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1 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 Verstile Grfting Approhes to tr-hped P-Contining Hyrid Polymers using RAFT Polymeriztion nd Clik Chemistry Yun-heng Ye, Wei-Chung hen, Chi-Yung Tseng, John Rik, Yo-Jheng Hung, Feng-Chih Chng, nd Bing-Joe Hwng * Deprtment of Chemil Engineering, tionl Tiwn University of iene nd Tehnology, Tipei, Tiwn. E-mil:jh@mil.ntust.edu.tw Institute of Applied Chemisty, tionl Chio-Tung University, Hsin-Chu, Tiwn E-Mil: jh@mil.ntust.edu.tw upplementry Informtion Tle of Contents Experimetnl Mtreils nd Chrteriztion... Generl Proedure for 8P-P... Generl Proedure for 8CTAs-P... 7 ynthesis Route for PMMA-g/t-P Hyrid... ynthesis of PMMA-g/f-P hyrid... Multifuntionl RAFT Agents Used in the ynthesis of tr Polymers... 6 Tle ~... 6 Figure 0~... 8 Referenes...

2 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 Experimentl Mterils uini nhydride (99%), proprgyl lohol (99%), romoenzene (99%, pure), mgnesium (99.9+%), sodium zide (99%), -hloro--hydroxypropne (98%),, -diylohexylrodiimide (DCC) (99%), -dimethylminopyridine (99%), llyllohol (99+%) nd Copper(I) Iodide ( 98%) were purhsed from Aros., -Azois(-ynovleri id) (V50) ws purhsed from igm Aldrih. Cron disulphide (99.9%) ws purhsed from Pnre.,-dimethylformmide (DMF; igm Aldrih), tetrhydrofurn (THF; Aros), dihloromethne (DCM; Aros) nd triethylmine (TEA; Aros) were vuum-distilled prior to use. Chrteriztion FT-IR spetr were otined with iolet Avtr 0 FTIR spetrometer; sns were olleted t spetrl resolution of m -. The smple for FTIR mesurement ws prepred y deposition of solutions on slt pltes. H (500 MHz) nd C (5 MHz) MR spetr were otined in CDCl -d or DM-d 6 on Vrin 500 MHz spetrometer model Unity IVA. The internl solvent pek ws used to lirte the hemil shift in the MR dt. Gel permetion hromtogrphy (GPC) nlysis ws performed on JAC HPLC Gulliver 900 with omintion of KF-80L (0 m, exlusion limit: 7.0 0, polystyrene) nd KF-80 (0 m, exlusion limit:.0 0 5, polystyrene) olumns (liner lirtion down to Mn = 00) with THF s n eluent t 5. Clirtion ws hieved with ommeril polystyrene stndrds rnging from 00 to 0 6 g mol -. For GPC hrteriztion of the HF-ethed smple, the PMMA-g/f-P hyrids were dissolved in THF prior to ething. After HF-ething, the produts in THF were used diretly for GPC mesurements. Thin-lyer hromtogrphy (TLC) ws performed on sili gel sheet oted with sili gel 60 F5 from E. Merk, visulized y UV light. Column hromtogrphy ws performed on sili gel 60 (Knto Chemil C., IC, Ct. o , 0-50 μm). Elementl nlyses (EA) were run on PerkinElmer model 00 CH nlyzer.

3 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 heme. ynthesis route for 8P-P nd 8CTAs-P. suini nhydride + H proprgyl lohol Br + Mg + C THF Reflux P Q 8 M 8 H + H llyllohol PCPB H BDTPA + H C C V-50 H Pd/Toluene 0 o C Cl Reflux H C i H CH P 8 + 8H-P PCPCL Cl C Croxyli CTA H + H -zidopropn--ol DMF H Cl -hloropropn- -ol THF/TEA 0 o C 0 o C DCC / DCM H C i CH P 8P-P 8 CuI + DMF C Azido CTA H C i CH P C 8 8CTAs-P

