Electronic Supplementary Material (ESI) for Polymer Chemistry
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Supporting Information to
Reversible-Deactivation
Radical
Polymerization
Mediated
by
CuSO4•5H2O: an Alternative and Promising Copper(II)-Based Catalyst
Junfei Zhao, Wenxiang Wang, Liangjiu Bai, Lili Zhou, Zhenping Cheng, Zhengbiao Zhang*, Xiulin Zhu*
Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of
Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science,
Soochow University, Suzhou, 215123, P. R. China.
E-mail: [email protected] (Zheng B. Zhang) or [email protected] (Xiu L. Zhu)
Experimental part:
Materials
Methyl methacrylate (MMA) (>99%), methyl acrylate (MA) (>99%), styrene (St) (>99%), were
purchased from Shanghai Chemical Reagents Co. (Shanghai, China). The monomers were washed three
times with an aqueous solution of sodium hydroxide (5%wt), followed by washes with deionized water
until the solution was neutralized. The resulting solution was then dried over anhydrous magnesium
sulfate, distilled twice at reduced pressure, 2-(dimethylamino)ethyl methacrylate (DMAEMA) (>99%)
was purchased from Aldrich, it was passed through basic alumina columns, then vacuum-distilled from
CaH2, and all of them were stored at -18 oC. N,N,N’,N”,N”-pentamethyldiethylenetriamine (PMDETA)
(98%, Jiangsu Liyang Jiangdian Chemical Factory, China) was dried with 4 Å molecular sieves and
distilled under vacuum. Tris-(2-dimethylaminoethyl) amine (Me6TREN) was synthesized as described in
the literature.1 2,2′-bipyridine (bpy) (99%), and tri(3,6-dioxaheptyl) amine (TDA-1) (97%) were
purchased from Shanghai Chemical Reagents and used as received. Zero-valent iron powder (Fe(0), <200
mesh, 99%, metals basis), and iron wire (99.9%) were purchased from Alfa Aesar and used as received.
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Copper(II) suflate pentahydrate (CuSO4∙5H2O) (99%), copper(II) bromide (CuBr2, 98.5%), ascorbic acid
(AA) (99.9%, Shanghai guanghua Chemical Factory, China), 2,2-dichloroacetophenone (DCAP) (97%,
Alfa Aesar Co.), methyl 2-bromopropionate (MBP) (97%, Alfa Aesar Co.), ethyl 2-bromoisobutyrate
(EBiB) (98%, Acros), methyl alpha-bromophenylacetate (MBPA) (97%, J & K Scientific LTD.),
dimethyl sulfoxide (DMSO) (99.9%, Shanghai Chemical Reagents Co.), N,N-dimethylformamide (DMF)
(99.9%, Shanghai Chemical Reagents Co.), N-methyl-2-pyrrolidone (NMP) (98%, Sinopharm Chemical
Reagents Co.), toluene (99.5%, Nanjing Chemical Reagents Co.) and anisole (98%, Sinopharm Chemical
Reagents Co.) were used as received. All other chemicals were obtained from Shanghai Chemical
Reagents Co. and used as received unless mentioned.
Characterization
The number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the polymers
were determined using a Waters 1515 size exclusion chromatography (SEC) equipped with a
refractive-index detector (Waters 2412), using HR 1 (pore size: 100 Å, 100-5000 Da), HR 2 (pore size:
500 Å, 500-20,000 Da), and HR 4 (pore size 10,000 Å, 50-100 000 Da) columns (7.8 × 300 mm, 5 µm
beads size) with molecular weights ranging from 0.1 to 500 kg/mol. For PMMA, PMA and PS samples,
THF was used as the eluent at a flow rate of 1.0 mL/min and 30 oC. SEC samples were injected using a
Waters 717 plus autosampler and calibrated with poly(methylmethacrylate) standards for PMMA, PMA
and PDMAEMA and poly(styrene) standards for PS purchased from Waters. The apparent SEC values
were subjected to correction by using Mark–Houwink–Kuhn–Sakurada (MHKS) parameters with
equation: Log(MWMA) = 0.105+0.956Log(MWMMA).2 For PDMAEMA samples, DMF was used as the
eluent at a flow rate of 1.0 mL/min and 35 oC. The apparent SEC values were subjected to correction by
multiplying of an approximate factor of 1.5 according to literature.3 The 1H NMR spectrum of the
Electronic Supplementary Material (ESI) for Polymer Chemistry
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precipitated polymer was recorded on an INOVA 400 MHz nuclear magnetic resonance instrument using
CDCl3 as the solvent and tetramethylsilane (TMS) as an internal standard. The UV-vis spectra were
recorded on a Shimadzu UV-3150 spectrophotometer.
