Supporting Information
Copolymerization of 2-Isothiocyanatoethyl Methacrylate and 2-Hydroxyethyl Methacrylate or
Methacrylic Acid Based on a Nucleophile-Tolerant Property of the Isothiocyanato Group
Ryota Seto,1 Kozo Matsumoto,1,2 Takeshi Endo*1
1
Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka Prefecture
820-8555, Japan
2
Department of Biological & Environmental Chemistry, Kinki University, 11-6 Kayanomori, Iizuka,
Fukuoka Prefecture 820-8555, Japan
*Correspondence to: T. Endo (E-mail: tendo@moleng.fuk.kindai.ac.jp)
Contents
I. Reactivity of Isothiocyanate with ethanol
II. Reactivity of Isothiocyanate with acetic acid
III. Copolymer composition curve of poly(ITEMA-co-HEMA)
IV. Copolymer composition curve of poly(ITEMA-co-MAA)
V. Original spectra of copolymers
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I. Reactivity of Isothiocyanate with ethanol or acetic acid
To a NMR tube, ITEMA 10.3 mg (0.06 mmol), ethanol 3.5 μL (27.6 mg, 0.60 mmol, 10 eq.), acetone-d6
565 μL (0.1 mol/L) were charged and heated to 60 °C.
Figure S1 showed time evolution of 1H NMR
spectra of the reaction mixture.
Figure S1.
1
H NMR spectra of ITEMA with ethanol (400 MHz, acetone-d6, 293 K).
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II. Reactivity of Isothiocyanate with acetic acid
To a NMR tube, ITEMA 10.3 mg (0.06 mmol), acetic acid 34 μL (36.0 mg, 0.60 mmol, 10 eq.),
acetone-d6 566 μL (0.1 mol/L) were charged and heated to 60 °C.
1
Figure S2 showed time evolution of
H NMR spectra of the reaction mixture.
Figure S2.
1
H NMR spectra of ITEMA with acetic acid (400 MHz, acetone-d6, 293 K).
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III. Copolymer composition curve of poly(ITEMA-co-HEMA)
To discus the copolymerization characteristics between ITEMA and HEMA, copolymer composition
curve was drawn in Figure S3.
To get the copolymer compositions of lower conversion,
copolymerization was quenched at 40 minutes.
with various monomer compositions.
Table S1 shows the results of the copolymerizations
Monomer conversions were determined by 1H NMR measurement
of the copolymerization mixtures and ITEMA/HEMA ratios of the copolymer were determined by 1H
NMR measurement of the isolated copolymers.
It was confirmed that the copolymers of ITEMA and
HEMA are random copolymers by plotting a copolymer composition curve at low monomer conversions.
Isothiocyanato group is placed at far away from polymerize vinyl group, so Q value and e value of
ITEMA may be similar to HEMA or methyl methacrylate (MMA).
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Table S1.
Results of copolymerizations of ITEMA and HEMA (low conversion).
feed ratioa
copolymer compositiona,b
monomer conversiona
isolated
run
a
ITEMA
HEMA
ITEMA
HEMA
ITEMA
HEMA
(mol%)
(mol%)
(mol%)
(mol%)
(mol%)
(mol%)
1
91
9
89
11
10
18
10
2
78
22
76
24
11
17
10
3
51
49
48
52
9
18
11
4
28
72
22
78
12
21
11
5
18
83
9
91
8
19
11
Determined by 1H NMR.
Figure S3.
b
yield (%)b
Diethyl ether-insoluble part.
Copolymer composition curve of poly(ITEMA-co-HEMA).
Measured copolymer
composition of ITEMA in poly(ITEMA-co-HEMA) (red dots) and ideal copolymerization line (blue line).
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IV. Copolymer composition curve of poly(ITEMA-co-MAA)
To discus the copolymerization characteristics between ITEMA and MAA, copolymer composition curve
was drawn in Figure S4.
To get the copolymer compositions of lower conversion, copolymerization
was quenched at 40 minutes.
compositions.
Table S2 shows the results of the copolymeriztions with various monomer
Monomer conversions were determined by
1
H NMR measurement of the
copolymerization mixtures and ITEMA/MAA ratios of the copolymer were determined by 1H NMR
measurement of the isolated copolymers.
It was confirmed that the copolymers of ITEMA and HEMA
are random copolymers by plotting a copolymer composition curve at low monomer conversions.
6/17
Table S2.
Results of copolymerizations of ITEMA and MAA (low conversion).
feed ratioa
copolymer compositiona,b
monomer conversiona
isolated
run
a
ITEMA
MAA
ITEMA
MAA
ITEMA
MAA
(mol%)
(mol%)
(mol%)
(mol%)
(mol%)
(mol%)
1
89
11
93
7
19
12
15
2
78
22
82
18
22
16
16
3
49
51
56
44
25
17
20
4
24
76
32
68
23
17
12
5
12
88
26
74
14
12
12
Determined by 1H NMR.
Figure S4.
b
yield (%)b
Diethyl ether-insoluble part.
Copolymer composition curve of poly(ITEMA-co-MAA).
Measured copolymer
composition of ITEMA in poly(ITEMA-co-MAA) (red dots) and ideal copolymerization line (blue line).
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V.
Original spectra of copolymers
Figure S5.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-HEMA) (compositions of ITEMA/HEMA = 88/12).
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Figure S6.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-HEMA) (compositions of ITEMA/HEMA = 72/28).
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Figure S7.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-HEMA) (compositions of ITEMA/HEMA = 51/49).
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Figure S8.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-HEMA) (compositions of ITEMA/HEMA = 23/77).
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Figure S9.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-HEMA) (compositions of ITEMA/HEMA = 11/89).
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Figure S10.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-MAA) (compositions of ITEMA/MAA = 91/9).
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Figure S11.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-MAA) (compositions of ITEMA/MAA = 76/24).
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Figure S12.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-MAA) (compositions of ITEMA/MAA = 49/51).
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Figure S13.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-MAA) (compositions of ITEMA/MAA = 25/75).
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Figure S14.
1
H NMR spectrum (top) (400 MHz, 353 K, DMSO-d6), and IR spectra (bottom) (ATR, 293
K) of poly(ITEMA-co-MAA) (compositions of ITEMA/MAA = 10/90).
17/17