4 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 Generl Proedure for 8P-P Preprtion of -proprgyl ronyl propioni Aid (PCPA): Proprgyl lohol (0g, 0.8 mol), suini nhydride (.6g, 0.mol), 7. ml (0. mol) pyridine nd 6 ml (0. mol) triethyl mine were dissolved in 00 ml of dry THF. The mixture ws stirred t 80 o C for h. The mixture ws evported under vuum nd then dissolved in dihloromethne nd wshed with hilled M HCl. After extrting three times, the orgni phse ws dried over, filtered, nd evported. The produt ws rystllized from toluene (yield: 8 %). H MR (CDCl ): δ =.9 (s, H, CH C-),.6 (m, H, CH-CH -CH -CH),.7 (d, H, CH C-CH --),.6 (s, H, CH) ppm. C MR (CDCl ): δ = 9.5 (CH-CH -CH -CH), 5.8 (CH C-CH --), (CH C-), (CH C-CH -), 7.98 (CH -CH-CH -), 78. (-CH -CH) ppm. () d H e,d () H 5,6 7 e Chemil shift (ppm) Chemil shift (ppm) Figure. () H-MR nd () C-MR of spetr of PCPA. Preprtion of -proprgylronyl propioni hloride (PCPCl): -Proprgylronyl propioni hloride (PCPCl) ws prepred from PCPA s follows: PCPA (0.0 g, 0.8 mol) ws introdued into dried hlenk flsk nd mixed with 5 ml of nhydrous dihloromethne. Freshly distilled thionyl hloride (0 ml) ws dded dropwise to the PCPA mixture solution over 0 min.

5 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 Then the retion mixture ws heted t reflux for 5 h. The solvent ws removed y first distilling t tmospheri pressure, nd then under vuum overnight t room temperture, leving the produt s yellow nd highly visous liquid, whih distilled under vuum ( P) t 0 o C to give olorless visous produt (yield 9 %). H MR (CDCl ): δ =.5 (s, H, CH C-),.7 (t, H, -C-CH -CH -),. (t, H, CH -CH -CCl),.69 (s, H, CH C-CH -) ppm. C MR (CDCl ): δ =.88 (-C-CH -CH -), 5. (-CH -CH -CCl), (CH C-CH -), 79.0 (CH C-), 80.9 (CH C-CH ), 7.09 (CH -CCl), (-C-CH ) ppm. () () d Cl Cl 6 5 d 7 6 Chemil shift (ppm) Chemil shift (ppm) Figure. () H-MR nd () C-MR of spetr of PCPCl. Preprtion of tkis(dimethylsilyloxy)hydroxypropyl silsesquioxne (8H-P): 8H-P ws synthesized ording to our previous reports. - Q8M8 H ( g,.95 mmol) ws dissolved in nhydrous toluene in 00 ml round-ottom flsk under rgon. Allyl lohol (.7g, 9.6 mmol) ws dded in 5% exess to the Q 8 M H 8. Krstedt s tlyst [Pt(dvs)] (0.6 ml of 6 mmol solution in toluene) ws dded, nd n immedite inrese from room temperture to 5 C ws oserved. The retion ws monitored y H MR. After h, the dispperne of the i-h proton shift δ =.7 ppm) onfirmed tht the hydrosilyltion hd gone to ompletion. The retion mixture ws onentrted under redued pressure, nd the exess strting llyl lohol ws 5

