Introduction
Experimental
Raw materials and reagents
Method for the synthesis of linear polyurethane
Sample no. | Type of diisocyanate | Type of polyol | Type of chain extender | Two theta angles, grad | Crystallisation degree, % | Two theta angle, grad | Crystallisation degree, % |
---|---|---|---|---|---|---|---|
Synthesis in dioxane | Synthesis in chlorobenzene | ||||||
PU-1 | MDI | POG 2,000 |
N-MDA | 19.48, 23.61 | 23.31 | 19.52, 23.64 | 25.80 |
26.81, 27.52 | 26.94, 29.83 | ||||||
29.76, 36.17 | 36.22, 43.59 | ||||||
21.02, 44.62 | 21.48, 44.65 | ||||||
PU-2 |
N-BDA | ||||||
PU-3 | TFBD | 19.34,23.47 | 19.16 | ||||
26.72,36.03 | |||||||
61.61,20.89 | |||||||
44.28, | |||||||
PU-4 | POG 600 | BD | 6.7, 29.17 | 4.92 | |||
29.49, 39.21 | |||||||
42.95, 47.32 | |||||||
48.32, 57.21 | |||||||
65.1, 20.79 | |||||||
44.32 | |||||||
PU-5 | TFBD | ||||||
PU-6 | IPDI | POG 2,000 | BD | 19.41, 23.54 | 34.06 | ||
26.79, 36.12 | |||||||
43.07, 49.53 | |||||||
20.43 | |||||||
PU-7 |
N-MDA | ||||||
PU-8 |
N-BDA | ||||||
PU-9 | TDI | POG 2,000 | BD | 19.25, 23.37 | 31.82 | ||
26.55, 29.14 | |||||||
35.92, 39.15 | |||||||
42.9, 47.25 | |||||||
48.27, 50.23 | |||||||
57.16, 60.77 | |||||||
20.35 | |||||||
PU-10 | HDI | POG 2,000 | BD | ||||
PU-11 |
N-MDA |
Method for the synthesis of urethane cationomers
Sample no. | Type of diisocyanate | Type of polyol | Type of tertiary amine | Type of quaternisation reagent |
---|---|---|---|---|
KPU-1 | MDI | PPG 450 |
N-BDA | HCOOH |
KPU-2 | C4H9Br | |||
KPU-3 | C10H21Br | |||
KPU-4 | POG 600 |
N-MDA | HCOOH | |
KPU-5 |
N-MDA + 5% TFBD | |||
KPU-6 |
N-MDA + 10% TFBD | |||
KPU-7 |
N-MDA + 15% TFBD | |||
KPU-8 |
N-NDA + 15% TFBD | |||
KPU-9 | IPDI | PPG 450 |
N-MDA | |
KPU-10 | POG 600 | |||
KPU-11 | POG 600 |
N-BDA | ||
KPU12 | TDI | PPG 450 |
N-MDA | |
KPU-13 |
N-PhDA | |||
KPU-14 | HDI | PPG 450 |
N-MDA | |
KPU-15 |
N-PhDA |
WAXS analysis
DSC method
Atomic force microscopy
Method for determination of components of surface free energy for solids
Model measuring liquid | Surface free energy parameters [mJ/m2] | ||||||
---|---|---|---|---|---|---|---|
γ
L
|
\( \gamma_{\text{L}}^{\text{LW}} \)
|
\( \gamma_{\text{L}}^{\text{AB}} \)
|
\( \gamma_{\text{L}}^{ - } \)
|
\( \gamma_{\text{L}}^{ + } \)
|
\( \gamma_{\text{L}}^{\text{d}} \)
|
\( \gamma_{\text{L}}^{\text{p}} \)
| |
Water | 72.8 | 21.8 | 51 | 25.5 | 25.5 | 21.8 | 51 |
Formamide | 58.0 | 39.0 | 19.0 | 2.28 | 39.6 | – | – |
Diiodomethane | 50.8 | 50.8 | 0 | 0 | 0 | 48.5 | 2.3 |
α-Bromonaphthalene | 44.4 | 44.5 | 0 | 0 | 0 | – | – |
Results and discussion
Structures of synthesised polyurethanes
-
i = 1,2
-
A1 is the structure derived from POG (M n = 600 g/mol)$$ {\text{HO}} - \left[ {{{\left( {{\text{C}}{{\text{H}}_{{2}}} - {\text{C}}{{\text{H}}_{{2}}} - {\text{O}}} \right)}_{{{13}.{25}}}} - } \right] - {\text{H}} $$
-
A2 is the structure derived from POG (M n = 2,000 g/mol)$$ {\text{HO}} - \left[ {{{\left( {{\text{C}}{{\text{H}}_{{2}}} - {\text{C}}{{\text{H}}_{{2}}} - {\text{O}}} \right)}_{{{45}}}} - } \right] - {\text{H}} $$
-
Bi is the structure derived from MDI, IPDI, TDI or HDI diisocyanate
-
C is the structure derived from chain extender: BD, TFBD, N-MDA or N-BDA.
