self-healing supramolecular polyurethanes...1.00e+04 1.00e+05 1.00e+06 1.00e+07 1.00e+08-75 -50 -25...
TRANSCRIPT
Wayne HayesDepartment of Chemistry, University of Reading
Clive SiviourDepartment of Engineering Science, University of Oxford
Self-Healing Supramolecular Polyurethanes
EP/D07434711, EP/G026203/1, EP/J010715/1, EP/J011436/1, EP/L020599/1 and NSF-DMR-
0602869; Henkel Ltd
Covalent cross-links
Material Properties → Cross-link density and microphase separation
Soft segment phase
Cross-linked Polymer Networks
• Simple Bisurethanes display polymeric properties such as high viscosity
Room Temperature
Left: MDI Urethane TetrolRight: MDI Urethane Tetrabutyl
ca. 50 °C
MDI Urethane Tetrol MDI Urethane Tetrabutyl
NH
O
O
NH
O
O
N
OH
OHN
HO
HO
NH
O
O
NH
O
O
NN
Urethane Supramolecular
Polymers
‘Novel material forming supramolecular structures, process and uses’,
W. Hayes, P.J. Woodward, A. Clarke, A.T. Slark, EU Patent, 2007, EP1792925.
P. Woodward, A. Clarke, B.W. Greenland, D. Hermida Merino, L. Yates, A.T. Slark, J.F. Miravet,
W. Hayes Soft Matter, 2009, 5, 2000-2010.
Urethane Supramolecular Polymer
Networks
‘Novel material forming supramolecular structures, process and uses’,
W. Hayes, P.J. Woodward, A. Clarke, A.T. Slark, EU Patent, 2007, EP1792925.
P. Woodward, A. Clarke, B.W. Greenland, D. Hermida Merino, L. Yates, A.T. Slark, J.F. Miravet,
W. Hayes Soft Matter, 2009, 5, 2000-2010.
Reversible properties → external stimuli (heat, light, ultrasound, mechanical)
Supramolecular Polymer Networks
The final assembly
produced represents
the thermodynamic
minimum
E.W. Meijer et al., Chem. Rev., 2001, 101, 4071. K. A. Houton, A. J. Wilson, Polymer, 2015, 64, 165.
Soft segment phase
Hard segment phase
• Require efficient binding
• Phase separation of recognition unit(s) from bulk phase - advantageous
• Require accessible activation mechanism for repair – heat/light/pressure
H. M. Colquhoun, W. Hayes et al., Chem. Soc. Rev., 2010, 39, 1973.
H M Colquhoun, W Hayes et al., Polym. Chem., 2013, 4, 4860.
Routes to Healable Polymers -
Supramolecular Self-Assembly
Hydrophobic
Block
Hydrophilic
Block
Hydrogen Bonding End Groups:–
Binding Constant Analysis Supramolecular polymers -
Design
Hydrophilic
Block
End Group
Functionality
End Group
Functionality
Aust. J. Chem., 2009, 62, 790–793. Macromolecules, 2010, 43, 2512-2517.
Supramolecular Polymers via
Oligomer Modification
Aust. J. Chem., 2009, 62, 790–793. Macromolecules, 2010, 43, 2512-2517.
NH
O
O
OHN
O
HN O
O
N
OH
OHNH
O
O
N
HO
HO
n
NH
O
O
OHN
O
HN
HN
O
N
OH
OHNH
NH
O
N
HO
HO
n
NH
O
O
OHN
O
HN O
O
N
OH
OHNH
O
O
N
HO
HO
n
NH
O
O
OHN
O
HN
HN
O
N
OH
OHNH
NH
O
N
HO
HO
n
NH
O
OHN
O
HN O
O
N
OH
OHNH
O
O
N
HO
HO
n
O
m
co
NH
O
OHN
O
HN
HN
O
N
OH
OHNH
NH
O
N
HO
HO
n
O
m
co
NH
O
O
OHN
O
HN O
O
NNH
O
O
N
n
NH
O
O
OHN
O
HN O
O
NNH
O
O
N
n
NH
O
OHN
O
HN O
O
NNH
O
O
N
n
O
m
co
NH
O
O
OHN
O
HN
HN
O
NNH
NH
O
N
n
NH
O
O
OHN
O
HN
HN
O
NNH
NH
O
N
n
NH
O
OHN
O
HN
HN
O
NNH
NH
O
N
n
O
m
co
Three MDI terminated oligomers were employed and reacted with alcohol and butyl terminated
alcohols and amines to give hydrogen bonding polymeric urethanes and ureas
Urethane End Group Urea-Urethane End Group
Supramolecular Polymers
NH
O
OHN
O
HN O
O
N
OH
OHNH
O
O
N
HO
HOO
NH
O
OHN
O
HN
HN
O
N
OH
OHNH
NH
O
N
HO
HOO
NH
O
OHN
O
HN O
O
NNH
O
O
N ONH
O
OHN
O
HN
HN
O
NNH
NH
O
N O
1.00E+00
1.00E+01
1.00E+02
1.00E+03
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
-75 -50 -25 0 25 50 75 100 125
Sto
rag
e M
od
ulu
s G
' (P
a)
Temperature (°C)
HO
n
OH
m
co
Rheology: Effect of End Group
NH
O
O
OHN
O
HN O
O
N
OH
OHNH
O
O
N
HO
HO
n
NH
O
O
OHN
O
HN O
O
NNH
O
O
N
n
NH
O
O
OHN
O
HN O
O
NH
O
O
n
Butyl
Methyl
PIB
Diol
Polymer central block (Glassy state)
Hydrogen bonding (Rubbery State)
Two transitions suggest
phase separation
~ Block Copolymer
Behaviour
Flow
Aust. J. Chem., 2009, 62, 790–793. Macromolecules, 2010, 43, 2512-2517.