6 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 removed y vuum distilltion giving white wxy solid (yield: 95 %. M w = 500 g mol - ). H MR (CDCl ): δ = 0.7 (m, 6H, -i-(ch ) -), 0.6 (m, H, i-ch -CH -),.6 (m, H, -CH -CH -CH -),.59 (m, H, -CH -CH -H) ppm. C MR (CDCl ): δ = 0.0 (-i-(ch ) -),.86 (i-ch -CH -), 6.68 (-CH -CH -CH -), 65.9 (-CH -CH -H) ppm H C i d e H 8 CH. H C i H 8 CH d d,e 5 Chemil shift (ppm) Chemil sfhit (ppm) Figure. () H-MR nd () C-MR of spetr of 8H-P. tkis(dimethylsilyloxy)proprgyl ronyl-silsesquioxne (8P-P): 8H-P ( g,.00 mmol,.0 equiv) ws dissolved in 0 ml of solute THF, nd distilled with triethylmine (TEA) (.0g, 0 mmol, 0 equiv). A solution of PCPCl (.9g, 0 mmol, 0 equiv) in 0 ml of solute THF ws slowly dded to the ove 8H-P solution t 0 o C. After stirring for h t room temperture under nitrogen, the mixture solution ws filtered. The filtrte ws onentrted y rotry evportion. The resulting oily residue ws purified y olumn hromtogrphy (sili gel, eluent: ethyl ette/hexne (:)) to give the produt. Yield: 89 %. M w = 679 g mol -. H MR (CDCl ): δ = 0.8 (m, 6H, -i-(ch ) -), 0.6 (m, H, i-ch -CH -),.68 (m, H, -CH -CH -CH -),.5 (s, H, -C CH),.7~.6 (m, H, -C-CH -CH -C-),.05 (t, H, CH -CH -C-),.7 (s, H, -C-CH -C CH) ppm. C MR (CDCl ): δ = 0.5 (-i-(ch ) -),.0 (i-ch -CH -),.67 (CH -CH -CH -), 9.60 (-C-CH -CH -C-), 5.59 (-C-CH -C CH), 67.7 (CH -CH -C-), 75.5 (-C CH), (-CH -C CH), (-C-CH -CH -C-) ppm. 6

7 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 () C H P0.06 d i e CH f g h 8 () C H P0.06 i 5 CH 6 7 0, d ,7 g d e,f h 5,8 5 Chemil shift (ppm) Chemil shift (ppm) Figure. () H-MR nd () C-MR of spetr of 8H-P. Generl Proedure for 8CTAs-P Preprtion of Di(thioenzoyl) Disulfide: Di(thioenzoyl) disulfide ws synthesized ording to umerlin s report. Bromoenzene (.6 ml) in 90 ml of dry THF ws dded dropwise to mgnesium turnings (g, 0. mol) in 00 ml of dry THF with stirring under nitrogen. After the mgnesium hd finished reting, the solution ws ooled to 0 o C nd ron disulte (9.5g, 0. mol) ws dded dropwise to the Grignrd mixture with ooling. The Grignrd regent ws then hydrolyzed y the slow ddition of wter (0 ml). The mgnesium slts were removed y filtrtion nd wshed with wter. To this, 00 ml of.0 HCl solution ws dded hnging the olor to virnt pink. The pink solution ws trnsferred to L seprting tunnel nd wshed with 50 ml of ethyl ether. The olorless queous lyer ws disrded. The red ether lyer ws wshed with 50 ml of.0 H solution nd the yellow ether lyer disrded. The drk red queous lyer ws wshed with 50 ml of ethyl ether nd the yellow ether lyer disrded, leving drk red solution of the sodium slt of dithioenzoi id. A solution of the sodium slt of dithioenzoi id (50 ml) ws pled in L round-ottomed flsk equipped with n ddition tunnel, nd reflux ondenser. A solution of potssium ferriynide 7

8 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 (Ш) (.g, 0.065mol) in 00 ml distilled wter ws dded dropwise, to vigorously stirred solution, over.5 h. The red preipitte ws olleted in Buhner tunnel y vuum filtrtion. Yield:.88g. H MR (CDCl ): δ =7.7 (m, H, Ph-C nd C 5 ), 7.6 (m, H, Ph-C ), 8. (m, H, Ph-C ) ppm. C MR (CDCl ): δ = 7.6 (Ph-C nd C 6 ), 8.7 (Ph-C nd C 5 ),.00 (Ph-C ),.9 (Ph-C ), 9.5 (Ph-C=-) ppm. d C C C 5 C Chemil shift (ppm) Chemil shift (ppm) Figure 5. () H-MR nd () C-MR of spetr of Di(thioenzoyl) Disulfide. Preprtion of -yno--(thioenzoyl) sulfonyl pentnoi id (CTB; RAFT hin trnsfer gents (CTAs)): Bis (thioronyl) disulfide (8.6g, 0.06 mmol,.0 equiv) nd, zo-is-(-ynovleri id) (6.69 g, 0.06 mol,.0 equiv) were refluxed in ethyl ette t 85 o C for h, under nitrogen, in free rdil retion. The solvent ws then removed y rotry evportion nd the rude produt ws purified y olumn hromtogrphy (sili gel, eluent: ethyl ette/hexne (:8)) to give the red oily produt. The oily produt ws further rerystllized in enzene to otin the finl produt (yield: 75%). H MR (CDCl ): δ =.96 (s, H, --C(CH )-C),.5 to.80 (m, H, -CH -CH -CH), 7.0 8