The UV-Vis spectroscopic analyses of Fe/CuSO4∙5H2O/PMDETA complex in DMSO at different
time
Fe(0) (1.3 mg), CuSO4∙5H2O (2.9 mg) and PMDETA (4.9 μL) were placed in a quartz UV-vis cell (1 mm
path length), And another, without Fe(0), that is CuSO4∙5H2O (2.9 mg) and PMDETA (4.9 μL), then
supplement to 3 mL with dimethyl sulfoxide (DMSO) for each, all systems were deoxygenated. After
vigorous shaking, the cells were placed in the UV-vis spectrometer for measurement. Then the cells were
put into a water bath equipped with a thermostat at 25 ± 1 oC for reaction and get out for measurement
after a preset time, the absorbance was recorded in the 200-900 nm range.
Typical procedures for the polymerization of MMA
A
typical
polymerization
procedure
with
DMSO
as
the
solvent
for
the
ratio
of
[MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/1/0.5/1 is as follows. The monomer
(MMA, 1.0 mL, 9.4 mmol), solvent (DMSO, 1.0 mL), initiator (DCAP, 6.7 μL, 0.0472 mmol), catalyst
(CuSO4∙5H2O, 5.9 mg, 0.0236 mmol), and ligand (PMDETA, 9.8 μL, 0.0472 mmol), reducing agent
(Fe(0), 2.6 mg, 0.0472 mmol) were added to a 5.0 mL ampule in the following order: catalyst, monomer,
ligand, solvent, initiator, and then reductant. The solution deoxygenated with six standard freeze - pump thaw cycles. The ampoule was then flame sealed and placed in a stirred water bath equipped with a
thermostat at 25 ± 1 oC. After 2.5 hours, the ampule was cooled by immersion in ice water. Afterward, the
ampule was opened, and the contents were dissolved in 5.0 mL of THF and passed through a small basic
Al2O3 chromatographic column to remove Cu and Fe compounds. The resulting solution was precipitated
into 200 mL of cold methanol with stirring. The polymer was isolated by filtration and dried under
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vacuum until a constant weight was recorded at room temperature. The monomer conversion was 35.7%
determined by gravimetrical calculation. The Mn and Mw/Mn values were determined by SEC (THF) with
poly(methylmethacrylate) (PMMA) standards (Mn,SEC = 12.8 kg/mol, Mw/Mn = 1.31).
Chain extension with PMMA as a macroinitiator
A predetermined quantity of obtained PMMA was added to a dried ampoule and then the predetermined
quantity of MMA, Fe(0), CuSO4·5H2O, PMDETA and DMSO was added. The polymerization
temperature was then stabilized at 25 ± 1 oC. The rest of the procedure was identical to that described
earlier except that DCPA replaced by obtained PMMA.
