y pltinum-tlyze hyrosilyltion (Sheme A.4) in mnner similr to the synthesis of CB4. 1,2-Polyutiene (.14 g, 2.5 mmol) is issolve in 5 ml of nhyrous tetrhyrofurn (THF) in inert tmosphere. A threefol exess of freshly purifie CB4 (2.1 g, 7.4 mmol) is e long with rop of pltinum tlyst (PC85 pltinum ylovinyl omplex in vinylmehtylsiloxnes, Unite Chemil Tehnologies, Bristol, PA) n the mixture hete t 5 C for etween four n seven ys. Retion progress is monitore perioilly y proton NMR. When the retion is omplete, s eviene y

4 194 the ispperne of the 1,2-PB vinyl resonne pek t δ = 4.9, it is quenhe y heting t 5 C overnight fter ition of exess styrene (~2-5 ml). After quenhing with styrene the polymer is onentrte y evporting pproximtely hlf the solvent uner vuum. Unrete mesogen is remove y preipitting the polymer from solution using n exess of methnol. The preipitte polymer is then repetely issolve in THF n preipitte with methnol. The methnol use for preipittion ontins 1 of ril inhiitor (BHT) to improve stility uring longterm storge. After the finl preipittion the soli polymer is rie in vuum. Polymer onversion is nerly quntittive; yiel is greter thn 95% of the theoretil vlue. Cross-linking retions re seemingly unvoile; polymers lmost lwys hve imol moleulr weight istriution with smll frtion of high moleulr weight, ross-linke polymers, whih is remove y solvent frtiontion. A solution of pproximtely ten perent polymer in THF is psse through.45 µm syringe filter then ilute with toluene n THF for finl omposition of.5% polymer issolve in mixture of 6% THF n 4% toluene. While stirring vigorously, methnol is e until the solution eomes louy (the mount of methnol require is typilly lmost equl to the volume of the solution). THF is then slowly e until the solution eomes ler; t this point it is very ner its room-temperture lou point. Next, smll mount of methnol is e, usully etween 5 n 15 ml. The mount of methnol e etermines the egree to whih the polymer will frtionte: more methnol will result in more polymer ropping out of solution. The louy solution is hete to 7 C n stirre until it eomes ler gin. Finlly, the ler, hot solution is poure into hot seprtory funnel wrppe in plenty of insultion. The insulte funnel is isolte from ir urrents n left to ool very slowly overnight. A visous syrup ompose lrgely of high moleulr weight polymer seprtes into the ottom of the seprtory funnel while low moleulr weight polymer remins in the ilute solution ove. The high moleulr weight frtion is esily rine off, preipitte with methnol, n rie in vuum. The low moleulr weight frtion is reovere y evporting the solvent n rying in vuum.

5 195 A.1.4 Chrteriztion of Polyutiene-Contining Prepolymers The moleulr weight of the SGLCP preursor polymers is mesure y the mnufturer using light sttering. Proton NMR is use to mesure the perentge of 1,2-PB monomers n to verify the mss frtion of PB in lok opolymers (Figure A.1-Figure A.12). A 3 MHz Vrin NMR spetrometer is use to ollet proton NMR spetr from solutions of polymers in euterte hloroform (CDCl 3 ). Hyrogen toms in the vinyl group of 1,2- utiene ontriute to the intensities of peks t δ = 4.9 (two hyrogens) n δ = 5.4 (one hyrogen). The two hyrogen toms tthe to the oule-one rons of 1,4-utiene ontriute to the pek intensity t δ = 5.4. The 1,2-utiene ontent is lulte from these pek intensities: x 1,2 = I δ =4.9 / (I δ =4.9 + I δ =5.4 - ½ I δ =4.9 ). The mole frtion of PB in PB-polystyrene (PS) lok opolymer is ompute y ompring the intensity per mole of hyrogen of PB peks (oth 1,4- n 1,2- ition) to tht of romti peks in the rnge of δ = The mole frtion is esily onverte to the mss frtion using the monomers molr msses. The polymers moleulr weight istriutions, hrterize y the polyispersity inex (PDI = M w / M n ), is mesure using gel permetion hromtogrphy (GPC) (Figure A.1- Figure A.12). A ilute solution of the polymer in THF is elute through four gel olumns (Polymer Lortories PLgel 1 µm nlytil olumns, 3 m long) using THF flowing t rte of.9 ml/min n is etete t the outlet y Wters 41 ifferentil refrtometer. The hromtogrph is lirte with monoisperse PS stnrs n the PDI is lulte using the Millenium softwre from Wters. The totl time to trverse ll four olumns is pproximtely 45 minutes. In some ses (when the GPC tre only goes from zero to 3 minutes) only two olumns were use. Prepolymer properties re summrize in Tle A.1-Tle A.4. NMR n GPC t from prepolymers re presente in Figure A.1-Figure A.12. A.1.5 Chrteriztion of e-group Liqui Crystl Polymers The egree of onversion (perentge of rete 1,2-PB monomers) of SGLCPs is mesure y proton NMR (Figure A.13-Figure A.25). Just s ws the se in the