9 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 (m, H, Ph-C nd C 6 ), 7.57 (m, H, Ph-C ), 7.90 (m, H, Ph-C nd C 5 ) ppm. C MR (CDCl ): δ =.89 (--C(CH )-C), 9.8 (-CH -CH -CH),.8 (-CH -CH -CH), 6.6 (--C(CH )-C), 9.0 (C ), 7.6 (Ph-C nd C 6 ), 8.97 (Ph-C nd C 5 ),.5 (Ph-C ), 5.9 (Ph-C ), 77.6 (C=),.69 (Ph-C=-) ppm. C e d f H d 5 C H d d e f Chemil shift (ppm) Chemil shift (ppm) Figure 6. () H-MR nd () C-MR of spetr of CTB. Preprtion of -Azidopropnol: -Chloro--propnol (0.0g, 0. mol) nd sodium zide (7.8g, 0.6 mol) were reted in H (00 ml) t 95 o C for h. The retion mixture ws ooled to room temperture, poured into 00 ml of ethyl ether, nd extrted with sturted queous 800 ml of Cl solution. The orgni lyer ws seprted, dried over Mg, nd filtered. The superntnt ws onentrted to otin the produt (yield: 98%). H MR (CDCl ): δ =.86 (m, H, H-CH -CH -CH - ),.6 (t, H, -CH -CH - ),.76 (t, H, H-CH -CH -) ppm. C MR (CDCl ): δ =.8 (H-CH -CH -CH - ), 8.65 (-CH -CH - ), (H-CH -CH -) ppm. 9

10 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 () () H H d Chemil shift (ppm) Chemil shift (ppm) Figure 7. () H-MR nd () C-MR of spetr of -Azidopropnol. Preprtion of -zidopropyl -yno--((phenylronothioyl)thio)utnote (Azido-CTAs): CTB (g,.77 mmol,.0 equiv) nd -Azidopropnol (0.8g,.77 mmol,.0 equiv) were dissolved in 0 ml of dry dihloromethne in 00 ml round ottom flsk nd ooled to pproximtely 0 o C. A solution of,'-diylohexylrodiimide (DCC) (0.78g,.77mmol,.0 equiv) in 0 ml of dry dihloromethne ws dded dropwise, nd the retion mixture ws llowed to wrm to room temperture nd stir for h. The white solid ws filtrted, nd the orgni lyer ws wshed with 0% sodium ironte solution, wter, nd sturted Cl solution. The resulting oily residue ws purified y olumn hromtogrphy (sili gel, eluent: ethyl ette/hexne (:8)) to give the produt (yield: 9%). H MR (CDCl ): δ =.96~.8 (m, H, -CH -CH -CH -),.9 (s, H, --C(CH )-C),.68~.6 (m, H, -CH -CH -C-),. (m, H, -CH -CH - ),.0 (t, H, -C-CH -CH -), 7.9 (m, H, Ph-C nd C 5 ), 7.56 (Ph-C ), 7.9 (m, H, Ph-C nd C 6 ) ppm. C MR (CDCl ): δ =.5 (--C(CH )-C), 8.0 (CH -CH -C-), 0.00 (-CH -CH -CH -),.6 (-CH -CH -CH), 5.9 (--C(CH )-C), 8.8 (-CH -CH - ), 6.8 (-C-CH -CH -), 8.68 (-C ), 6.87 (Ph-C nd C 6 ), 8.68 (Ph-C nd C 5 ),. (Ph-C ),.6 (Ph-C ), 0