[MMA]0/[EBiB]0/[CuSO4·5H2O]0/[PMDETA]0/[AA]0= 200/1/1/1/2
(a)
[MMA]0/[EBiB]0/[CuSO4·5H2O]0/[PMDETA]0/[AA]0= 200/1/1/1/0
3.0
2.0
1.5
app
1.0
kp =0.071h
Mn,SEC (kg/mol)
ln[M]0/[M]
-1
Mw/Mn
app
kp =0.690h
2.5
-1
0.5
0.0
0
5
10
15
Time (h)
20
[MMA]0/[EBiB]0/[CuSO4·5H2O]0/[PMDETA]0/[AA]0= 200/1/1/1/2
(b)
[MMA]0/[EBiB]0/[CuSO4·5H2O]0/[PMDETA]0/[AA]0= 200/1/1/1/0
2.0
1.8
1.6
1.4
1.2
36.0
30.0
24.0
18.0
12.0
6.0
0.0
25
0
20
0
20
Mn,SEC = 17.1 kg/mol, Mw/Mn= 1.32
(c)
40
60
40
60
Conversion (%)
Mn,SEC = 13.2 kg/mol, Mw/Mn= 1.22
Mn,SEC = 16.6 kg/mol, Mw/Mn= 1.26
Mn,SEC = 13.9 kg/mol, Mw/Mn= 1.22
(d)
Mn,SEC = 17.9 kg/mol, Mw/Mn= 1.28
Mn,SEC = 15.3 kg/mol, Mw/Mn= 1.30
Mn,SEC = 18.8 kg/mol, Mw/Mn= 1.26
Mn,SEC = 17.6 kg/mol, Mw/Mn= 1.24
Mn,SEC = 21.6 kg/mol, Mw/Mn= 1.25
Mn,SEC = 21.6 kg/mol, Mw/Mn= 1.22
Mn,SEC = 22.8 kg/mol, Mw/Mn= 1.29
Mn,SEC = 22.3 kg/mol, Mw/Mn= 1.21
Mn,SEC = 26.7 kg/mol, Mw/Mn= 1.30
Mn,SEC = 29.3 kg/mol, Mw/Mn= 1.20
Mn,SEC = 28.2 kg/mol, Mw/Mn= 1.36
3.6
4.0
4.4
Slice LogMW
4.8
5.2
3.2
3.6
4.0
4.4
Slice LogMW
4.8
80
100
80
100
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Mn,SEC = 24.2 kg/mol, Mw/Mn= 1.70
(e)
Mn,SEC = 13.0 kg/mol, Mw/Mn= 1.08
Mn,SEC = 19.4 kg/mol, Mw/Mn= 1.69
Mn,SEC = 18.8 kg/mol, Mw/Mn= 1.57
3.2
Mn,SEC = 17.8 kg/mol, Mw/Mn= 1.14
(f)
Mn,SEC = 19.9 kg/mol, Mw/Mn= 1.70
Mn,SEC = 19.7 kg/mol, Mw/Mn= 1.15
Mn,SEC = 18.7 kg/mol, Mw/Mn= 1.42
Mn,SEC = 26.3 kg/mol, Mw/Mn= 1.23
Mn,SEC = 20.3 kg/mol, Mw/Mn= 1.36
Mn,SEC = 31.5 kg/mol, Mw/Mn= 1.33
Mn,SEC = 27.4 kg/mol, Mw/Mn= 2.42
Mn,SEC = 34.7 kg/mol, Mw/Mn= 1.44
4.0
4.8
Slice LogMW
5.6
6.4
3.6
4.0
4.4
4.8
Slice LogMW
5.2
Fig. S1. (a) Kinetic investigation (ln([M]0/[M]) versus time) of methyl methacrylate (MMA) with toluene
as solvent at various concentrations of AA. [MMA]0 = 4.71mol/L, MMA/toluene = 1/1 (v/v), temperature
= 80 oC. [M]0 and [M] refer to the initial concentration of MMA and instant concentration of MMA,
respectively. kpapp refer to apparent rate constant of propagation. (b) Number average molecular weight
(Mn) and molecular weight distribution (Mw/Mn) of poly(methylmethacrylate) (PMMA) versus the
conversion
of
MMA
at
various
concentrations
[MMA]0/[EBiB]0/[CuSO4·5H2O]0/[PMDETA]0/[AA]0
[MMA]0/[EBiB]0/[CuSO4·5H2O]0/[PMDETA]0/[AA]0
=
=
200/1/1/1/1
of
AA.
200/1/1/1/2.
(Fig.
(c)
(d)
1).
