Supporting Information for Hydrogen-transfer and condensation-addition polymerizations of acrylic

26 Pages·2017·1.2 MB·English

Electronic Supplementary Material (ESI) for Polymer Chemistry.
This journal is © The Royal Society of Chemistry 2018

Supporting Information for

Hydrogen-transfer and condensation-addition polymerizations of acrylic acid
Takuya Murase, Shin-ichi Matsuoka,* Masato Suzuki

Department of Life Science and Applied Chemistry, Graduate School of Engineering,
Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, Aichi 466-8555, Japan
Fax: [phone]; Tel: [phone];
E-mail: [email protected]

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Contents
Figure S1. 1H NMR spectrum of Poly(AA) obtained by Ph P (Entry 1 in Table 1) ..................................... 3
3
Figure S2. 1H NMR spectrum of Poly(AA) obtained by TPT (Entry 5 in Table 1) ...................................... 4
Figure S3. 1H NMR spectrum of Poly(AA) obtained by DNBS (Entry 13 in Table 1) ................................ 5
Figure S4. ESI-MS spectrum of Poly(AA) obtained by Ph P (Entry 1 in Table 1) ...................................... 6
3
Figure S5. ESI-MS spectrum of Poly(AA) obtained by TPT (Entry 5 in Table 1) ....................................... 7
Figure S6. ESI-MS spectrum of Poly(AA) obtained by DNBS (Entry 12 in Table 1) .................................. 8
Figure S7. Time vs Conv. vs M : GPC profiles of poly(AA)s obtained by DNBS (5 mol%) at 100 ºC ....... 9
n
Figure S8. 1H NMR spectrum of Poly(AA) end-capped with n-butyl acrylate (Scheme 2) ....................... 10
Figure S9. ESI-MS spectrum of Poly(AA) end-capped with n-butyl acrylate (Scheme 2) ......................... 11
Figure S10. 1H NMR spectrum of the graft copolymer (Entry 1 in Table 2) .............................................. 12
Figure S11. 1H NMR spectrum of the graft copolymer (Entry 4 in Table 2) .............................................. 13
Figure S12. 1H NMR spectrum of the graft copolymer (Entry 7 in Table 2) .............................................. 14
Figure S13. DSC profile of copolymer of Poly(AA) with MMA (Entry 2 in Table 2) ............................... 15
Figure S14. DSC profile of copolymer of Poly(AA) with MMA (Entry 3 in Table 2) ............................... 15
Figure S15. DSC profile of copolymer of Poly(AA) with MA (Entry 4 in Table 2) .................................. 16
Figure S16. DSC profile of copolymer of Poly(AA) with MA (Entry 6 in Table 2) .................................. 16
Figure S17. DSC profile of copolymer of Poly(AA) with St (Entry 7 in Table 2) ..................................... 17
Figure S18. DSC profile of copolymer of Poly(AA) with St (Entry 8 in Table 2) ..................................... 17
Figure S19. TGA profile of copolymer of Poly(AA) with MMA ............................................................... 18
Figure S20. TGA profile of copolymer of Poly(AA) with MA ................................................................... 19
Figure S21. TGA profile of copolymer of Poly(AA) with St ...................................................................... 20
Figure S22. 1H NMR spectrum of the poly(ester-ether) (Entry 2 in Table 3) ............................................. 21
Figure S23. 1H NMR spectrum of the poly(ester-ether) (Entry 5 in Table 3) ............................................. 22
Figure S24. 1H NMR spectrum of the poly(ester-ether) (Entry 7 in Table 3) ............................................. 23
Figure S25. 13C NMR spectrum of the poly(ester-ether) (Entry 7 in Table 3) ............................................ 24
Figure S26. 1H NMR spectrum of the crude mixture obtained by the reaction of AA with EG for 10 min
(Scheme 3) ................................................................................................................................................... 25
Figure S27. ESI-MS spectrum of poly(ester-ether) (Entry 2 in Table 3) .................................................... 26

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1 7 7 3 7
TMS
6 5 n 2, 4 5 n
5 7
4.42 2.68
1
8
6
7.
2 3 4
7.82 6.436.386.146.12 5.84 6
6.47 5.89 3.58
3.29 0.990.891.00 5.59 0.33 6.23
8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)

Figure S1. 1H NMR spectrum of Poly(AA) obtained by Ph P (Entry 1 in Table 1)
3

- 3 -
1
1
8 7 3 7
n n
6 5 2, 4 5
1
5
5
3
4.
7
4
6
2.
2 4
1 9 6.39 3 5.86
5 2
7. 6.1 6 8
9 0
0 3
3. 2.
3.71 0.990.961.00 9.28 0.08 7.730.09
8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)

Figure S2. 1H NMR spectrum of Poly(AA) obtained by TPT (Entry 5 in Table 1)

- 4 -
2 5
O O
H
n
1, 3 4 TMS
O O
4 5
7
6
7 2.
3
4.
1 2 3
6.39 6.12 5.85
0.990.961.00 12.28 12.35
8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)

Figure S3. 1H NMR spectrum of Poly(AA) obtained by DNBS (Entry 13 in Table 1)

- 5 -
Figure S4. ESI-MS spectrum of Poly(AA) obtained by Ph P (Entry 1 in Table 1)
3

- 6 -
1
4
3
1 7
8. 6
9 5
2n = 0 1
.
0
7 n = 1
3 n
72.02
n = 2
4 n = 3
7
7 6 n = 4
1 8 n = 5 n = 6
72.02 442. 514.19 86.2208 8.2417 0.2638
5 5 3
6 7
200 300 400 500 600 700 800
m/z

Figure S5. ESI-MS spectrum of Poly(AA) obtained by TPT (Entry 5 in Table 1)

- 7 -
n
H O
3 2
94= 4 = 5 n
0
.n n
3 9
8 4
3 3 1
1
= .
5
n 5
4 4 4 6
07= 3 = n =
11.n n6 5 64
3835 104 n = .136 = 7
186.2226 n = 2239.0529n = 2257.0634 298.1342 329.0727.022.02401.72.02473.1255 527n = 545.1461 n 599.1569n = 7617.1672 n = 8671.1768n = 889.188 n = 943.1975n = 91.209
6 76
72.02 7
100 200 300 400 500 600 700 800
m/z

Figure S6. ESI-MS spectrum of Poly(AA) obtained by DNBS (Entry 12 in Table 1)

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1h, Conv. = 22 %,
M = 220,M /M = 1.06
n w n
6h, Conv. = 62 %,
M = 260, M /M = 1.46
n w n
18h, Conv. = 81 %,
M = 390, M /M = 1.41
n w n
24h, Conv. = 78 %,
M = 460, M /M = 1.59
n w n
8765 4 3
48h, Conv. = 81 %, 2 mer
M = 500, M /M = 1.59
n w n
10 12 14 16 18 20 22 24
Elution Times (min.)

Figure S7. Time vs Conv. vs M : GPC profiles of poly(AA)s obtained by DNBS (5
n
mol%) at 100 ºC

- 9 -
2 5
4 n 9
1, 3
4
9
0.
6 8 5
6
R = H, 2.6
7 9
4
2
4
4.
6
2
1
4.
1 3 7 8
2
6.39 6.12 5.86 1.62 1.391.37
7
5
2.
1.01 0.971.00 5.071.81 5.42 1.821.79 2.77
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)

Figure S8. 1H NMR spectrum of Poly(AA) end-capped with n-butyl acrylate (Scheme 2)

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