Inducing hardening and healability in poly(ethylene-co-acrylic … · 2018-11-28 · Tables S1-S3...
Transcript of Inducing hardening and healability in poly(ethylene-co-acrylic … · 2018-11-28 · Tables S1-S3...
Inducing hardening and healability in poly(ethylene-co-acrylic acid) via blending
with complementary low molecular weight additives
Benjamin C. Bakera; I. Germanb; Gary C. Stevensb; Howard M. Colquhouna; and Wayne Hayes a*
a Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK. Email:
[email protected], Telephone: +44 118 378 6491, Fax: +44 118 378 6331
b Gnosys Global Ltd., 17-18 Frederick Sanger Road, The Surrey Research Park, Guildford, Surrey, GU2 7YD,
UK
Supplementary Information
Contents Page
Scheme S1 Synthetic route to compounds 3-5. S1
Figures S1-S9 1H and 13C NMR spectra of 3-6 in DMSO-d6 or CD3OD plus S2
IR spectra.
Figures S10-S12 Gelator 3: rheology and UV-vis absorption characteristics. S9
Figure S13 DSC data for pEAA15/1 (10% wt). S11
Figures S14-S20 Stress-strain curves for pEEA15 and additives 1-7 (1/5% wt). S11
Figures S21-S24 DSC thermograms for pEAA15/1-3 (0, 1 and 5% wt). S15
Figures S25-S28 Relaxation DSC scans of pEEA15/1-3 (0, 1 and 5% wt). S16
Tables S1-S3 Tensile properties of pEAA15 and pEEA15/1-3 after healing. S18
Figures S29-S39 Stress-strain curves for pEAA15 and pEEA15/1-3 after healing. S19
Figures S40-S41 DSC thermograms of pEAA5 and pEAA20 with 1 and 3. S24
Figures S42-S45 Stress strain curves for pEAA20 with 1 and 3. S25
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2018
S1
Scheme S1; Generic synthesis of compounds 3-5 (3: R1 = H, R2 = NO2. 4: R1 = NO2, R2 = H. 5: R1
= H, R2 = H).
S2
Figure S1; 1H and 13C NMR spectra of 3 in DMSO-d6
S3
Figure S2; 1H NMR spectrum of 3 in CD3OD
Figure S3; IR spectra of 3
40
50
60
70
80
90
100
800130018002300280033003800
Ab
sorb
ance
(%
)
Wavenumber (cm-1)
S4
Figure S4; 1H and 13C NMR spectra of 4 in DMSO-d6
S5
Figure S5; IR spectra of 4
75
80
85
90
95
100
800130018002300280033003800
Ab
sorb
ance
%
Wavenumber cm-1
S6
Figure S6; 1H and 13C NMR spectra of 5 in DMSO-d6
S7
Figure S7; IR spectra of 5
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96
98
100
102
800130018002300280033003800
Ab
sorb
ance
(%
)
Wavenumber (cm-1)
S8
Figure S8; 1H and 13C NMR spectra of 6 in DMSO-d6
S9
Figure S9; IR spectra of 6
Figure S10; Hydrogelator 3, CGC 2.7 mM (0.1%wt)
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65
70
75
80
85
90
95
100
105
110
800130018002300280033003800
Ab
sorb
ance
(%
)
Wavenumber (cm-1)
S10
Figure S11; Rheology of aqueous gel of hydrogelator 3 (20 mM).
Figure S12; UV/vis absorption spectra of stirred solution of aqueous methylene blue (250 mL, 8 mg
L-1) after addition of hydrogelator 3 (1 mL, 80 mM).
5 50 500
1
10
100
1000
10000
Shear rate (rad/s)
Mo
du
lus
(KP
a)
G'
G"
500 550 600 650 700
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Wavenlength (nm)
Ab
sorb
ance
0 min
1 hour
24 hour
48 hour
S11
Figure S13; DSC heating (lower) and cooling (upper) curves for pEAA15 /1 (10% wt) showing
phase separation of polymer and dicarboxylic acid 1 (represented by the melting transition at 120
C).
Figure S14; Stress strain curves (average of five samples) for; pEEA15 (black), pEEA15/1 (1% wt.)
(red) and pEEA15/1 (5% wt.) (blue).