(e)
[MMA]0/[EBiB]0/[CuSO4·5H2O]0/[PMDETA]0/[AA]0 = 200/1/1/1/0. (f) [MMA]0/[EBiB]0/[CuBr2]0
/[PMDETA]0/[AA]0 = 200/1/1/1/1 (Fig. 2). Theoretical molecular weight Mn,th = ([MMA]0/[EBiB]0) ×
MMMA × Conversion + MEBiB.
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Table S1. The compared chain end functionalization degrees (FD) of polymers mediated by CuSO4·5H2O
and CuBr2.
Time
Entry
a
Catalyst
Mn,SEC
Mn,NMR
Con. (%)
(h)
Mw/Mn
FD
(kg/mol)
(kg/mol)
1
CuSO4·5H2O
1.0
19.7
13.2
1.22
6.9
0.527
2
CuSO4·5H2O
1.25
24.4
13.9
1.22
8.8
0.630
3
CuSO4·5H2O
2.0
47.3
15.3
1.30
9.2
0.602
4
CuSO4·5H2O
4.0
81.9
22.3
1.21
19.9
0.894
5
CuBr2
0.5
24.7
13.0
1.08
7.0
0.535
6
CuBr2
0.67
41.7
17.8
1.14
11.5
0.646
7
CuBr2
0.83
48.9
19.7
1.15
13.5
0.687
8
CuBr2
3
82.4
34.7
1.44
19.1
0.552
a)
[MMA]0/[EBiB]0/[Catalyst]0/[PMDETA]0/[AA]0 = 200/1/1/1/1, MMA = 1.0 mL; toluene = 1.0 mL, the
polymerization temperature was 80 oC for all cases. MMA = methyl methacrylate; EBiB = ethyl
2-bromoisobutyrate; PMDETA = N,N,N’,N”,N”-pentamethyldiethylenetriamine. Mn,SEC and Mw/Mn refer
to the number-average molecular weight and molecular weight distribution by SEC, respectively. Mn,NMR
refer to the number-average molecular weight by 1H NMR. FD = Mn,NMR/Mn,SEC.
1.8
app
ln[M]0/[M]
kp =0.267h
1.2
-1
app
kp =0.136h
-1
0.6
0.0
0
3
6
9
Time (h)
12
15
[MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/1/1/1
(b)
[MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/0.5/1/1
Mw/Mn
[MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/0.5/1/1
Mn,SEC (kg/mol)
[MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/1/1/1
(a)
1.80
1.65
1.50
1.35
1.20
1.05
30.0
24.0
18.0
12.0
6.0
0.0
0
20
0
20
40
60
40
60
Conversion (%)
80
100
80
100
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Mn,SEC = 13.6 kg/mol, Mw/Mn = 1.32
(a)
Mn,SEC = 16.0 kg/mol, Mw/Mn= 1.12
(c)
Mn,SEC = 12.8 kg/mol, Mw/Mn = 1.31
Mn,SEC = 14.8 kg/mol, Mw/Mn = 1.48
Mn,SEC = 24.9 kg/mol, Mw/Mn = 1.31
Mn,SEC = 31.5 kg/mol, Mw/Mn = 1.18
3.2
3.6
4.0
4.4
Slice LogMW
4.8
Mn,SEC = 19.2 kg/mol, Mw/Mn = 1.21
(d)
Mn,SEC = 16.3 kg/mol, Mw/Mn= 1.28
Mn,SEC = 14.4 kg/mol, Mw/Mn = 1.32
Mn,SEC = 17.4 kg/mol, Mw/Mn= 1.31
Mn,SEC = 14.3 kg/mol, Mw/Mn = 1.46
Mn,SEC = 18.4 kg/mol, Mw/Mn= 1.27
Mn,SEC = 16.8 kg/mol, Mw/Mn = 1.24
Mn,SEC = 18.9 kg/mol, Mw/Mn= 1.33
Mn,SEC = 18.3 kg/mol, Mw/Mn = 1.21
Mn,SEC = 24.5 kg/mol, Mw/Mn= 1.22
5.2
3.6
4.0
4.4
Slice LogMW
4.8
3.6
5.2
4.0
4.4
Slice LogMW
4.8
5.2
Fig. S2. (a) Kinetic investigation (ln([M]0/[M]) versus time) of methyl methacrylate (MMA) with DMSO
as solvent. [MMA]0 =4.71mol/L, MMA/DMSO = 1/1 (v/v), temperature = 25 oC. [M]0 and [M] refer to
the initial concentration of MMA and instant concentration of MMA, respectively. kpapp refer to apparent
rate constant of propagation. (b) Number average molecular weight (Mn) and molecular weight
distribution (Mw/Mn) of poly(methylmethacrylate) (PMMA) versus the conversion of MMA at various
molar ratios of [Fe(0)]0/[CuSO4·5H2O]0. (c) [MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 =
200/1/1/0.5/1.