6 196 prepolymer, the mole frtion of unrete 1,2-utiene monomers is quntifie y the intensity of the pek t δ = 4.9. Using the pek t δ = 3.9 (two lkyl hyrogens jent to the ynoiphenyl ore) s onvenient mesure of the mesogeni sie groups, the egree of onversion is the rtio of this pek intensity to tht of 1,2 PB: x LC = I δ =3.9 / (I δ =4.9 + I δ =3.9 ). The mole frtion of unretive 1,4-PB n the moleulr weight of the oil lok(s) is ssume to e the sme s in the prepolymer. The moleulr weight of SGLCP lok is lulte using the mesure omposition n the known moleulr weight of polyutiene in the prepolymer. Polyispersity of the SGLCPs is mesure y GPC, just like the prepolymer (Figure A.13-Figure A.25). SGLCP properties re summrize in Tle A.5-Tle A.8. NMR n GPC t from SGLCPs re presente in Figure A.13-Figure A.25.

7 197 A.2 Tles Tle A.1 Moleulr weight, omposition, n polyispersity of 1,2-polyutiene prepolymers use to synthesize sie-group liqui rystlline homopolymers in Tle A.5. See Figure A.1-Figure A.3 for t use to lulte n omposition of the PB lok n polyispersity. Nme M n [kg/mol] Mole Frtion 1,2 PB Mole Frtion 1,4 PB PDI 5H H H PDI = Polyispersity Inex (M w /M n ) Informtion provie y the supplier, Polymer Soure (Montrel, Quee) Polymer synthesize y Steven Smith (Protor n Gmle, In.), M n inepenently mesure y Mihel Kempe using multi-ngle lser light sttering [4]

8 Tle A.2 Moleulr weight, omposition, n polyispersity of poly[styrene--1,2- utiene] ilok prepolymers use to synthesize PS-SGLCP ilok opolymers in Tle A.6. See Figure A.4-Figure A.1 for t use to lulte n omposition of the PB lok n polyispersity. 198 PS Blok PB Blok Nme M n [kg/mol] M n [kg/mol] Mole Frtion 1,2 PB Mole Frtion 1,4 PB PDI 3(6)AB (7)AB (19)AB (4)AB (6)AB (8)AB (12)AB PDI = Polyispersity Inex (M w /M n ) Informtion provie y the supplier, Polymer Soure (Montrel, Quee) Informtion provie y the supplier, Dvi Uhrig (Center for Nnophse Mterils enes, k Rige Ntionl Lortory)

9 Tle A.3 Moleulr weight, omposition, n polyispersity of poly[styrene--1,2- utiene--styrene] trilok prepolymer use to synthesize the PS-SGLCP-PS trilok opolymer in Tle A.7. See Figure A.11 for t use to lulte n omposition of the PB lok n polyispersity. 199 PS Bloks PB Blok Nme M n [kg/mol] M n [kg/mol] Mole Frtion 1,2 PB Mole Frtion 1,4 PB PDI (6)15(7)ABA 57, PDI = Polyispersity Inex (M w /M n ) Polymer purhse from Polymer Soure (Montrel, Quee), M n inepenently mesure y Mihel Kempe using multi-ngle lser light sttering [4] Tle A.4 Moleulr weight, omposition, n polyispersity of poly[(methyl methrylte)--1,2-utiene] ilok prepolymer use to synthesize the PMMA- SGLCP ilok opolymer in Tle A.8. See Figure A.12 for t use to lulte n omposition of the PB lok n polyispersity. PMMA Blok PB Blok Nme M n [kg/mol] M n [kg/mol] Mole Frtion 1,2 PB Mole Frtion 1,4 PB PDI 14(7)BMMA PDI = Polyispersity Inex (M w /M n ) Informtion provie y the supplier, Polymer Soure (Montrel, Quee)

