Supporting Information
Radical Addition-Coupling Polymerization
with Various Nitroso Compounds
Junjie Li, and Qi Wang*
Key Laboratory of Macromolecular Synthesis and Functionalization (Ministry of Education),
Department of Polymer Science & Engineering, Zhejiang University, Hangzhou, 310027, P. R.
China.
Email: wangq@zju.edu.cn
1. NMR and MS spectra of nitroso esters
Fig.S1 1H-NMR (CDCl3, 400MHz) spectrum of 2-nitroso-2-methyl-4-acetoxypentane
(NMAP)
Fig.S213C-NMR spectrum (CDCl3, 400MHz) of 2-nitroso-2-methyl-4-acetoxypentane
(NMAP)
Fig.S3
ESI mass spectrum of 2-nitroso-2-methyl-4-acetoxypentane (NMAP)
Fig. S4 1H-NMR spectrum (CDCl3, 400MHz) of 2-methyl-2-nitrosopropyl butyrate
(MNPB)
Fig. S5 ESI mass spectrum of 2-methyl-2-nitrosopropyl butyrate (MNPB)
Fig. S6 1H-NMR spectrum (CDCl3, 400MHz) of 2-methyl-2-nitrosopropyl hexanoate
(MNPH)
Fig. S7 ESI mass spectrum of 2-methyl-2-nitrosopropyl hexanoate (MNPH)
Fig. S8 1H-NMR spectrum (CDCl3, 400MHz) of 2-methyl-2-nitrosopropyl
undecanoate (MNPU)
Fig. S9 ESI mass spectrum of 2-methyl-2-nitrosopropyl undecanoate (MNPU)
2. Characterization of polymers
2.1 GPC Curves of polymers
o
25 C,Mn=59200,PDI=1.63
o
50 C,Mn=77100,PDI=1.71
o
60 C,Mn=71700,PDI=1.67
o
70 C,Mn=18700,PDI=1.43
3.0
3.5
4.0
4.5
5.0
logMw
5.5
6.0
6.5
Fig. S10 GPC curves of polymer prepared by RACP between DMDBT and MNP
o
25 C,Mn=34900,PDI=1.55
o
40 C,Mn=55200,PDI=1.43
o
50 C,Mn=70100,PDI=1.61
o
60 C,Mn=71100,PDI=1.63
o
70 C,Mn=79500,PDI=1.44
3.5
4.0
4.5
5.0
logMw
5.5
6.0
6.5
Fig. S11 GPC curves of polymer prepared by RACP between DMDBT and NMAP
o
25 C,Mn=59100,PDI=1.62
o
50 C,Mn=31700,PDI=1.52
o
60 C,Mn=10400,PDI=1.42
o
70 C,Mn=10400,PDI=1.49
2.5
3.0
3.5
4.0
4.5
logMw
5.0
5.5
6.0
Fig. S12 GPC curves of polymer prepared by RACP between DMDBT and MNPB
o
25 C,Mn=71300,PDI=1.74
o
50 C,Mn=77500,PDI=1.85
o
60 C,Mn=59800,PDI=1.63
o
70 C,Mn=83900,PDI=1.80
3.5
4.0
4.5
5.0
5.5
6.0
6.5
logMw
Fig. S13 GPC curves of polymer prepared by RACP between DMDBT and MNPH
o
25 C, Mn=9400, PDI=1.92
o
70 C, Mn=7200, PDI=2.22
2.5
3.0
3.5
4.0
logMw
4.5
5.0
5.5
Fig.S14 GPC curves of polymer prepared by RACP between BBEB and MNPH
o
25 C,Mn=17100,PDI=1.41
o
50 C,Mn=11900,PDI=1.42
o
60 C,Mn=11700,PDI=1.40
o
70 C,Mn=13300,PDI=1.43
2.5
3.0
3.5
4.0
4.5
5.0
5.5
logMw
Fig. S15 GPC curves of polymer prepared by RACP between DMDBT and MNPU
2.2 1H-NMR spectra of polymers
Fig. S16 1H-NMR spectrum (CDCl3, 400MHz) of polymer prepared by RACP
between DMDBT and MNP at 25oC
Let nDMDBT=x, nMNP=y, then 1) SHa + Hb + Hc + Hd = 12x = 12.76, 2) SHe + Hf = 16x + 9y =
26.54. We got [DMDBT]/[MNP] = x/y = 1.00
Fig. S17 1H-NMR spectrum (CDCl3, 400MHz) of polymer prepared by RACP
between DMDBT and MNP at 70oC
Let nDMDBT=x, nMNP=y, then 1) SHa + Hb + Hc + Hd = 12x = 12.53, 2) SHe + Hf = 16x + 9y =
25.59. We got [DMDBT]/[MNP] =x/y=1.06
Fig. S18 1H-NMR spectrum (CDCl3, 400MHz) of polymer prepared by RACP
between DMDBT and NMAP at 70oC
Let nDMDBT=x, nNMAP=y, then 1) SHa + Hb + Hd = 8x = 7.99, 2) SHc = y = 1. We got
[DMDBT]/[NMAP] = x/y = 1.00.
Fig. S19 1H-NMR spectrum (CDCl3, 400MHz) of polymer prepared by RACP
between DMDBT and MNPB at 25oC
Let nDMDBT=x, nMNPB=y, then 1) SHa + Hg + Hb + Hh = 8x + 2y = 10.11, 2) SHc = y = 2. We
got [DMDBT]/[MNPB] = x/y = 1.01
Fig. S20 1H-NMR spectrum (CDCl3, 400MHz) of polymer prepared by RACP
between DMDBT and MNPB at 70oC
Let nDMDBT=x, nMNPB=y, then 1) SHa + Hg + Hb + Hh = 8x + 2y = 10.11, 2) SHc = y = 2. We
got [DMDBT]/[MNPB] = x/y = 1.01
Fig. S21 1H-NMR spectrum (CDCl3, 400MHz) of polymer prepared by RACP
between DMDBT and MNPH at 70oC
Let nDMDBT=x, nMNPH=y, then 1) SHa + Hb + Hg + Hh = 8x + 2y = 10, 2) SHc = y = 2. We got
[DMDBT]/[MNPH] = x/y = 1
Fig.S22 1H NMR spectrum (CDCl3,400MHz) of polymer prepared by RACP of
BBEB and MNPH at 25oC
Let nBBEB=x, nMNPH=y, then 1) Se =2x=1.98, 2) Sa =4y=4. We got [BBEB]/[MNPH] =
x/y = 0.99
Fig. S23 1H-NMR spectrum (CDCl3, 400MHz) of polymer prepared by RACP
between DMDBT and MNPU at 25oC
Let nDMDBT=x, nMNPU=y, then 1) SHa + Hb + Hg + Hh =8x+2y=10.11, 2) SHc =y=2. We got
[DMDBT]/[MNPU] = x/y = 1.01
Fig. S24 1H-NMR spectrum (CDCl3, 400MHz) of polymer prepared by RACP
between DMDBT and MNPU at 70oC
Let nDMDBT=x, nMNPU=y, then 1) SHa + Hb + Hg + Hh = 8x + 2y = 10.01, 2) SHc = y = 2. We
got [DMDBT]/[MNPU] = x/y = 1.00
2.3 Calculation of polymer yield
Original GPC curve
Integral area
1.0
Integral area
0.8
0.6
0.4
monomer
0.2
0.0
(3.01, 0.015)
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
logMw
Fig. S25 GPC curves of crude polymer prepared by RACP between DMDBT and
NMAP at 70oC and its integral area curve
The weight fraction of monomer is about 1.5%. So the polymer yield is about 98.5%.