Phase structures
Sample no. | Type of polymer | Glass transition, °C | |
---|---|---|---|
Midpoint | ΔC
p, J/g·deg | ||
PU-4 | Linear PU | −23.1 | 0.349 |
45.6 | 0.166 | ||
PU-5 | −3.1 | 0.308 | |
KPU-4 | PU cationomer | 47.5 | 0.594 |
KPU-5 | 31.1 | 0.430 | |
KPU-6 | 42.8 | 0.532 | |
KPU-7 | 46.1 | 0.655 |
Polyurethane sample no. by Table 1
| van Oss–Good method by formamide–iiodomethane–water, [mJ/m2] | Owens–Wendt method by formamide–diiodomethane, [mJ/m2] | Owens–Wendt method by water–diiodomethane, [mJ/m2] | ||||||
---|---|---|---|---|---|---|---|---|---|
γ
S
|
\( \gamma_{\text{S}}^{\text{LW}} \)
|
\( \gamma_{\text{S}}^{\text{AB}} \)
|
γ
S
|
\( \gamma_{\text{S}}^{\text{d}} \)
|
\( \gamma_{\text{S}}^{\text{p}} \)
|
γ
S
|
\( \gamma_{\text{S}}^{\text{d}} \)
|
\( \gamma_{\text{S}}^{\text{p}} \)
| |
PU-3 | 23.91 | 22.80 | 1.11 | 26.21 | 25.62 | 0.59 | 26.38 | 23.78 | 2.60 |
PU-7 | 41.00 | 40.70 | 0.30 | 40.91 | 37.64 | 3.27 | – | – | – |
PU-8 | 43.46 | 43.15 | 0.31 | 43.17 | 40.72 | 2.45 | – | – | – |
PU-10 | 44.30 | 43.56 | 0.74 | 43.55 | 41.56 | 1.99 | – | – | |
PU-9 | 40.54 | 38.59 | 1.95 | 44.49 | 43.78 | 0.71 | 44.17 | 42.49 | 1.68 |
Cationomer sample no. by Table 2
| van Oss–Good method by formamide–diiodomethane–water, [mJ/m2] | van Oss–Good method by formamide-α–bromonaphtalene–water, [mJ/m2] | Owens–Wendt method by water–α-bromonaphtalene, [mJ/m2] | Owens–Wendt method by water–α-bromonaphtalene, [mJ/m2] | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
γ
S
|
\( \gamma_{\text{SL}}^{\text{LW}} \)
|
\( \gamma_{\text{S}}^{\text{AB}} \)
|
γ
S
|
\( \gamma_{\text{SL}}^{\text{LW}} \)
|
\( \gamma_{\text{S}}^{\text{AB}} \)
|
γ
S
|
\( \gamma_{\text{S}}^{\text{d}} \)
|
\( \gamma_{\text{S}}^{\text{p}} \)
|
γ
S
|
\( \gamma_{\text{S}}^{\text{d}} \)
|
\( \gamma_{\text{S}}^{\text{p}} \)
| |
KPU-4 | 51.83 | 43.00 | 8.83 | 50.77 | 42.09 | 8.68 | 50.92 | 35.76 | 15.16 | 49.33 | 36.29 | 13.04 |
KPU-5 | 37.64 | 33.35 | 4.29 | 42.83 | 41.20 | 1.63 | 42.02 | 38.41 | 3.61 | 38.39 | 33.30 | 5.09 |
KPU-6 | 35.21 | 29.92 | 5.29 | 38.36 | 35.92 | 2.44 | 35.97 | 35.81 | 0.16 | 35.13 | 28.71 | 6.42 |
KPU-7 | 33.62 | 33.12 | 0.49 | 27.92 | 27.91 | 0.01 | 27.55 | 27.52 | 0.03 | 31.02 | 24.80 | 6.22 |