10 Tle A.5 Moleulr weight, omposition, n polyispersity of the sie-group liqui rystl homopolymers synthesize from prepolymers in Tle A.1. See Figure A.4- Figure A.1 n Figure A.17-Figure A.23 for t use to lulte omposition, polyispersity, n the moleulr weight of the SGLCP lok. 2 Nme M n [kg/mol] Mole Frtion 1,2 PB Mole Frtion 1,4 PB Mole Frtion LC PDI 35HCB HCB HCB HCB PDI = Polyispersity Inex (M w /M n )

11 21 Tle A.6 Moleulr weight, omposition, n polyispersity of the sie-group liqui rystl ilok opolymers with oil lok ompose of polystyrene (PS), synthesize from prepolymers in Tle A.2. See Figure A.4-Figure A.1 n Figure A.17-Figure A.23 for t use to lulte omposition, polyispersity, n the moleulr weight of the SGLCP lok. Nme PS Blok M n [kg/mol] M n [kg/mol] SGLCP Blok Mole Frtion 1,2 PB Mole Frtion 1,4 PB Mole Frtion LC PDI 21(6)ABCB (7)ABCB (19)ABCB (4)ABCB (6)ABCB (8)ABCB (12)ABCB PDI = Polyispersity Inex (M w /M n )

12 Tle A.7 Moleulr weight, omposition, n polyispersity of the sie-group liqui rystl trilok opolymer with polystyrene enloks, synthesize from the prepolymer in Tle A.3. See Figure A.11 n Figure A.24 for t use to lulte omposition, polyispersity, n the moleulr weight of the SGLCP lok. 22 Nme PS Bloks M n [kg/mol] M n [kg/mol] SGLCP Blok Mole Frtion 1,2 PB Mole Frtion 1,4 PB Mole Frtion LC PDI 11ABACB4 57,67 1, PDI = Polyispersity Inex (M w /M n ) Tle A.8 Moleulr weight, omposition, n polyispersity of the sie-group liqui rystl ilok opolymer with oil lok ompose of poly(methyl methrylte) (PMMA), synthesize from the prepolymer in Tle A.4. See Figure A.12 n Figure A.25 for t use to lulte omposition, polyispersity, n the moleulr weight of the SGLCP lok. Nme PMMA Blok M n [kg/mol] M n [kg/mol] SGLCP Blok Mole Frtion 1,2 PB Mole Frtion 1,4 PB Mole Frtion LC PDI 95(7)BMMACB PDI = Polyispersity Inex (M w /M n )

13 23 A.3 Shemes N C H + H 1.1 eq. PPh3 1.1 eq. DIAD THF, 3-5 h R.T. CHB 4H CBV4 N C Sheme A.1 Synthesis of 4-yno-4 -(3-utenoxy)-iphenyl (CBV4) y Mitsunou retion etween 4-yno-4 -hyroxyiphenyl (CHB) n 3-uten-1-ol (4H) using iisopropyl zoiroxylte (DIAD) n triphenylphosphine (TPP) in tetrhyrofurn (THF) t room temperture H + 2 Cl S CH 3 1 eq. Pyriine DCM, 1 h R.T. S CH 3 4H TsCl 4Ts S CH 3 + N C H 1.7 eq. K2C3 DMF, 8 h 9 C N C 4Ts CHB CBV4 Sheme A.2 Synthesis of 4-yno-4 -(3-utenoxy)-iphenyl (CBV4) y Willimson ether synthesis. 3-uten-1-ol (4H) is first onverte to 3-utenyl-1-tosylte (4Ts) y retion with p-toluenesulfonyl hlorie (TsCl) n is susequently rete with 4-yno- 4 -hyroxyiphenyl (CHB) to yiel the finl prout.

