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Supporting Information to
SET-LRP of NIPAM in Water via In Situ Reduction of Cu(II) to Cu(0) with NaBH4.
Mikhail Gavrilov1, Timothy J. Zerk2, Paul V. Bernhardt2, Virgil Percec3 and Michael J.
Monteiro1,*
1. Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, St Lucia, Brisbane QLD 4072, Australia.
2. School of Chemistry and Molecular Biosciences, The University of Queensland, St Lucia, Brisbane QLD 4072, Australia.
3. Roy ans Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 190104-6323.
* To whom correspondence should be addressed. m.monteiro@uq.edu.au
Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2015
1.01.52.02.53.03.54.04.5 ppm
OHO
OH
Br
O
a
b d
c
e
c
d
e
a
b
Figure S1. 1H NMR of 11 at 298K (500 MHz), recorded in CDCl3.
2030405060708090100110120130140150160170 ppm
OHO
OH
Br
O
a
b d
fe
c g
c
g d
b e
a
f
Figure S2. 13C NMR of 11 at 298K (500 MHz), recorded in CDCl3.
1
1.1
1.2
1.3
1.4
0 20 40 60 80 100
Mw
/Mn
Conversion (%)
0
1000
2000
3000
4000
5000
6000
0 20 40 60 80 100
Mn
Conversion (%)
[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 1/0.8/0.8/0.2
0
1000
2000
3000
4000
5000
6000
0 20 40 60 80 100
Mn
Conversion (%)
(A)
(C)
(B)
(a)
(b)
(c)(d)
SEC-RI
SEC-RI
Mark-Houwink
Figure S3. Aqueous SET-LRP of NIPAM catalyzed by the in situ generation of Cu(0) from NaBH4 by varying [NIPAM]o/[I]o from (a) 20/1 ■, (b) 30/1 , (c) 40/1 ▲, (d) 50/1 ●. (A) Mn
determined from SEC using RI and polystyrene standards (dashed lines represent theoretical Mn values). (B) Mn calculated using the Mark-Houwink equation from correlation between SEC and MALDI Mn's, and (C) Mw/Mn values after re-calculation using the Mark-Houwink equation . Reaction conditions: [I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
[NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o = 30/1/0.8/0.8
0
500
1000
1500
2000
2500
3000
3500
4000
0 20 40 60 80 100
Mn
Conversion (%)
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0 20 40 60 80 100
Mn
Conversion (%)
1
1.1
1.2
1.3
1.4
0 20 40 60 80 100
Mw
/Mn
Conversion (%)
(A)
(C)
(B)SEC-RI
SEC-RI
Mark-Houwink
(a) (b) (c)
(d)
Figure S4. Aqueous SET-LRP of NIPAM catalyzed by the in situ generation of Cu(0) from NaBH4 at [NIPAM]o/[I]o = 30 and varying [CuBr2]o/[NaBH4]o from (a) 0.8/0.2 , (b) 0.8/0.4 ■, (c) 0.8/0.6 ▲, (d) 0.8/0.8 ●. (A) Mn determined from SEC using RI and polystyrene standards (dashed lines represent theoretical Mn values), (B) Mn calculated using the Mark-Houwink equation and (C) Mw/Mn values from SEC using the Mark-Houwink equation. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o = 30/1/0.8/0.8. [I]=0.0267 M in 3.48 mL of water.
Figure S5. MALDI-ToF and SEC (RI using polystyrene standards, red line) for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 20/1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
Figure S6. MALDI-ToF and SEC (RI using polystyrene standards, red line) for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
Figure S7. MALDI-ToF and SEC (RI using polystyrene standards, red line) for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 40/1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
Figure S8. MALDI-ToF and SEC (RI using polystyrene standards, red line) for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 50/1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
Figure S9. MALDI-ToF and SEC (RI using polystyrene standards, red line) for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.4. [I]=0.0267 M in 3.48 mL of water.
Figure S10. MALDI-ToF and SEC (RI using polystyrene standards, red line) for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.6. [I]=0.0267 M in 3.48 mL of water.
Figure S11. MALDI-ToF and SEC (RI using polystyrene standards, red line) for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.8. [I]=0.0267 M in 3.48 mL of water.
1112.656
1225.781
0
200
400
600
800
1000
Inte
ns. [
a.u.