11 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 7. (CH -C-),.8 (Ph-C=) ppm. Figure 8. () H-MR nd () C-MR of spetr of Azido-CTAs. Preprtion of tkis(dimethylsilyloxy)--yno--((phenylronothioyl)thio)utnotesilsesquioxne (8CTAs-P): 8P-P (g, 0.7mmol,.0 equiv) nd zido-ctas (.6g, 7.0 mmol, 0 equiv) in 0 ml of DMF ws purged with nitrogen nd trnsferred vi nnul to vil ontining CuBr (.6 mg, 0.5 mmol) under nitrogen environment. The retion mixture stirred t room temperture in the sene of oxygen for h. The retion mixture ws exposed to ir, nd the solution ws pssed through olumn of neutrl lumin. DMF ws evported under vuum ( P) system t 0 o C to otin n red visous oil. The resulting oily residue ws purified y olumn hromtogrphy (sili gel, eluent: methnol/dihloromethne (:9) to give the produt. Yield: 9%. H MR (CDCl ): δ = 0.8 (m, 6H, -i-(ch ) -),.96~.9 (s, H, --C(CH )-C; m, H, -CH -CH -CH -),.7~.9 (-C-CH -CH -),.76~.57 (m, H, -C-CH -CH -C-; m, H, --C(CH )-C),.09 (t, H, -CH -CH -C-),.8 (t, H, -CH -CH -C-),.9 (t, H, -C-CH -CH -), 5.5 (s, H, -C-CH --), 7. (m, H, Ph-C nd C 5 ), 7.58 (m, H, Ph-C ), 7.9 (7.75, H, --C=C-), 7.9 (m, H, Ph-C nd C 6 ) ppm. C MR (CDCl ): δ = 0.5 (-i-(ch ) -),

12 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0.8 (-i-ch -CH -),. (-CH -CH -CH -),. (--C(CH )-C), 8.9 (-C-CH -CH -), 9. (-C-CH -CH -C-), 9.7 (-CH -CH -CH -),. (CH -CH -C(C)-), 5.69 (--C(CH )-C), 7.66 (-C-CH -CH -), 57.7 (-C-CH --), 6.77 (-CH -CH -C-), 67.6 (-CH -CH -C-), 8.5 (-C ),.0 (--CH=C-), 6.58 (Ph-C nd C 6 ), 8.58 (Ph-C nd C 5 ),. (Ph-C ),.66 (-CH-C-CH ),.66 (Ph-C ), 7.7 (-C-CH -CH -C-), 7.7 (-C-CH -),.56 (Ph-C=) ppm. M w = 556 g mol -. P CH i d CH 5 6 e f g 0 h i j 5 k 6 l C 9 0 m 7 CH n 8 o p q 5 8CTAs-P () () d 7 6,7 6 8 d o p q h g i kd e,f,m l n,j 5 5 5, Chemil shift (ppm) Chemil shift (ppm) Figure 9. () H-MR nd () C-MR of spetr of 8CTAs-P.

13 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 heme. ynthesis route for PMMA-g/t-P hyrid. () RAFT Polymeriztion () Grfting to Approh MMA + CTAs- Azide + P DMF 70 o C PMMA- n C DMF CuI 8P-P PMMA- () Model Retion n C PMMA- + PCPA H P DMF CuI n C H Model Compound PMMA-g/t-P Generl Proedure for RAFT Polymeriztion of MMA with Azido-CTAs (zido-terminted polymer, PMMA- ) [heme ()] Polymeriztions were onduted in DMF using AIB s the primry rdil soure nd zido-cta s the funtionl hin trnsfer gent. In typil polymeriztion (run of Tle ), MMA (g, 0.0 mmol, 50 equiv)), zido-ctas (0.7g, 0.6 mmol,.0 equiv), nd AIB (088 mg, 0. mmol, 0. equiv) were dded to glss tue with mgneti stirring r, nd DMF ws dded until the totl onentrtion ws M. The tues were sujeted to three yles of freeze-pump-thw to remove oxygen. The tue ws susequently immersed into n oil th preheted to 70 o C. After h, the polymeriztion ws quenhed y pling the tue into n ie-wter th. The polymeriztion solution ws drwn nd dissolved into CDCl to hek H-MR, nd the monomer onversion ws