14 H 24 N C + H H Pt Toluene, 16 h R.T. CBV4 TMDS C N CB4 Sheme A.3 Synthesis of 4-yno-4 -(5-(1,1,3,3,-tetrmethylisiloxne)utoxy)iphenyl (CB4) y pltinum-tlyze hyrosilyltion H + Pt THF, 4-7 ys 5 C 1,2 PB C N CB4 C N HCB4 Sheme A.4 Atthment of CB4 to 1,2-polyutiene monomer y pltinumtlyze hyrosilyltion

15 25 A.4 Figures 3 PDI = 1.6 5H , Figure A.1 3 MHz proton NMR spetrum of 5H, 1,2-polyutiene homopolymer with M n = 47.5 kg/mol, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.1. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

16 PDI = H , Figure A.2 3 MHz proton NMR spetrum of 6H, 1,2-polyutiene homopolymer with M n = 63 kg/mol, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.1. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

17 PDI = H, Figure A.3 3 MHz proton NMR spetrum of 1H, 1,2-polyutiene homopolymer with M n = 14 kg/mol, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.1. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

18 PDI = (6)AB e f e,f , Figure A.4 3 MHz proton NMR spetrum of 3(6)AB, poly[styrene--1,2- utiene] lok opolymer with M PS = 63.5 kg/mol n M PB = 33 kg/mol, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.2. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

19 PDI = (7)AB e f e,f , Figure A.5 3 MHz proton NMR spetrum of 1(7)AB, poly[styrene--1,2- utiene] lok opolymer with M PS = 7 kg/mol n M PB = 97 kg/mol, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.2. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

20 PDI = (19)AB e f e,f , Figure A.6 3 MHz proton NMR spetrum of 1(19)AB, poly[styrene--1,2- utiene] lok opolymer with M PS = 191 kg/mol n M PB = 97 kg/mol, in CDCl3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.2. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

21 PDI = (4)AB e f e,f.54.31, Figure A.7 3 MHz proton NMR spetrum of 6(4)AB, poly[styrene--1,2- utiene] lok opolymer with M PS = 43 kg/mol n M PB = 59 kg/mol, in CDCl3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.2. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

22 PDI = 1.8 6(6)AB e f e,f.9.62, Figure A.8 3 MHz proton NMR spetrum of 6(6)AB, poly[styrene--1,2- utiene] lok opolymer with M PS = 59 kg/mol n M PB = 57 kg/mol, in CDCl3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.2. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

23 213 9 PDI = (8)AB e f e,f , Figure A.9 3 MHz proton NMR spetrum of 6(8)AB, poly[styrene--1,2- utiene] lok opolymer with M PS = 83 kg/mol n M PB = 57 kg/mol, in CDCl3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.2. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

24 PDI = (12)AB e f e,f , Figure A.1 3 MHz proton NMR spetrum of 5(12)AB, poly[styrene--1,2- utiene] lok opolymer with M PS = 121 kg/mol n M PB = 5 kg/mol, in CDCl3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.2. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

25 PDI = 1.43 e' ' f' (6)15(7)ABA f e e,e',f,f'.97,'.5, Figure A.11 3 MHz proton NMR spetrum of (6)15(7)ABA, poly[styrene--1,2- utiene--styrene] trilok opolymer with M PS = 57 n 67 kg/mol n M PB = 146 kg/mol, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.3. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

26 PDI = (7)BMMA , Figure A.12 3 MHz proton NMR spetrum of 14(7)BMMA, poly[(methyl methrylte)--1,2-utiene] lok opolymer with M PMMA = 68 kg/mol n M PB = 142 kg/mol, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition reporte in Tle A.4. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

27 PDI = HCB ,.11 2x C N Figure A.13 3 MHz proton NMR spetrum of 35HCB4, n SGLCP homopolymer synthesize from 5H, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight reporte in Tle A.5. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

28 PDI = HCB D D, C N Figure A.14 3 MHz proton NMR spetrum of 2 35HCB4, euterium-lele SGLCP homopolymer synthesize from 5H, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight reporte in Tle A.5. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

