Supporting Information for:
Cosolvent Gel-like Materials from Partially Hydrolyzed
Poly(vinyl acetate)s and Borax
Lora V. Angelova,1 Pierre Terech,2 Irene Natali,3 Luigi Dei,3 Emiliano Carretti,3 Richard G.
Weiss1*
1
Department of Chemistry, Georgetown University, Washington, DC 20057-1227, USA.
2
SPrAM, UMR CEA/UJF-Grenoble 1, INAC, Grenoble, F-38054, France.
3
Department of Chemistry “Ugo Schiff” & CSGI Consortium, University of Florence, via della
Lastruccia, 3 – 50019 Sesto Fiorentino (Florence) – Italy.
Email: [email protected]
Equation for calculation of degree of hydrolysis:
DMSO‐d5
2
1
5 a 3
H2O
4 c
b
Figure S1. 1H NMR spectra of 75PVAc in DMSO-d6 showing relevant peak assignments. Peaks
at (1) encompass all methylenes between two hydroxyl monomers (a), between a hydroxyl and
an acetate monomer (b) and between two acetate monomers (c).
1
Figure S2. 1H NMR spectra of polymers in DMSO-d6: (A) PVA, (B) 80PVAc, (C) 75PVAc, (D)
45PVAc, and (E) 40PVAc.
2
CH3OH 3
1
2 4 Figure S3. 13C NMR spectra of polymers: (A) PVA in D2O; (B) 80PVAc in D2O; (C) 75PVAc in
D2O; (D) 45PVAc in 1:1 methanol-d4:D2O; (E) 40PVAc in 1:1 methanol-d4:D2O.
3
Figure S4. 1H NMR spectrum of 75PVAc in DMSO-d6 showing integrated areas of methylene
and acetate hydrogens (assumed to be 3H).
Complexed Borate (%)
45
40
35
30
25
20
24
32
40
48
Observation Pulse (µs)
Figure S5. Ratios of complexed to free borate species at different pulse observation times.
HVPDs composed of 4 wt % 75PVAc, 1 wt % borax and 50/50 acetone/water. Data are from
integrations of peaks in 11B NMR spectra (weighing 4 copies of the relevant peaks); the error
bars are one standard deviation in the weight ratios.
3500
3000
2500
G' and G" (Pa)
2000
1500
1000
500
0.01
0.1
1
10
100
Strain (%)
Figure S6. Strain sweep performed on a HVPD composed of 6 wt % 75PVAc and 1.4 wt %
borax with 30/70 1-propanol/water.
4
100000
10000
100
1000
η0 (Pa⋅s)
η0 (Pa⋅s)
100
10
10
1
1
0.1
0.01
2
4
6
8
10
12
0.1
14
4
40PVAc (wt %)
6
8
10
12
14
16
18
20
45PVAc (wt %)
1000000
10000
100000
10000
1000
η0 (Pa⋅s)
η0 (Pa⋅s)
1000
100
10
1
100
10
1
0.1
0.01
0.1
1E-3
0
2
4
6
8
10
0.1
12
1
10
PVA (wt %)
75PVAc (wt %)
Figure S7. Plots of η0 versus xPVAc concentration in H2O. The [xPVAc]/[Borax] concentration
ratios can be calculated from the data in Table 2 in the main text. A similar plot of the
80PVAc_3 data from another experiment is available in the literature.1
5
100
90
100
A
90
Temperature (°C)
Temperature (°C)
80
70
60
50
40
*
*
30
20
80
70
60
30
40
30
20
40
50
60
70
10
80
wt % of Organic Liquid (of Total Liquid)
20
30
40
50
60
100
C
D
90
*
*
70
70
wt % Organic Liquid (of Total Liquid)
Temperature (°C)
Temperature (°C)
80
*
*
0
0
90
*
50
10
10
100
B
*
60
50
40
30
20
10
*
*
80
70
60
50
40
30
20
10
0
0
10
20
30
40
50
10
60
15
20
25
30
35
40
wt % Organic Liquid (of Total Liquid)
wt % of Organic Liquid (of Total Liquid)
Figure S8. Melting temperature ranges (indicated by vertical lines) of HVPDs prepared with
varying amounts of methanol (), ethanol (), 1-propanol (), and NMP (). (A) 11 wt %
40PVAc and 2 wt % borax, (B) 6 wt % 75PVAc and 1.4 wt % borax, (C) 4 wt % 80PVAc_3 and
1 wt % borax, and (D) 4 wt % PVA and 1.1 wt % borax. * Data averaged from two runs.