(d)
[MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0
=
200/1/1/1/1.
(e)
[MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/0.5/1/1. Theoretical molecular weight
Mn,th = ([MMA]0/[DCAP]0) × MMMA × Conversion + MDCAP.
d
c
b
a
Cl
C
b a
c
C
H
O
e
H2
C
O
f
e
OCH3
d
8.10
7.95
7.80
7.65
5.0
7.50
e
OCH3
g
f
g
234.8
7.5
f
CH 3
CH 3
H2
C C C Cl
n
C O C
147.1 221.6
6.0
4.5
3.0
1.5
Chemical Shift (ppm)
0.0
Fig. S3. 1H NMR spectrum of poly (methyl methacrylate) (PMMA, Mn,SEC = 9.9 kg/mol, Mw/Mn = 1.25)
obtained from [MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/1/0.5/1. CDCl3 was used
as the solvent and tetramethylsilane (TMS) as the internal standard. Mn,SEC and Mw/Mn refer to the
number-average molecular weight and molecular weight distribution by SEC, respectively.
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original PMMA, Mn,SEC = 9.8 kg/mol, Mw/Mn = 1.25
chain extended PMMA, Mn,SEC = 71.2 kg/mol, Mw/Mn = 1.50
3.6
4.0
4.4
4.8
5.2
5.6
6.0
Slice logMW
Fig. S4. SEC curves before and after chain extension in DMSO with poly (methyl methacrylate) (PMMA)
(obtained from [MMA]0/[DCAP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/1/0.5/1) as the
macro-initiator
at
25
o
C.
The
condition
of
the
chain-extension:
[MMA]0/[PMMA]0
/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 500/1/3/5/6, [MMA]0 = 1.95 mol/L, MMA = 0.26 mL, DMSO =
1.0 mL, 6 h, 64.2% conversion.
Table S2. Polymerizations of St and MA under various conditions. a)
Monomer
Entry
initiator
catalyst
Ligand
solvent
(equiv)
Con.
Mn,SEC
Time (h)
(equiv)
(equiv)
(equiv)
Mn,th
Mw/Mn
(%)
(kg/mol)
(kg/mol)
1
St (200)
DMSO
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
TDA -1(1)
12.0
2.9
38.7
1.92
0.7
2
St (200)
DMSO
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
TDA -1(1)
112.0
49.6
31.9
2.29
10.1
3
St (200)
DMF
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
24.0
14.4
3.6
1.12
3.1
4
St (200)
DMF
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
124.0
44.7
10.4
1.19
9.5
5
St (200)
NMP
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
32.0
15.2
3.8
1.73
3.2
6
St (200)
NMP
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
96.0
40.2
6.4
1.29
8.2
7
St (200)
anisole
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
57.0
32.3
6.4
1.27
6.6
8
St (200)
anisole
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
95.0
35.5
9.5
1.73
7.3
9
St (200)
toluene
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
57.0
14.3
4.0
1.24
3.0
10
St (200)
toluene
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
167.0
39.6
8.6
1.16
8.1
11
MA (200)
DMSO
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
TDA-1 (1)
8.0
23.3
45.7
1.98
3.8
12
MA (200)
DMSO
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
TDA-1 (1)
32.0
59.2
50.1
1.78
10.4
13
MA (200)
DMF
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
6.0
36.6
17.3
1.59
6.5
14
MA (200)
DMF
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
12.0
65.7
14.4
1.41
11.4
15
MA (200)
NMP
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
1.0
36.9
95.5
1.52
6.5
16
MA (200)
NMP
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
6.0
88.6
102.3
1.47
15.4
17
MA (200)
anisole
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
32
0.0
---
---
---
18
MA (200)
anisole
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
298
0.0
---
---
---
19
MA (200)
toluene
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
32
0.0
---
---
---
20
MA (200)
toluene
MBP (1)
Fe(0)/CuSO4·5H2O (1/0.5)
PMDETA (1)
298
0.0
---
---
---
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a)
All polymerizations were conducted with MA (or St) = 1.0 mL, temperature = 25 oC, solvent = 1.0 mL.