0
0.5
1
1.5
2
2.5
3
3.5
4
0 0.02 0.04 0.06 0.08 0.1 0.12
Stre
ss (
MP
a)
Strain
S12
Figure S15; Stress strain curves (average of five samples) for pEEA15/2 (1% wt) (red) and
pEEA15/2 (5% wt) (blue).
Figure S16; Stress strain curves (average of five samples) for pEEA15/3 (1% wt) (red) and
pEEA15/3 (5% wt) (blue).
0
0.5
1
1.5
2
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Stre
ss (
MP
a)
Strain
0
0.5
1
1.5
2
2.5
3
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2
Stre
ss (
MP
a)
Strain
S13
Figure S17; Stress strain curves (average of five samples) for pEAA15 and 4 at 1% (red) and 5%
(blue) wt.
Figure S18; Stress strain curves (average of five samples) for pEAA15 and 5 at 1% (red) and 5%
(blue) wt.
0
0.5
1
1.5
2
2.5
0 0.05 0.1 0.15 0.2
Stre
ss (
MP
a)
Strain
0
0.5
1
1.5
2
2.5
0 0.05 0.1 0.15 0.2
Stre
ss (
MP
a)
Strain
S14
Figure S19; Stress strain curves (average of five samples) for pEAA15 and 6 at 1% (red) and 5%
(blue) wt.
Figure S20; Stress strain curve (average of five samples) for pEAA15 and 7 at 1% wt.
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 0.05 0.1 0.15 0.2 0.25
Stre
ss (
MP
a)
Strain
0
0.5
1
1.5
2
2.5
0 0.05 0.1 0.15 0.2
Stre
ss (
MP
a)
Strain
S15
Figure S21; DSC heating scan (below) and subsequent cooling scan (above) of pEEA15.
Figure S22; DSC heating/cooling scans of pEEA15/1 at 1% (red) and 5% weight (blue).
Figure S23; DSC heating/cooling scans of pEEA15/2 at 1% (red) and 5% weight (blue).
S16
Figure S24; DSC heating/cooling scans of pEEA15/3 at 1% (red) and 5% weight (blue).
Figure S25; Relaxation DSC scan of pEEA15 (48 hours after scan shown in Figure S19).
Figure S26; Relaxation DSC scans of pEEA15 /1 at 1% (red) and 5% wt. (blue) (taken 48 hours
after scan shown in Figure S20).
S17
Figure S27; Relaxation DSC scan of pEEA15/2 at 1% (red) and 5% wt. (blue) (taken 48 hours after
scan shown in Figure S21).
Figure S28; Relaxation DSC scan of pEEA15/3 at 1% (red) and 5% wt. (blue) (taken 48 hours after
scan shown in Figure S22).
S18
Table S1; Tensile properties after heating fractured films at 50 °C for 8 hours.
Table S2; Tensile properties after heating fractured films at 60 °C for 2 hours.
Film
System
% wt
additive
Tensile
Strength
(MPa)
Fracture
Stress
(MPa)
Uniform
Strain
(%)
Strain to
Fracture
(%)
Energy
absorbed
(MPa)
Young’s
Modulus
(MPa)
pEEA15 0.39 0.37 1.67 1.74 0.008 14.22
pEEA15/1 5 - - - - - -
pEEA15/2 1 0.72 0.63 4.43 5.26 0.03 17.97
pEEA15/3 5 1.12 1.12 2.29 2.37 0.021 28.53
Table S3; Tensile properties after pressing (0.98 MPa) fractured films for 8 hours.