]
1075 1100 1125 1150 1175 1200 1225 1250 1275 1300m/z
Cal. [X+ Na]+= 1112.70Exp. [X+ Na]+=1112.656
O
HO
HO
O
NH
S
On
Conv = 27%Time = 20 min
[NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 20/1/0.8/0.8/0.2
1565.094
1678.205
0
200
400
600
800
1000
Inte
ns. [
a.u.
]
1500 1550 1600 1650 1700 1750m/z
Cal. [X+ Na]+=1565.04Exp. [X+ Na]+=1565.094
O
HO
HO
O
NH
S
On
Conv = 46%Time = 40min
2244.647
2357.731
2271.686
0
2000
4000
6000
Inte
ns. [
a.u.
]
2200 2250 2300 2350 2400m/z
Cal. [X+ Na]+=2244.55Exp. [X+ Na]+=2244.647
O
HO
HO
O
NH
S
On
Conv = 72%Time = 60min
2583.9172697.008
0
1000
2000
3000
4000
5000
Inte
ns. [
a.u.
]
2525 2550 2575 2600 2625 2650 2675 2700 2725 2750 2775m/z
Cal. [X+ Na]+=2583.80Exp. [X+ Na]+=2583.917
O
HO
HO
O
NH
S
On
Conv = 95%Time = 100min
(A) (B)
(C) (D)
Figure S12. MALDI-ToF for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 20/1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
1225.8431338.930
1256.961 1306.8440.00
0.25
0.50
0.75
1.00
1.25
1.50
5x10
Inte
ns. [
a.u.
]
1200 1250 1300 1350 1400m/z
Cal. [X+ Na]+= 1225.79Exp. [X+ Na]+=1225.843
O
HO
HO
O
NH
S
On
Conv = 22%Time = 20min
2018.479
2131.576
0
1000
2000
3000
4000
5000
6000
Inte
ns. [
a.u.
]
1950 2000 2050 2100 2150 2200m/z
Cal. [X+ Na]+= 2018.38Exp. [X+ Na]+= 2018.479
O
HO
HO
O
NH
S
On Conv = 45%
Time = 40min
[NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.2
(A) (B)
(C) (D)2923.288
3036.388
2949.283
0
2000
4000
6000
8000
Inte
ns. [
a.u.
]
2850 2900 2950 3000 3050 3100m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+= 2923.05Exp. [X+ Na]+= 2923.288
Conv = 76%Time = 60min
3602.8353715.936
0
2000
4000
6000
8000
Inte
ns. [
a.u.
]
3500 3550 3600 3650 3700 3750 3800m/z
Cal. [X+ Na]+=3602.56Exp. [X+ Na]+=3602.835
O
HO
HO
O
NH
S
On Conv = 99%
Time = 100min
O
HO
HO
O
O ONH OH
n
Figure S13. MALDI-ToF for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
4621.417 4734.562
0.0
0.2
0.4
0.6
0.8
1.04x10
Inte
ns. [
a.u.
]
4600 4700 4800m/z
Cal. [X+ Na]+=4620.31Exp. [X+ Na]+=4621.417
Unknown
O
HO
HO
O
NH
S
On
Conv = 94%Time = 100min
2131.5242244.617
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
2100 2200 2300m/z
Cal. [X+ Na]+=2131.46Exp. [X+ Na]+=2131.524
O
HO
HO
O
NHO ONH
n
Cal. [X+Na+] = 2148.54Exp. [X+Na+] =2147.484
O
HO
HO
O
NH
S
On
Conv = 39%Time = 40min
2810.011 2923.091
0
250
500
750
1000
1250
1500
Inte
ns. [
a.u.
]
2800 2900 3000m/z
Cal. [X+ Na]+=2809.97Exp. [X+ Na]+=2810.011
O
HO
HO
O
NH
S
On
Conv = 57%Time = 60min
1338.9011451.984
0
500
1000
1500
2000
2500
Inte
ns. [
a.u.
]
1300 1400 1500m/z
Cal. [X+ Na]+=1338.87Exp. [X+ Na]+=1338.904
O
HO
HO
O
NHO ONH
n
Cal. [X+Na+] =1355.95Exp. [X+Na+] =1355.910
O
HO
HO
O
NH
S
On Conv = 21%
Time = 20min
[NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 40/1/0.8/0.8/0.2 (A) (B)
(C) (D)
Figure S14. MALDI-ToF for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 40/1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
1905.348
0
1000
2000
3000
4000
5000
Inte
ns. [
a.u.