MA = methyl acrylate; St = styrene;
MBP = methyl 2-bromopropionate; PMDETA =
N,N,N’,N”,N”-pentamethyldiethylenetriamine; TDA-1 = tris-(3,6-dioxa-heptyl) amine; DMSO =
dimethyl sulfoxide; DMF = N,N-dimethylformamide; NMP = N-methyl-2-pyrrolidone. Mn,SEC and Mw/Mn
refer to the number-average molecular weight and molecular weight distribution by SEC, respectively.
Mn,th (PMA) = ([MA]0/[MBP]0) × MMMA × Conversion + MMBP; Mn,th (PSt) = ([St]/[MBP]0) × MSt ×
Conversion + MMBP.
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200/1/1/0.5/1
(a)
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200: 1: 0.5: 1: 1
1.6
1.8
0.6
0.0
0
10
20
30
Time (h)
40
50
Mn,SEC = 10.9 kg/mol, Mw/Mn = 1.14
20
20
40
60
40
60
Conversion (%)
80
100
80
100
Mn,SEC = 11.4 kg/mol; Mw/Mn = 1.12
Mn,SEC = 11.5 kg/mol, Mw/Mn = 1.08
(b)
Mn,SEC = 13.2 kg/mol, Mw/Mn = 1.09
3.6
1.2
Mn,SEC = 11.5 kg/mol, Mw/Mn = 1.11
Mn,SEC = 12.8 kg/mol, Mw/Mn = 1.13
(a)
1.4
1.0
0
24.0
18.0
12.0
6.0
0.0
0
1.2
Mn,SEC (kg/mol)
ln([M]0/[M])
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200: 1: 1: 1: 1
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200/1/0.5/1/1
Mw/Mn
2.4
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200: 1: 1: 0.5: 1
(b)
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200/1/1/1/1
(c)
Mn,SEC = 12.0 kg/mol, Mw/Mn = 1.08
Mn,SEC = 11.2 kg/mol; Mw/Mn = 1.20
Mn,SEC = 12.3 kg/mol; Mw/Mn = 1.10
Mn,SEC = 13.8 kg/mol, Mw/Mn = 1.09
Mn,SEC = 13.8 kg/mol, Mw/Mn = 1.11
Mn,SEC = 12.8 kg/mol; Mw/Mn = 1.09
Mn,SEC = 18.6 kg/mol, Mw/Mn = 1.20
Mn,SEC = 14.1 kg/mol, Mw/Mn = 1.08
Mn,GPC = 14.8 kg/mol; Mw/Mn = 1.05
4.0
4.4
Slice LogM W
4.8
5.2
3.6
4.0
4.4
3.6
4.8
4.0
4.4
4.8
Slice LogM W
Slice LogM W
Fig. S5. (a) Kinetic investigation (ln([M]0/[M]) versus time) of methyl acrylate (MA) with DMSO as
solvent. [MA]0 =5.55mol/L, MA/DMSO = 1/1 (v/v), temperature = 25 oC. [M]0 and [M] refer to the initial
concentration of MA and instant concentration of MA, respectively. (b) Number average molecular
weight (Mn) and molecular weight distribution (Mw/Mn) of poly(methyl acrylate) (PMA) versus the
conversion
of
MA
at
various
molar
ratios
of
[Fe(0)]0/[CuSO4·5H2O]0.
(c)
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0
=
200/1/1/0.5/1
(d)
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0
=
200/1/1/1/1.