Microphase separation of domains of ~10 nm
TEM Analysis: Phase Separation
100 nm
Staining via Uranyl Acetate
L. Leibler et al., Nature, 2008, 451, 977.
• Hydrogen bonding Approach
Routes to Healable Polymers -
Supramolecular Self-Assembly
C6H13HO2C-H2C
C6H15 CH2-CO2H
C6H13HO2C-H2C
C8H15 CH2-CO2H
CH2-CO2HC6H13
HO2C
CO2H
HO2C
CO2H
CO2H
+
1. Diethylene triamine / 160 °C
2. Urea / 135-160 °C
O
N
H
NN
O
H Amidoethylimidazolidone
O
N
H
N
O NH2
N
H
O
Di(amidoethyl)urea
O
N
H
N
O NH2
N
H
O O
N
H
N
OH2N
N
H
Diamidotetraethyl triurea
7
7
7
7
7
Now commercialised as
‘ReverlinkTM’ by Arkema
H.M. Colquhoun et al. Chem. Commun., 2004, 2650. J. Am. Chem. Soc., 2007, 129, 16163.
Chain-folding polymers : Iverson et al. J. Am. Chem. Soc., 2006, 128, 7996.
S. Burattini, H.M. Colquhoun, B.W. Greenland, W. Hayes, Faraday Discussions, 2009, 143, 251.
Healable p-p Stacked
Supramolecular Networks
Ka = 24,000 M-1
Healable Supramolecular Polymer
S. Burattini, H.M. Colquhoun, J.D. Fox, D. Friedmann, B.W. Greenland, P.J.F. Harris,
W. Hayes, M.E. Mackay, S.J. Rowan, Chem. Commun., 2009, 6717.
HN
O
HN
O
O
HN
O
HN
On
m
NO
Nn
N
O
O
O
O
N
O
O
O
O
O O
N N
O
O
O
O
Bu
Et
Bu
Et
m n
Control
Mn = 16000 g/mol
Tg = 190 °C
Mn = 6000 g/mol
Tg = -7 °C
Mn = 6000 g/mol
Tg = -5 °C
NO
Nn
N
O
O
O
O
N
O
O
O
O
O O
N N
O
O
O
O
Bu
Et
Bu
Et
m n
HN
O
HN
O
O
HN
O
HN
On
m
4
6
810
5
2
4
6
810
6
2
4
6
810
7
Mo
du
lus (
Pa
)
10090807060504030
Temperature (°C)
G' G"
100 rad/s
• Storage (G') and loss (G") moduli as a function
of temperature for the blend at a frequency of
100 rad/s and a strain of 0.1%
• The change in rheometric shift factor, aT,
(a function of viscosity) relative to Tg for the
blend (♦) and polystyrene (■)
Simple thermoplastics?
4 5
S. Onogi, T. Masuda, K. Kitagawa, Macromolecules, 1970, 3, 109.
-80 -60 -40 -20 0 20 40 60 80 100120
104
105
106
107
108
G',G
'' / [P
a]
Temperature / [°C]
-80 -60 -40 -20 0 20 40 60 80 100120
104
105
106
107
108
G',G
'' /
[Pa
]
Temperature / [°C]
NO
Nn
N
O
O
O
O
N
O
O
O
O
O O
N N
O
O
O
O
Bu
Et
Bu
Et
m m
• Temperature sweep analysis
Bis-pyrene polymer alone
Viscous properties dominate
above 100 °C
Elastic properties dominate
at all temperatures
Rheology of a supramolecular blend
Blend
Healable Hydrogen Bonded
Supramolecular Networks
A. Feula, et al., Chem. Sci., 2016, 7, 4291-4300 ; A. Feula, et al., Macromolecules, 2015, 48, 6132-6141.
Healable Linear Polymer Systems
H. M. Colquhoun, W. Hayes et al., Chem. Soc. Rev., 2010, 39, 1973.
• Linear thermoplastics can be thermally re-healed when two broken sections are
brought together as a consequence of the thermal diffusion of polymer chains
across the interface
• Healing is only observed when the polymer is held above its glass transition
temperature (Tg), for a period of time greater than the reptation time (Tr)
Rheological Characteristics
A. Feula, X. Tang, I. Giannakopoulos, A. M. Chippindale, I. Hamley, F. Greco, C. P. Buckley, C. R.
Siviour and W. Hayes, Chem. Sci., 2016, 7, 4291-4300.
