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, 560012, INDIA Sumtt to Polymr Cmstry *Corrsponn Autor: rmn@pc.sc.rnt.n
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
PCDMI = 312806 = 2840974 / = 9.1 PEOI = 815798 = 2601850 / = 3.2 Intnsty PII = 787381 = 3457520 / = 4.4 PDI = 15368 = 402617 / = 26.2. 0 2 4 6 8 10 12 14 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.
7.38 7.36 7.26 7.22 7.20 4.06 4.03 4.01 3.33 3.31 3.30 3.11 3.09 3.06 3.05 3.03 2.82 2.80 2.78 2.76 2.73 2.72 2.69 2.68 1.57 1.25-0.00 m o m p o p, 7.5 7.26 4.12 4.11 4.10 4.08 4.07 4.05 3.81 3.80 3.73 3.70 3.63 3.57 3.56 3.55 3.53 3.07 2.91 2.78 2.77 2.76 2.75 2.74 2.72 2.68 2.67 2.65 2.63 2.61 1.63 1.61 1.27-0.01 1.75 1.42 1.03 1.04 1.94 2.11 18.25 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.,,, 1.01 1.01 1.55 0.96 1.14 5.07 17.51 Fur S3(): 1 H NMR spctr o PDI-TG.
7.26 5.36 4.52 4.09 4.07 4.06 3.76 3.76 3.02 3.00 2.98 2.97 2.95 2.92 2.88 2.87 2.78 2.76 2.75 2.74 2.73 2.72 2.71 2.70 2.66 2.65 2.65 2.63 2.28 2.27 1.58 1.44 1.26-0.01 p c 3.75 ppm c p,,, 7.26 4.11 4.10 4.08 4.07 3.75 3.74 3.72 3.08 3.06 3.05 3.03 2.92 2.88 2.87 2.76 2.75 2.74 2.73 2.73 2.72 2.68 1.63 1.61 1.59 1.26-0.01 0.85 0.86 2.75 3.78 2.97 8.58 18.22 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.,, 1.88 0.98 1.11 4.86 17.68 Fur S3(): 1 H NMR spctr o PDI-ME.
7.26 4.08 4.07 4.06 4.06 4.03 3.64 3.55 3.54 3.37 3.05 3.03 3.02 2.93 2.92 2.90 2.89 2.72 2.71 2.69 1.61 1.59 1.58 1.25-0.02 c y 15.3 c,, 2.05 21.74 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). 2.86 7.26 4.09 4.07 4.06 4.05 4.03 4.02 4.02 3.53 3.50 3.49 3.45 3.11 3.09 3.08 2.67 2.65 2.63 2.50 2.48 2.47 2.45 2.17 1.61 1.59 1.29 1.25-0.01 1.04 1.11 4.92 17.74 o m p o,m,p, 6.79 1.98 1.01 2.81 1.20 2.85 17.25 Fur S4(): 1 H NMR spctr o PDI-MBA.
7.26 5.80 5.78 5.76 5.74 5.16 5.16 5.12 5.12 5.10 4.07 4.05 4.03 4.02 3.13 3.11 3.09 3.04 3.02 3.00 2.99 2.68 2.66 2.63 2.61 2.59 2.52 2.50 2.49 1.57 1.29 1.26-0.01,, 7.26 4.05 4.03 3.69 3.67 3.35 3.34 3.33 3.32 3.26 3.25 3.24 2.99 2.98 2.97 2.80 2.76 2.74 2.69 2.68 2.67 2.67 2.66 2.63 2.53 2.51 2.43 2.41 2.28 2.27 2.05 2.04 1.91 1.90 1.89 1.89 1.88 1.87 1.86 1.81 1.79 1.59 2.04 3.58 1.96 2.70 2.88 1.04 16.70 Fur S4(): 1 H NMR spctr o PDI-DAA. c p 3.7 ppm c,,, p p, 2.64 0.49 0.44 2.30 3.78 0.49 1.15 3.30 18.59 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.
PDI-CYS = 21403 = 108600 / = 5.1 PDI-TG = 4096 = 5693 / = 1.4 PDI-PEG750 Intnsty = 51666 = 108499 / = 2.1 PDI-ME = 9094 = 26554 / = 2.9 PDI-TP = 913466 = 2265235 / = 2.5 0 2 4 6 8 10 12 14 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.
PDI-PRO = 754526 = 3526993 / = 4.7 PDI-DAA Intnsty = 613884 = 873778 / = 1.4 PDI-MBA = 460378 = 874004 / = 1.9 0 2 4 6 8 10 12 14 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.
8 4-12 o C 0-4 -8-8 o C Ht low ( mw) Eno 8 4 0-4 -8 1.50 0.75 53 o C H c = 104 J/ 58 o C H m = 107 J/ 7 o C H c = 44 J/ 0.00-0.75-1.50 43 o C H m = 45 J/ -20 0 20 40 60 80 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.
Ht low (mw) 15 10 5 0-5 -10-15 -9 o C rst cycl scon cycl 42 o C -20 0 20 40 60 80 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) 9 6 3 0-3 -6-9 rst cycl scon cycl 53 o C 58 o C -20 0 20 40 60 80 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.
Ht low (mw) 9 6 3 0-3 -6-9 -12-12 o C -8 o C rst cycl scon cycl -20 0 20 40 60 80 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) 2 0-2 -4 41 o C H c = 45 J/ 43 o C H m = 47 J/ -20 0 20 40 60 80 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.