(e)
[MA]0/[MBP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/0.5/1/1. Theoretical molecular weight Mn,th
= ([MA]0/[MBP]0) × MMA × Conversion + MMBP.
Electronic Supplementary Material (ESI) for Polymer Chemistry
This journal is © The Royal Society of Chemistry 2012
[St]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200: 1: 1: 0.5: 1
[St]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200/1/1/0.5/1
(a)
(b)
[St]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200/1/1/1/1
Mw/Mn
1.50
1.35
1.20
1.05
Mn,SEC(kg/mol)
[St]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200/1/0.5/1/1
18.0
12.0
6.0
0.0
1.2
ln([M]0/[M])
0.9
0.6
0.3
0.0
0
(a)
20
40
60
80
Time (h)
100
120
[St]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200: 1: 0.5: 1: 1
0
20
0
20
Mn,SEC = 2.2 kg/mol, Mw/Mn = 1.08
Mn,SEC = 9.8 kg/mol, Mw/Mn = 1.28
Mn,SEC = 3.3 kg/mol, Mw/Mn = 1.09
Mn,GPC = 4.9 kg/mol, Mw/Mn = 1.09
Mn,SEC = 4.5 kg/mol, Mw/Mn = 1.09
Mn,SEC = 5.7 kg/mol, Mw/Mn = 1.10
(b)
Mn,SEC = 6.5 kg/mol, Mw/Mn = 1.10
3.2
3.6
4.0
Slice LogM W
40
60
40
60
Conversion (%)
4.4
3.2
4.0
100
80
100
Mn,SEC = 2.5 kg/mol, Mw/Mn = 1.06
Mn,SEC = 3.6 kg/mol, Mw/Mn = 1.09
(c)
Mn,SEC = 8.0 kg/mol, Mw/Mn = 1.15
3.6
80
Mn,SEC = 2.8 kg/mol, Mw/Mn = 1.08
Mn,SEC = 4.8 kg/mol, Mw/Mn = 1.09
Mn,SEC = 5.4 kg/mol, Mw/Mn = 1.09
Mn,SEC = 6.7 kg/mol, Mw/Mn = 1.11
Mn,SEC = 12.2 kg/mol, Mw/Mn = 1.25
2.8
[St]0/[MBP]0/[Fe(0)]0/[CuSO4.5H2O]0/[PMDETA]0 = 200: 1: 1: 1: 1
4.4
3.2
Slice LogM W
3.6
Slice LogM W
4.0
Fig. S6. (a) Kinetic investigation (ln([M]0/[M]) versus time) of styrene (St) with DMSO as solvent. [St]0
=4.35mol/L, St/DMSO = 1/1 (v/v), temperature = 25 oC. [M]0 and [M] refer to the initial concentration of
St and instant concentration of St, respectively. (b) Number average molecular weight (Mn) and molecular
weight distribution (Mw/Mn) of poly(styrene) (PSt) versus the conversion of St at various molar ratios of
[Fe(0)]0/[CuSO4·5H2O]0. (c) [St]0/[MBP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0 = 200/1/1/0.5/1 (d)
[St]0/[MBP]0/[Fe(0)]0/[CuSO4·5H2O]0/[PMDETA]0
=
200/1/1/1/1.
(e)
[St]0/[MBP]0/[Fe(0)]0/[CuSO4·5H2O]0 /[PMDETA]0 = 200/1/0.5/1/1. Theoretical molecular weight Mn,th =
([St]0/[MBP]0) × MSt × Conversion + MMBP.
