ELECTRONIC SUPPLEMENTARY INFORMATION

Transcription

1 Elctronc Supplmntry Mtrl (ESI) or Polymr Cmstry. Ts ournl s T Royl Socty o Cmstry 2015 ELECTRONIC SUPPLEMENTARY INFORMATION Poly(lyln tcont)s An ntrstn clss o polystrs wt proclly loct xo-cn oul ons suscptl to Mcl ton Snn Cn n S. Rmrsnn* Dprtmnt o Inornc n Pyscl Cmstry Inn Insttut o Scnc, Bnlor, , INDIA Sumtt to Polymr Cmstry *Corrsponn Autor: rmn@pc.sc.rnt.n

2 Fur S1: 1 H NMR spctr o t prnt lnr polystrs, poly(ocyl tcont) (PDI) (), poly(cosyl tcont) (PII) (), poly(olotylnoxy tcont) (PEOI) (c) n poly(cdm-tcont) (PCDMI) (). All t spctr wr rcor n CDCl 3. trns trns l,m l m x 3 p q p,q cs, cs c

3 PCDMI = = / = 9.1 PEOI = = / = 3.2 Intnsty PII = = / = 4.4 PDI = = / = Rtnton Tm (Mn.) Fur S2: Stc plot o t GPC cromtorms o t prnt polystrs rcor usn CHCl 3 s t lunt. T molculr wts wr stmt usn polystyrn-s stnr clrton curv. T unusully molculr wt n PDI o som smpls s proly rlcton o t ormton o som mcrols, wc r o smll nou mnson tt ty pss trou t 0.45 μm ltr.

4 m o m p o p, Fur S3(): 1 H NMR spctr o PDI-TP. T xpn ron rom 5.5 to 6.5 ppm clrly rvls t complt spprnc o t olnc protons sustn tt t Mcl ton s nrly quntttv.,,, Fur S3(): 1 H NMR spctr o PDI-TG.

5 p c 3.75 ppm c p,,, Fur S3(c): 1 H NMR spctr o PDI-CYS. It s ntrstn tt t protons o t mtyl str o t cystn unt ppr s two stnct ps o qul ntnsty; spt t rly rmot locton o t mtyl str roup wt rspct to t nw stronc cntr tt s orm, two stnct ps r osrv rlctn t two stromrc orms.,, Fur S3(): 1 H NMR spctr o PDI-ME.

6 c y 15.3 c,, Fur S3(): 1 H NMR spctr o PDI-PEG750. It s vnt tt t Mcl rcton s on to complton s t rto o t ntnsty o t p u to t trmnl CH 3 O- roup o t rt PEG smnt (mr ) to t p u t mtyln protons cnt to t str roup (mr ) mtcs rsonly wll wt t xpct vlu (4:3) o m p o,m,p, Fur S4(): 1 H NMR spctr o PDI-MBA.

7 ,, Fur S4(): 1 H NMR spctr o PDI-DAA. c p 3.7 ppm c,,, p p, Fur S4(c): 1 H NMR spctr o PDI-PRO. Expnson o t ron rom 5.5 ppm to 6.5 ppm ncts vry smll prsnc o t olnc protons; convrson o t Mcl rcton ws clcult to 99%. Smlr to PDI-CYS, protons o t mtyl str o t proln unt ppr s two stnct ps o qul ntnsty nctn t prsnc o t two stromrc orms tr Mcl ton.

8 PDI-CYS = = / = 5.1 PDI-TG = 4096 = 5693 / = 1.4 PDI-PEG750 Intnsty = = / = 2.1 PDI-ME = 9094 = / = 2.9 PDI-TP = = / = Rtnton Tm (Mn.) Fur S5(): Stc plot o t GPC cromtorms o t vrous tolt polystrs rcor usn CHCl 3 s t lunt. T molculr wts wr stmt usn polystyrn-s stnr clrton curv. T unusully molculr wt n PDI o som smpls s proly rlcton o t ormton o som mcrols, wc r o smll nou mnson tt ty pss trou t 0.45 μm ltr.

9 PDI-PRO = = / = 4.7 PDI-DAA Intnsty = = / = 1.4 PDI-MBA = = / = Rtnton Tm (Mn.) Fur S5(): Stc plot o t GPC cromtorms o t vrous mn rvtz polymrs rcor usn CHCl 3 s t lunt. T molculr wts wr stmt usn polystyrn-s stnr clrton curv. T unusully molculr wt n PDI o som smpls s proly rlcton o t ormton o som mcrols, wc r o smll nou mnson tt ty pss trou t 0.45 μm ltr.

10 o C o C Ht low ( mw) Eno o C H c = 104 J/ 58 o C H m = 107 J/ 7 o C H c = 44 J/ o C H m = 45 J/ Tmprtur ( o C) Fur S6: DSC trmorms o PDI (lc), PII (lu) n PCDMI (r); t scns wr run t tn rt o 10 /mn n ll t trmorms r compltly rproucl.

11 Ht low (mw) o C rst cycl scon cycl 42 o C Tmprtur ( o C) Fur S7(): DSC trmorm o PDI; t scns wr run t tn rt o 10 /mn n ll t trmorms r compltly rproucl. T r n lc runs v n sltly y-xs splc or clrty o t rprouclty. Ht low (mw) rst cycl scon cycl 53 o C 58 o C Tmprtur ( o C) Fur S7(): DSC trmorm o PII; t scns wr run t tn rt o 10 /mn n ll t trmorms r compltly rproucl. T r n lc runs v n sltly y-xs splc or clrty o t rprouclty.

12 Ht low (mw) o C -8 o C rst cycl scon cycl Tmprtur ( o C) Fur S7(c): DSC trmorm o PCDMI; t scns wr run t tn rt o 10 /mn n ll t trmorms r compltly rproucl. T r n lc runs v n sltly y-xs splc or clrty o t rprouclty. Ht low (mw) o C H c = 45 J/ 43 o C H m = 47 J/ Tmprtur ( o C) Fur S8: DSC trmorm o PII-PRO; t scns wr run t tn rt o 10 /mn n ll t trmorms r compltly rproucl.