Mechanical properties and interplay between rate (frequency) and
temperature.
Small strain oscillatory loading
Large strain monotonic loading
Peel Testing
Mechanical testing overview
Tensile Testing in Instron 5982
Application of Digital Image Correlation for strain measurements
d
5 mm
40 mmt = 0.5 mm
hS2
hS1
correlation value
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
0 1 2 3 4 5 6 7 8
0.0
0.2
0.4
0.6
0.8
1.0
Str
ess (
MP
a)
Strain
sample 1
sample 2
sample 3
sample 4
sample 5
pristine15 min
Str
ess (
MP
a)
Strain
sample 1
sample 2
sample 3
sample 4
sample 5
sample 6
sample 7
30 min
Str
ess (
MP
a)
Strain
sample 1
sample 2
sample 3
sample 4
sample 5
sample 6
120 min60 minS
tress (
MP
a)
Strain
sample 1
sample 2
sample 3
sample 4
sample 5
Str
ain
(M
Pa)
Strain
sample 1
sample 2
sample 3
sample 4
120 (HT)
Str
ess (
MP
a)
Strain
sample 1
sample 2
sample 3
sample 4
sample 5
sample 6
Mechanical testing overview
2D and 3D microscopy:
monitoring healing processes
Tensile testing
0
1
2
3
4
5
6
7
8
9
10
pris ne
healing15min
healing30min
healing60min
healing120min
0
100
200
300
400
500
600
pris ne
healing15min
healing30min
healing60min
healing120min
• Complete recovery of the Young’s modulus
after 15 minutes of healing at 37 ºC
• Complete recovery of the elongation to break
after 60 minutes of healing at 37 ºC
• Overall healing efficiency > 100%
after 60 minutes of healing at 37 ºC
Yo
un
g’s
mo
dulu
s (
MP
a)
Elo
nga
tio
n to
bre
ak (
%)
Adhesive Properties
A. Feula, X. Tang, I. Giannakopoulos, A. M. Chippindale, I. Hamley, F. Greco, C. P. Buckley, C. R.
Siviour and W. Hayes, Chem. Sci., 2016, 7, 4291-4300.
Healing in situ on pig skin
A. Feula, X. Tang, I. Giannakopoulos, A. M. Chippindale, I. Hamley, F. Greco, C. P. Buckley, C. R.
Siviour and W. Hayes, Chem. Sci., 2016, 7, 4291-4300.
A new polymer with interesting
history dependence
X Tang, A Feula, B C Baker, K Melia, D Hermida Merino, I W Hamley, C P Buckley, W Hayes and
Clive R. Siviour, Polymer, 2017, DOI:10.1016/j.polymer.2017.11.005. .
cast
annealed (1 hour 70 °C)
quenched
0 50 100 15010
0
102
104
106
108
Sh
ea
r s
tora
ge
mo
du
lus
(P
a)
Temperature (°C)
0 20 40 60 80 100 120 140 160 18010
0
101
102
103
104
105
106
107
108
Temperature (°C)
60 min
45 min
30 min
15 min
0 min
Sh
ea
r s
tora
ge
mo
du
lus
(P
a)
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.40.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Str
es
s (
MP
a)
Strain
Cast
120 min
60 min
30 min
15 min
0 min
Summary• Using a careful combination of design and synthesis supramolecular polymer
networks can be realised.
• A picture of the basic design rules is starting to become apparent – healing
parameters can be adjusted by varying the ‘hard segments’ (i.e. p-p stacking and
hydrogen bonding units) in relation to ‘soft’ segments
Past and Present Research Group
Oxford
Dr Xuegang Tang
Dr Ioannis Giannakopoulos
Mr Richard Duffin
Professor Christina Prisacariu
Reading
Dr Antonio Feula
Dr Barny Greenland
Dr Lewis Hart
Dr Daniel Hermida Merino
Dr Kelly Melia
Dr Philip Woodward
Collaborators
Professor Paul Buckley (Oxford)
Professor Christine Cardin (Reading)
Dr Ann Chippindale (Reading)
Professor Howard Colquhoun (Reading)
Dr Francesca Greco (Reading)
Professor Ian Hamley (Reading)
Sponsors
EPSRC
University of Reading (RETF)
Henkel Ltd (Dr Andrew Slark)
Acknowledgements
• Storage modulus and loss modulus cross at a temperature < 50 ºC,
indicating a nominal transition from elastic behaviour to a viscous state
• Over 6 orders decrease of storage modulus from 0 to 120 ºC
viscoelastic
region
Healable Hydrogen Bonded
Supramolecular Networks
Mn ~ 4000
Tg -44 C
Rheological testing in Anton Parr Physica MCR 301
Oscillatory shear loading
Temperatures from c.a. -10 °C to +120 °C
Frequencies from ~0.1 to 100 Hz, using isothermal frequency sweeps for TTS
Mechanical testing overview