Electronic Supplementary Material (ESI) for Polymer Chemistry
This journal is © The Royal Society of Chemistry 2012
CH3 c d
H2 H
C C C nBr
H
O C
b
H 3C
O
a
C
O
OCH3
b
a
c
d
3.0
320.3
4.0
221.5
108.2
3.2
2.4
1.6
0.8
Chamical Shifts (ppm)
0.0
Fig. S7. 1H NMR spectrum of poly (methyl acrylate) (PMA, Mn,SEC = 13.2 kg/mol, Mw/Mn = 1.12)
obtained from the Fe(0)/CuSO4.5H2O mediated polymerization. CDCl3 was used as the solvent and
tetramethylsilane (TMS) as the internal standard. Mn,SEC and Mw/Mn refer to the number-average
molecular weight and molecular weight distribution by SEC, respectively.
a
b
O
H3C O
C
c
CH 3
C
H
d
f
H2 H H 2 H
C C n C C Br
e
a
a
d
f
284.7
7.5
2.0
b
3.0
e
c
1.1 169.2 3.4
6.0
4.5
3.0
1.5
Chemical Shifts (ppm)
0.0
Fig. S8. 1H NMR spectrum of poly (styrene) (PSt, Mn,SEC = 6.5 kg/mol, Mw/Mn = 1.10) obtained from
the Fe(0)/CuSO4.5H2O mediated polymerization. CDCl3 was used as the solvent and tetramethylsilane
Electronic Supplementary Material (ESI) for Polymer Chemistry
This journal is © The Royal Society of Chemistry 2012
(TMS) as the internal standard. Mn,SEC and Mw/Mn refer to the number-average molecular weight and
molecular weight distribution by SEC, respectively.
original PMA, Mn,SEC = 13.2 kg/mol, Mw/Mn = 1.12
chain extended PMA, Mn,SEC = 43.6 kg/mol, Mw/Mn = 1.23
4.0
4.4
4.8
Slice LogMW
5.2
Fig. S9. SEC curves before and after chain extension in DMSO with poly (methyl acrylate) (PMA) as the
macro-initiator
at
25
o
C.
The
condition
of
the
chain-extension:
[MA]0/[PMA]0/[Fe(0)]0
/[CuSO4.5H2O]0/[PMDETA]0 = 450/1/4/2/5, [MA]0 = 1.85 mol/L, MA = 0.2 mL, DMSO = 1.0 mL, 10 h,
80.2% conversion.
original PSt, Mn,SEC = 6.5 kg/mol, Mw/Mn = 1.10
chain extended PSt, Mn,SEC = 11.1 kg/mol, Mw/Mn = 1.42
3.2
3.6
4.0
Slice LogMW
4.4
4.8
Fig. S10. SEC curves before and after chain extension in DMSO with poly styrene (PSt) as the
macro-initiator
at
25
o
C.
The
condition
of
the
chain-extension:
[St]0/[PSt]0/[Fe(0)]0
Electronic Supplementary Material (ESI) for Polymer Chemistry
This journal is © The Royal Society of Chemistry 2012
/[CuSO4.5H2O]0/[PMDETA]0 = 450/1/4/2/5, [St]0 = 1.51 mol/L, St = 0.2 mL, DMSO = 1.0 mL, 10 h,
10.2% conversion.
1.5
Abs
(b)
0min
10min
110min
130min
150min
170min
210min
230min
290min
300min
2.0
1.0
1.0
0.5
0.5
0.0
0.0
300
400
500
600
700
Wavelength(nm)
0min
30min
60min
90min
120min
150min
180min
210min
240min
270min
300min
330min
2.0
1.5
Abs
(a)
800
300
400
500
600
700
Wavelength(nm)
800
Fig. S11. (a) UV-Vis spectra of [Fe(0)]0/[CuSO4·5H2O]0 /[PMDETA]0 = 0.024/0.012/0.024 in DMSO
changed over time; (b) UV-Vis spectra of [CuSO4·5H2O]0/[PMDETA]0 = 0.012/0.024 in DMSO changed
over time. Solvent = 3.0 mL, T = 25 oC. PMDETA = N,N,N’,N”,N”-pentamethyldiethylenetriamine;
DMSO = dimethyl sulfoxide.
References
1 M. Ciampolini and N. Nardi, Inorg. Chem. 1966, 5, 41–44.
2 T. Gruendling, T. Junkers, M. Guilhaus, C. Barner-Kowollik, Macromol. Chem. Phys. 2010, 211, 520.
3 M. Sahnoun, M. Charreyre, L. Veron, T. Delair, F. D’agosto, J. Polym. Sci., Part A: Polym. Chem.
2005, 43, 3551.