Film
System
% wt
additive
Tensile
Strength
(MPa)
Fracture
Stress
(MPa)
Uniform
Strain
(%)
Strain to
Fracture
(%)
Energy
absorbed
(MPa)
Young’s
Modulus
(MPa)
pEEA15 1.00 0.84 6.15 7.38 0.06 26.31
pEEA15/1 5 1.35 0.93 6.75 9.68 0.10 21.83
pEEA15/2 1 0.20 0.15 1.07 1.23 0.007 18.60
pEEA15/3 5 1.95 0.96 5.62 7.48 0.14 41.43
Film
System
% wt
additive
Tensile
Strength
(MPa)
Fracture
Stress
(MPa)
Uniform
Strain
(%)
Strain to
Fracture
(%)
Energy
absorbed
(MPa)
Young’s
Modulus
(MPa)
pEEA15 0.12 0.12 1.56 1.60 0.002 5.68
pEEA15/1 5 0.09 0.09 0.53 0.56 0.001 13.12
pEEA15/2 1 0.57 0.57 1.50 1.58 0.013 23.23
pEEA15/3 5 0.88 0.88 2.30 2.42 0.013 18.61
S19
Figure S29; Stress-strain curve (average of five samples) for pEAA15 after healing at 60 ˚C (2
hours)
Figure S30; Stress-strain curve (average of five samples) for pEAA15/2 (1% wt) after healing at 60
˚C (2 hours)
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0 0.005 0.01 0.015 0.02
Stre
ss (
MP
a)
Strain
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0 0.01 0.02 0.03 0.04 0.05 0.06
Stre
ss (
MP
a)
Strain
S20
Figure S31; Stress-strain curve (average of five samples) for pEAA15/3 (5% wt) after healing at 60
˚C (2 hours)
Figure S32; Stress-strain curve (average of five samples) for pEAA15 after healing at 50 ˚C (8
hours).
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.005 0.01 0.015 0.02 0.025
Stre
ss (
MP
a)
Strain
0.00
0.02
0.04
0.06
0.08
0.10
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0.14
0 0.005 0.01 0.015 0.02
Stre
ss (
MP
a)
Strain
S21
Figure S33; Stress-strain curve for pEAA15/1 (5% wt) after healing at 50 ˚C (8 hours)
Figure S34; Stress-strain curve (average of five samples) for pEAA15/3 (5% wt) after healing at 50
˚C (8 hours)
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0 0.001 0.002 0.003 0.004 0.005 0.006
Stre
ss (
MP
a)
Strain
0
0.2
0.4
0.6
0.8
1
1.2
0 0.005 0.01 0.015 0.02 0.025 0.03
Stre
ss (
MP
a)
Strain
S22
Figure S35; Stress-strain curve (average of five samples) for pEAA15/2 (1% wt) after healing at 50
˚C (8 hours)
Figure S36; Stress-strain curve (average of five samples) for pEAA15 after healing under pressure
(0.98 MPa, 8 hours)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0 0.005 0.01 0.015 0.02
Stre
ss M
Pa
Stress
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
Stre
ss (
MP
a)
Strain
S23
Figure S37; Stress-strain curve (average of five samples) for pEAA15/1 (5% wt) after healing under
pressure (0.98 MPa, 8 hours)
Figure S38; Stress-strain curve (average of five samples) for pEAA15/2 (1% wt) after healing under
pressure (0.98 MPa, 8 hours)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 0.02 0.04 0.06 0.08 0.1 0.12
Stre
ss (
MP
a)
Strain
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014
Stre
ss (
MP
a)
Strain
S24
Figure S39; Stress-strain curve (average of five samples) for pEAA15/3 (5% wt) after healing under
pressure (0.98 MPa, 8 hours)
Figure S40; DSC thermograms for pEAA20 (black) and pEAA20/1 (blue) and 3 (red) each at 10%
wt. The three lower traces are the heating scans and the three upper traces are the cooling scans.
0
0.5
1
1.5
2
2.5
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
Stre
ss (
MP
a)
Strain
S25
Figure S41; DSC thermograms for pEAA5 (black) and pEAA5/1 (red) at 2% wt.
Figure S42; Stress-strain curve (average of five samples) of pEAA20.
0
1
2
3
4
5
6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Stre
ss (
MP
a)
Strain
131 °C
S26
Figure S43; Stress-strain curve of pEAA20/1 (10% wt).
Figure S44; Stress-strain curve (average of five samples) of pEAA20/3 (10% wt).
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Stre
ss (
MP
a)
Strain
0
1
2
3
4
5
6
7
8
9
10
0 0.2 0.4 0.6 0.8 1 1.2
Stre
ss (
MP
a)
Strain
S27
Figure S45; Stress-strain curve (average of five samples) of pEAA20/3 (10% wt) after healing under
pressure (0.98 MPa, 8 hours).
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Stre
ss (
MP
a)
Strain