14 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 determined to e 95.6 % ompring the integrted res of hrteristi signls of monomer nd polymer. After preipitting into lrge mount of methnol, zido-terminted PMMA ws isolted, nd its moleulr weight nd polydispersity (PDI) were otined y gel permetion hromtogrphy (GPC) in Tle. ther polymers were synthesized ording to similr pproh. Model Clik Retion for Azido-terminted Polymer [heme ()] The low-moleulr-weight zido-terminted PMMA ws reted with PCPA whih hs sme lkyne struture s 8P-P. A solution of PMMA- (PMMA- (50) M n = 676 g mol - ; g, 0. mmol,.0 equiv) in 0 ml of DMF, PCPA (0.05g, 0.mmol,.5 equiv) ws purged with nitrogen nd trnsferred vi nnul to vil ontining CuI (.6 mg, 0.0 mmol) under nitrogen environment. The retion mixture stirred t room temperture in the sene of oxygen for h. The retion mixture ws exposed to ir, nd the solution ws pssed through olumn of neutrl lumin. The polymer ws preipitted into methnol nd dried under vuum. Generl Proedure for Grfting to Approh [heme ()] 8P-P (0.05g, 0.08 mmol,.0 equiv) nd PMMA- (0. mmol, 8.0 equiv) were dissolved in 0 ml of DMF nd purged with nitrogen nd trnsferred vi nnul to vil ontining CuI (.05 mg, 0.0 mmol) under nitrogen environment. The retion mixture stirred t room temperture in the sene of oxygen for h. The retion mixture ws exposed to ir, nd the solution ws pssed through olumn of neutrl lumin. The polymer ws preipitted into methnol nd dried under vuum.

15 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 Multifuntionl RAFT Agents Used in the ynthesis of tr Polymers heme. Multifuntionl RAFT gents used in the synthesis of str polymers There re two types of multifuntionl RAFT gents used in the synthesis of str polymer: (A) the multifuntionl RAFT gents with the Z-group s prt of the ore will llow the growth of rms wy from the ore during polymeriztion. (B) For those RAFT gents with the R-group s prt of ore, hin growth must our on the surfe of ore. 5

16 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 Generl Proedure for Grfting from Approh (ynthesis of PMMA-g/f-P hyrid) MMA grft polymeriztion from 8CTAs-P ws onduted in DMF using AIB s the primry rdil soure nd 8CTA-P s the funtionl hin trnsfer gent. In typil polymeriztion (run of Tle ), MMA (g, 0.0 mmol, 50 equiv)), 8 CTAs -P (0.7g, mmol, 0.5 equiv), nd AIB (.6 mg, 0.05 mmol, 0.05 equiv) were dded to glss tue with mgneti stirring r, nd DMF ws dded until the totl onentrtion ws M. The tues were sujeted to three yles of freeze-pump-thw to remove oxygen. The tue ws susequently immersed into n oil th preheted to 70 o C. After h, the polymeriztion ws quenhed y pling the tue into n ie-wter th. The polymeriztion solution ws drwn nd dissolved into CDCl to hek H-MR, nd the monomer onversion ws determined to e 89. % y ompring the integrted res of hrteristi signls of monomer nd polymer. After preipitting into lrge mount of methnol, str PMMA ws isolted, nd its moleulr weight nd polydispersity (PDI) were otined y gel permetion hromtogrphy (GPC) in Tle. ther str polymers were synthesized ording to similr pproh. Tle. GPC nd EA hrteriztion of P derivtive. mple Theoretil M w Clulted M w Theoretil Elem. Anl. Clulted Elem. Anl. C H C H 8H-P P-P CTA-P Clulted from GPC. 6