]
1900 2000m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+=1905.29Exp. [X+ Na]+=1905.348
Conv = 30%Time = 40min
1225.831 1338.910
0
1000
2000
3000
Inte
ns. [
a.u.
]
1200 1300 1400m/z
Cal. [X+ Na]+=1225.79Exp. [X+ Na]+=1225.831
O
HO
HO
O
NH
S
On
Conv = 20%Time = 20min
[NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 50/1/0.8/0.8/0.2
(A) (B)
(C) (D)
2923.120
0
1000
2000
3000
4000
5000
Inte
ns. [
a.u.
]
2800 2900 3000m/z
Cal. [X+ Na]+=2923.05Exp. [X+ Na]+=2923.120
O
HO
HO
O
NHO ONH
n
Cal. [X+Na+] =2827.05Exp. [X+Na+] =2826.032
O
HO
HO
O
NH
S
On
Conv = 46%Time = 60min
4847.988 4961.154
4887.993
0
1000
2000
3000
4000
5000
6000
Inte
ns. [
a.u.
]
4800 4900 5000m/z
Cal. [X+ Na]+= 4846.48Exp. [X+ Na]+= 4847.988
Unknown
O
HO
HO
O
NH
S
On
Conv = 81%Time = 100min
Figure S15. MALDI-ToF for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 50/1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
1565.116
1679.223
1583.211 1646.301
0.0
0.5
1.0
1.5
2.0
4x10
Inte
ns. [
a.u.
]
1525 1550 1575 1600 1625 1650 1675 1700 1725 1750m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+= 1565.04Exp. [X+ Na]+=1565.116
Conv = 80%Time = 10min
[NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.4
(A) (B)
(C) (D)
2810.2042923.297
0
1000
2000
3000
4000
Inte
ns. [
a.u.
]
2775 2800 2825 2850 2875 2900 2925 2950 2975m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+=2809.97Exp. [X+ Na]+=2810.204
Conv = 87%Time = 20min
3489.6773602.786
0
1
2
3
4
5
4x10
Inte
ns. [
a.u.
]
3425 3450 3475 3500 3525 3550 3575 3600 3625 3650 3675m/z
Cal. [X+ Na]+=3488.47Exp. [X+ Na]+=3489.677
O
HO
HO
O
NH
S
On Conv = 99%
Time = 30min
3715.889
3829.001
0.00
0.25
0.50
0.75
1.00
1.25
4x10
Inte
ns. [
a.u.
]
3675 3700 3725 3750 3775 3800 3825 3850 3875m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+=3715.64Exp. [X+ Na]+=3715.889
Conv = 100%Time = 50min
O
HO
HO
O
O ONH OH
n
Figure S16. MALDI-ToF for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.4. [I]=0.0267 M in 3.48 mL of water.
3489.826 3602.936
0
1000
2000
3000
Inte
ns. [
a.u.
]
3450 3500 3550 3600 3650 3700m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+=3488.47Exp. [X+ Na]+=3489.826
Conv = 100%Time = 10min
1905.495 2018.594
0
2000
4000
6000
Inte
ns. [
a.u.
]
1850 1900 1950 2000 2050m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+=1905.29Exp. [X+ Na]+=1905.495 Conv = 98%
Time = 5min
[NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.6
(A) (B)
(C) (D)3376.711 3489.819
0.0
0.2
0.4
0.6
0.8
1.0
4x10
Inte
ns. [
a.u.
]
3350 3400 3450 3500 3550m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+= 3375.39Exp. [X+ Na]+= 3376.711
Conv = 100%Time = 15min
3489.882 3602.986
0
1000
2000
3000
4000
Inte
ns. [
a.u.
]
3400 3450 3500 3550 3600 3650 3700m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+= 3488.47Exp. [X+ Na]+= 3489.882
Conv = 100%Time = 25min
O
HO
HO
O
O ONH OH
n
Figure S17. MALDI-ToF for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.6. [I]=0.0267 M in 3.48 mL of water.
3376.397 3489.481
0.0
0.2
0.4
0.6
0.8
4x10
Inte
ns. [
a.u.