29 Figure A.15 3 MHz proton NMR spetrum of 49HCB4, n SGLCP homopolymer synthesize from 6H, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight reporte in Tle A.5. The GPC hromtogrph use to mesure polyispersity is shown in the inset. The reltive intensity of pek my e nomlously high ue to inomplete removl of unrete mesogen in this prtiulr smple. 219

30 PDI = HCB , C N Figure A.16 3 MHz proton NMR spetrum of 76HCB4, n SGLCP homopolymer synthesize from 1H, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight reporte in Tle A.5. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

31 Figure A.17 3 MHz proton NMR spetrum of 21(6)ABCB4, PS-SGLCP ilok opolymer synthesize from 3(6)AB, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.6. The GPC hromtogrph use to mesure polyispersity is shown in the inset. 221

32 Figure A.18 3 MHz proton NMR spetrum of 7(7)ABCB4, PS-SGLCP ilok opolymer synthesize from 1(7)AB, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.6. The GPC hromtogrph use to mesure polyispersity is shown in the inset. The reltive intensity of pek my e nomlously high n the presene of pek t δ = 3.85 my e ue to inomplete removl of unrete mesogen in this prtiulr smple. 222

33 Figure A.19 3 MHz proton NMR spetrum of 58(19)ABCB4, PS-SGLCP ilok opolymer synthesize from 1(19)AB, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.6. The GPC hromtogrph use to mesure polyispersity is shown in the inset. 223

34 PDI = (4)ABCB4 1. C N, 2 x Figure A.2 3 MHz proton NMR spetrum of 47(4)ABCB4, PS-SGLCP ilok opolymer synthesize from 6(4)AB, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.6. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

35 PDI = (6)ABCB4, C N Figure A.21 3 MHz proton NMR spetrum of 39(6)ABCB4, PS-SGLCP ilok opolymer synthesize from 6(6)AB, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.6. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

36 PDI = (8)ABCB4, C N Figure A.22 3 MHz proton NMR spetrum of 42(8)ABCB4, PS-SGLCP ilok opolymer synthesize from 6(8)AB, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.6. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

37 PDI = (12)ABCB , C N Figure A.23 3 MHz proton NMR spetrum of 32(12)ABCB4, PS-SGLCP ilok opolymer synthesize from 5(12)AB, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.6. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

38 PDI = ABACB C N, Figure A.24 3 MHz proton NMR spetrum of 11ABACB4, PS-SGLCP-PS trilok opolymer synthesize from (6)15(7)ABA, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.7. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

39 PDI = (7)BMMACB C N, Figure A.25 3 MHz proton NMR spetrum of 95(7)BMMACB4, PMMA- SGLCP ilok opolymer synthesize from 14(7)BMMA, in CDCl 3. Pek lels inlue the reltive intensity (integrte re) n their ssignments. This t ws use to lulte the polymer omposition n moleulr weight of the SGLCP lok reporte in Tle A.8. The GPC hromtogrph use to mesure polyispersity is shown in the inset.

40 23 A.5 Referenes [1] Lepore, S. D.; He, Y. Use of Sonition for the Coupling of Sterilly Hinere Sustrtes in the Phenoli Mitsunou Retion. J. rg. Chem. 23, 68, [2] Mitsunou,. The Use of Diethyl Azoiroxylte n Triphenylphosphine in Synthesis n Trnsformtion of Nturl Prouts. Synthesis 1981, 1, [3] Kempe, M. D.; Veruzo, R.; Sruggs, N. R.; Kornfiel, J. A. Rheologil stuy of struturl trnsitions in trilok opolymers in liqui rystl solvent. Soft Mtter 26, 2, [4] Kempe, M. D. Rheology n ynmis of sie-group liqui rystlline polymers in nemti solvents. Ph.D. Thesis, Cliforni Institute of Tehnology, Psen, CA, [5] vn Hest, J. C. M.; Kiik, K. L.; Tirrell, D. A. Effiient Inorportion of Unsturte Methionine Anlogues into Proteins in Vivo. J. Am. Chem. So. 2, 122, [6] Ren, X. F.; Turos, E.; Lke, C. H.; Churhill, M. R. Regiohemil n Stereohemil Stuies on Hloyliztion Retions of Unsturte Sulfies. J. rg. Chem. 1995, 6,