6
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
1
2
3
4
Cross-Linked Borate (%)
Absolute Concentration of
Cross-Linked Borate (mM)
8
5
80PVAc_3 (wt %)
Figure S9. Concentrations and % of borate ions participating in crosslinks (of total boron
species) when the polymer and borax concentrations are varied but the 80PVAc_3/borax wt %
ratio is always 4/1. Data calculated from 11B NMR spectral integrations as described in Figure S5
7
Figure S10. 1H NMR spectra of 80PVAc_1 (viscosity = 4.8 Ps·s), 80PVAc_2 (viscosity = 32.4
Pa·s) and 80PVAc_3 (viscosity = 46.6 Pa·s) in DMSO-d6. The bottom curve shows the 3
individual spectra normalized for peak intensity and overlaid.
8
14
10
8
6
4
50
45
40
35
30
0
25
2
20
Complexed Borate (%)
12
Polymer Mw (kDa)
Figure S11. Percentage of boron species as crosslinking borate ions in hydro HVPDs composed
of 1 wt % 80PVAc_1, 80PVAc_2 and 80PVAc_3 (points from left to right) and 0.25 wt %
borax, calculated from 11B NMR spectral integrations as described in Figure S5.
9
Cross-Over Frequency (rad/sec)
4.8
A
4.7
4.6
4.5
4.4
1.2
0.8
0.4
0.0
0
10
20
30
40
50
% 1-Propanol (of Total Liquid)
Cross-Over Frequency (rad/sec)
2.0
1.8
B
1.6
1.4
1.2
1.0
0.8
0.6
0.4
30
40
50
60
70
% 1-Propanol (of Total Liquid)
Figure S12. Cross-over frequencies for HVPDs composed of (A) 6 wt % 75PVAc and 1.4 wt %
borax and (B) 11 wt % 40PVAc and 2 wt % borax with varying amounts of 1-propanol showing
standard deviation from three or four runs.
10
4.5
0.10
4.0
0.08
Normal Force (N)
Normal Force (N)
5.0
3.5
3.0
2.5
2.0
A
0.06
0.04
0.02
0.00
1.5
0.6
0.8
1.0
Gap (mm)
1.0
1.2
1.4
0.5
0.0
0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4
Gap (mm)
5
B
4
3
2
1
50
45
40
35
30
25
0
20
Maximum Normal Force (N)
6
Polymer Mw (kDa)
Figure S13. (A) Extensional rheology of hydrogels composed of 4 wt % 80PVAc_1, 80PVAc_2,
or 80PVAc_3 with 1 wt % borax; (B) The maximum normal force found for each HVPD. The
vertical bars are one standard deviation from three runs.
11
0
10
A
-1
-10
Heat Flow (W/g)
Heat Flow W/g)
0
1
-20
2
-30
3
-40
-30
-20
-10
-2
0.3 wt% borax
0.5 wt% borax
0.7 wt% borax
1.0 wt% borax
1.3 wt% borax
1.6 wt% borax
2.0 wt% borax
2.5 wt% borax
3.0 wt% borax
-3
-4
-5
-6
4
-40
B
0
10
-7
-60
20
-50
-40
-30
-20
-10
Temperature (°C)
Temperature (°C)
Figure S14. (A) Heating DSC thermograms of 11 wt % 40PVAc and 1 wt % borax HVPDs with
(1) 75%, (2) 50%, (3) 25%, and (4) 10% 1-propanol in the aqueous component; (B) Heating
DSC thermograms of 11 wt % 40PVAc in 75/25 2-propanol/water HVPDs with varying amounts
of borax.
Table S1. Weight and density of liquid expelled (syneresis) from HVPDs of 6 wt % 75PVac, 0.7
wt % borax, and 50/50 1-pentanol/water. The reported density of 1-pentanol at room temperature
is 0.815 g/L.2
Total liquid (g)
Non-incorporated
liquid
(g)
Average (g)
Density (g/L)
HVPD 1
0.3400
0.0408
0.0412
0.0417
0.0415
0.0401
0.0406
0.812
HVPD 2
0.3420
0.0414
0.0408
0.0406
0.0411
0.0410
0.0410
0.82
HVPD 3
0.3531
0.0414
0.0402
0.0409
0.0408
0.0407
0.0408
0.816
1. Natali, I.; Carretti, E.; Angelova, L. V.; Baglioni, P.; Weiss, R. G.; Dei, L. Langmuir 2011,
Accepted.
2. Lide, D.R., Ed. CRC Handbook of Chemistry and Physics; 88th ed.; CRC Press: New York,
2008.
12