]
3300 3350 3400 3450 3500 3550m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+=3376.39Exp. [X+ Na]+=3376.397
Conv = 100%Time = 3min
[NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.8
(A) (B)
(C) (D)
3376.507 3489.589
0
500
1000
1500
2000
2500
Inte
ns. [
a.u.
]
3350 3400 3450 3500 3550m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+= 3376.39Exp. [X+ Na]+=3376.507
Conv = 100%Time = 6min
3602.616 3715.689
3677.638
0
500
1000
1500
2000
2500
Inte
ns. [
a.u.
]
3550 3600 3650 3700 3750 3800m/z
O
HO
HO
O
NH
S
On
Cal. [X+ Na]+ = 3602.56Exp. [X+ Na]+ = 3602.616
Conv = 100%Time = 9min
Unknown
3602.7433715.842
0
200
400
600
800
Inte
ns. [
a.u.
]
3550 3600 3650 3700 3750m/z
Cal. [X+ Na]+= 3602.56Exp. [X+ Na]+=3602.743
O
HO
HO
O
NH
S
On
Conv = 100%Time = 15 min
Cal. [X+ Na]+ = 3677.64Exp. [X+ Na]+ = 3677.638
O
HO
HO
O
O ONH OH
n
O
HO
HO
O
O ONH OH
n
Figure S18. MALDI-ToF for the aqueous SET-LRP of NIPAM over the conversion range. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.8. [I]=0.0267 M in 3.48 mL of water.
Figure S19. Aqueous SET-LRP of NIPAM catalyzed by the in situ generation of Cu(0) from NaBH4 at [NIPAM]o/[I]o = 30 in the absence and presence of inhibitor MEHQ added to the polymerization mixture after sampling, and varying [CuBr2]o/[NaBH4]o from (a) 0.8/0.6 ● without MEHQ, (b) 0.8/0.6 ● with MEHQ, (c) 0.8/0.4 ■ without MEHQ, (d) 0.8/0.4 *. Reaction conditions: [NIPAM]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o = 30/1/0.8/0.8. [I]=0.0267 M in 3.48 mL of water.
0
20
40
60
80
100
0 20 40 60 80 100
Conv
ersi
on (%
)
Time (min)
[M]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.6
[M]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o= 30/1/0.8/0.8/0.4
MEHQ
MEHQ
without MEHQ
without MEHQ
Figure S20. SEC chromatograms from aqueous SET-LRP of NIPAM catalyzed by the in situ generation of Cu(0) from NaBH4 by varying [NIPAM]o/[I]o from (A) 20/1 , (B) 30/1 , and (C) 40/1. Reaction conditions: [I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water. These SEC chromatograms are based on a polystyrene calibration curve and have not been adjusted using the Mark-Houwink parameters.
0.0E+00
1.0E-03
2.0E-03
3.0E-03
4.0E-03
5.0E-03
6.0E-03
2.3 2.8 3.3
w(M
)
LogMW
0.0E+00
1.0E-03
2.0E-03
3.0E-03
4.0E-03
5.0E-03
6.0E-03
2.3 2.8 3.3
w(M
)
LogMW
0.0E+00
5.0E-04
1.0E-03
1.5E-03
2.0E-03
2.5E-03
3.0E-03
2.3 2.8 3.3 3.8
w(M
)
LogMW
(A)
(B)
(C)
Increasing conversion
Increasing conversion
Increasing conversion
Figure S21. UV-vis spectra (measured in the 500-900 nm range) at the end of the aqueous SET-LRP of NIPAM polymerization before and after opening and bubbling with air for 1 min. (A) [M]0/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.4, and (B) [M]0/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.8. Reaction conditions: [I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 1/0.8/0.8/0.2. [I]=0.0267 M in 3.48 mL of water.
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
500 550 600 650 700 750 800 850 900
Abso
rban
ce
Wavelength (nm)
before added air
after added air
0
0.5
1
1.5
2
2.5
3
3.5
4
500 550 600 650 700 750 800 850 900
Abso
rban
ce
Wavelength (nm)
before added air
after added air
(A)
(B)
[M]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.4
[M]o/[I]o/[Me6TREN]o/[Cu(II)Br2]o/[NaBH4]o = 30/1/0.8/0.8/0.8
Recommended