17 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 Tle. RAFT polymeriztion of MMA medited y zido-ctas. M n M w PDI M n mple [M] : [CTA] : [I] M n (th) (GPC) (GPC) (M w /M n ) (MR) PMMA- (50) 50 : : PMMA- (75) 75 : : PMMA- (50) 50 : : PMMA- (0) 0 : : Clulted from H-MR. Tle. RAFT polymeriztion of MMA medited y 8CTAs-P. mple [M] : [CTA] : [I] M n (rm) (th) M n (rm) (GPC) PDI (str) M n (rm ) (Hydrolysis) M w (rm) (Hydrolysis) PDI (rm) PMMA-g/f-P 75 : : PMMA-g/f-P 50 : : PMMA-g/f-P 0 : : The numer-verge moleulr weight of the rm in the PMMA-g/f-P M n (rm) (GPC), lulted from GPC sed on eq. GPC mesurement of the hydrolysis produt. M n (str) (GPC) = M n (rm) (GPC) 8 + M 8CTAs-P... eq 7

18 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 5k (B) 0k 5k [M] : [CTA] : [I] 75 : : : : 0. 0 : : 0. 0k 5k Conversion (%) Fig. 0. (A) GPC tres s funtion of time for the RAFT polymeriztion of MMA with zido-ctas ([M] 0 : [CTAs] : [AIB] = 50 : : 0. (B) numer-verge moleulr weight (M n ) vs monomer onversion for the RAFT polymeriztion of MMA with zido-ctas. Fig.. H-MR spetr of pek ssignments for (A) PMMA- nd (B) the produt fter oupling with PCPA. 8

19 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 FTIR Result for 8P-P, Azido-CTAs nd 8CTAs-P. FTIR onfirmed tht CTAs-P ws suessfully prepred. Compred to the FTIR spetrum of 8P-P nd zido-ctas, the nds t 85 m - nd 097 m - (i.e. the respetive lkyne nd zide strething virtions) hve ompletely disppered. The nds ppering t 08 m - nd 086 m - in the spetrum of 8CTAs-P re ssigned to the strething virtion of C= nd o--i, respetively. -C CH -C CH 5 m - 85 m - C m - 8P-P zide 097 m - C= 7 m - i- 086 m - C= 08 m - Azido-CTAs 8CTAs-P Wvenumer (m - ) Fig.. FTIR spetr of 8P-P, Azido-CTAs nd 8CTAs-P. 9

20 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 Tle. FTIR wvenumer list mple Position ν s Wvenumer (m - ) -C CH P-P C= 7 i- 086 C Azido-CTAs zide 097 C= 7 C= 08 C 8CTAs-P C= 7 i- 086 C= 08 0 h 0.5 h h h 8 h h Elution Volume(mL) Fig.. GPC urve for the RAFT polymeriztion of MMA t 70 o C in DMF (M) in the presene of 8CTAs-P ([M] 0 : [CTAs] : [AIB] = 50 : : 0.). 0

21 Eletroni upplementry Mteril (EI) for Chemil Communitions This journl is The Royl oiety of Chemistry 0 k k 0k Liner Polymer tr Polymer.0.8 Mn 8k 6k.6 PDI k. k 0k Conversion (%) Fig.. Evolution of the moleulr weight nd PDIs with onversion for the RAFT polymeriztion of MMA t 70 o C in DMF in the presene of zido-ctas nd 8CTAs-P ([M] 0 : [CTAs] : [AIB] = 50 : : 0.). Referenes () Mrkovi, E.; Gini-Mrkovi, M.; Clrke,.; Mtisons, J.; Hussin, M.; imon, G. P. Mromoleules 007, 0, 69. () Ye, Y.-.; Chen, W.-Y.; Wng, Y.-Z. Journl of Polymer iene Prt A: Polymer Chemistry 006,, 59. () Ye, Y.-.; Yen, Y.-C.; Chen, W.-Y.; Cheng, C.-C.; Chng, F.-C. Journl of Polymer iene Prt A: Polymer Chemistry 008, 6, 696. () Gondi,. R.; Vogt, A. P.; umerlin, B.. Mromoleules 007, 0, 7.