Introduction
Experimental
Raw materials and reagents
Method for the synthesis of urethane cationomers
-
The reaction with HCOOH or C4H9Br was conducted at 50 °C during 2 h, and then it was allowed to continue at ambient temperature during 24 h.
Determination of –NCO group content
NMR spectroscopy
IR spectroscopy
Wide angle X-ray scattering analysis
Study on cationomer coat surface form
Confocal microscopic analysis
Atomic Force Microscopy
-
topographic image (height, h), two-dimensional or three-dimensional
-
phase image (phase, p), which represented the phase lag for probe vibrations at the boundary between two media (due to friction of the probe/needle tip on the sample surface (friction, f) or axial deflection z of the probe/needle tip after it hits any surface irregularity (deflection, d)
Method for determination of components of surface free energy for solids
-
for bipolar substances (liquids and surfaces of solids), which can be equivalent to synthesised PU ionomers—present in the form of aqueous dispersions or coatings:$$ \gamma ^{{{{AB}}}}_{{{i}}} = 2{\sqrt {\gamma ^{ + }_{{{i}}} \cdot \gamma ^{ - }_{{{i}}} } } $$(18)
-
for non-polar liquids and surfaces of solids (diiodomethane or PTFE):$$ {\gamma_{\rm{i}}}^{\rm{AB}} = 0 $$(19)(where: i = S—solid, L—liquid).
Thermal analysis by TGA and DTA methods
Results and discussion
Chemical structure of cationomers
Sample no. | 1 | 2 | 3 | 4 |
---|---|---|---|---|
Integration (conventional unit) | ||||
0.5(Ib + Ib’) | 15.6195 | 15.3972 | 1.576 | 22.7407 |
Ic
| 3.8294 | 2.9512 | 0.8067 | 3.4996 |
Ie
| 6.0066 | 4.6950 | 0.7197 | 3.4319 |
Iy
| – | 0.4587 | – | 0.9010 |
Ix + Iq + Iz
| 3.3265 | 2.3895 | 1.000 | 6.0409 |
I
P
|
28.782
|
25.8915
|
4.1024
|
36.6141
|
0.5(Ib + Ib’) | 15.6195 | 15.3972 | 1.576 | 22.7407 |
Ia
| – | 0.5820 | – | 0.7144 |
Iw
| – | 0.3111 | 3.886 | |
Ig
| 4.072 | 3.7700 | 0.8068 | 3.9641 |
Ik
| 3.0416 | 2.9328 | 0.4732 | 3.4844 |
Il
| 1.0000 | 1.5438 | 0.5640 | 1.3117 |
I
N
|
23.7331
|
24.2258
|
3.7311
|
36.1013
|
κ [%] | 54.807 | 51.662 | 52.237 | 50.352 |
Sample no. | 1 | 2 | 3 | 4 |
---|---|---|---|---|
Location and type of IR bands \( \overline v \) (cm−1) | Absorbance (conventional scale) | |||
3,200–3,490 N–H valence vibrations of urethane and ureas | 0.2872 | 0.2444 | 0.0466 | 0.0278 |
2,250–2,500 NH+ deformation vibrations | 0.0200 | 0.0286 | 0.0136 | 0.0315 |
1,680–1,720 C = O valence vibrations of urethane and ureas (I amide band) | 0.6113 | 1.2267 | 0.1648 | 0.1771 |
1,643–1,653 C = O ionic vibrations in COO– groups | 0.3052 | 0.3058 | 0.0704 | 0.0694 |
1,532–1,539 N–H deformation vibrations (II amide band of urethanes and ureas) | 0.6630 | 0.5888 | 0.1765 | 0.1078 |
1,222–1,224, 1,278–1,281 valence vibrations: C–OH in alcohols and C–O–C in ethers | 1.0963 | 1.0044 | – | – |
0.3990 | 0.3792 | |||
1,180 C–N vibrations in amines | 0.5821 | 0.5582 | 0.7222 | 0.4842 |
A
P
|
3.9641
|
4.3361
|
1.1941
|
0.8978
|
2,800–3,057 valence vibrations of alkyl groups | 0.3225 | 0.4926 | 0.079 | 0.1021 |
1,600–1,602, 1,451–1,457 C–C vibrations in aromatic rings | 0.4526 | 0.3310 | 0.1108 | 0.0601 |
0.4707 | 0.4394 | 0.0915 | 0.0432 | |
1,255–1,257 Palence vibrations of C–F linkage in CF2 groups | – | – | 0.3687 | 0.2612 |
A
N
|
1.2458
|
1.2630
|
0.6500
|
0.4666
|
α
|
76.089
|
77.443
|
64.752
|
65.802
|
Glass transition temperature of polyurethane coatings
Solid state structure and stability of synthesised cationomers
Sample no. | I stage degradation | II stage degradation | III stage degradation | Total mass loss | Ea
| |||
---|---|---|---|---|---|---|---|---|
Mass loss | T | Mass loss | T | Mass loss | T | |||
[%] | [°C] | [%] | [°C] | [%] | [°C] | [%] | [kJ/mol] | |
1 | 7.9831 | 128 | 23.0752 | 233 | 61.8665 | 411 | 92.7827 | 1 |
2 | 12.493 | 61 | 57.6712 | 231 | 11.623 | 410 | 81.2362 | 46 |
3 | – | – | 98.8291 | 244 | 1.171 | 454 | 100 | 45 |
4 | – | – | 99.9965 | 267 | 0.0035 | 453 | 100 | 147 |
Surface free energy of coatings obtained from polyurethane cationomers
Model measuring liquid | Surface free energy parameters [mJ/m2] | ||||
---|---|---|---|---|---|
γL
| γ
L
LW
| γ
L
AB
| γ
L
−
| γ
L
+
| |
Water | 72.8 | 21.8 | 51 | 25.5 | 25.5 |
Formamide | 58.0 | 39.0 | 19.0 | 2.28 | 39.6 |
Diiodomethane | 50.8 | 50.8 | 0 | 0 | 0 |
Sample no. | Experimental values of contact angles Θ [°] | Parameters of FSE [mJ/m2] | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Model measuring fluids | |||||||||||
CH2I2
| Standard deviation | Formamide | Standard deviation | Water | Standard deviation | γ
S
LW
| γ
S
−
| γ
S
+
| γ
S
AB
| γS
| |
1 | 42.98 | 1.33 | 61.97 | 1.17 | 77.85 | 0.79 | 33.282 | 0.025 | 13.819 | 1.176 | 34.5 |
2 | 51.66 | 0.15 | 68.44 | 0.17 | 85.78 | 0.24 | 29.143 | 0.071 | 7.967 | 1.504 | 30.6 |
3 | 79.26 | 0.25 | 84.63 | 0.16 | 89.01 | 0.48 | 15.662 | 0.020 | 16.586 | 1.152 | 16.8 |
4 | 84.21 | 0.18 | 88.31 | 0.24 | 99.85 | 0.11 | 13.453 | 0.326 | 4.948 | 2.540 | 16.0 |