Crystalline Structures and Structural Transitions of Copolyamides Derived from 1,4-Diaminobutane and Different Ratios of Glutaric and Azelaic Acids
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials and Synthesis of Copolyamides Based on 1,4-Diaminobutane and Glutaric and Azelaic Acids
2.2. Measurements
3. Results and Discussion
3.1. Synthesis of Nylons 4,5+9_X
3.2. Thermal Properties of Nylons 4,5+9_X
- (a)
- Melting enthalpies were clearly dependent on the specific composition and specifically decreased as the comonomer content increased (i.e., nylons 4,5+9_40 and 4,5+9_50 with fA values of 0.45 and 0.55 showed the lower melting enthalpies) for compositions with fA higher than 0.15. Thus, the enthalpies observed in the second heating scan varied from a minimum of 43.5 J/g (for fA = 0.55) and a maximum of 86.8 J/g (for fA = 1). Nevertheless, the minimum enthalpy was detected for nylon 4,5+9_15 (i.e., 31.0 J/g) probably due to the occurrence of some degradation before fusion as discussed later.
- (b)
- Melting enthalpies of solution-precipitated samples were clearly higher than those determined from melt crystallized samples and obviously than exhibited after fast cooling. Nevertheless, it is significant that the capacity to crystallize even for samples with a high comonomer content and even after the quenching process (e.g., 37.7 J/g for nylon 4,5+9_50).
- (c)
- A predominant melting peak in the 220–244 °C interval (second heating run) was always observed. This peak is associated to the fusion of lamellar crystals formed during the previous crystallization process. Peak temperature decreased with the comonomer content (e.g., 233 °C, 220 °C and 244 °C for samples with X equal to 100, 50 and 0, respectively).
- (d)
- A peak of variable intensity in the 228–244 °C interval is also usually observed. This peak can be associated with the fusion of lamellae recrystallized during the heating process and appeared at a practically constant temperature when copolymer composition was varied. Thus, the predominant initial lamellae followed a typical reorganization process that led to an increase of the thickness and obviously of the melting temperature. A hot crystallization exotherm can be observed in some cases between the two main melting peaks (e.g., see nylon 4,5+9_100 in Figure 2b and data corresponding to the third heating run in Table 2). Comparison between second and third heating traces points out that reordering was favoured when the sample was less crystalline (i.e., samples obtained by fast cooling) since probably more segments able to be incorporated into the crystalline lamellae are disposable on the lamellar surface.
- (e)
- Additional low-intensity endothermic processes can be envisaged at temperatures lower than the main melting peak temperature. These processes may correspond to the fusion of high defective crystals or the melting of crystals having a different crystalline structure.
- (f)
- Samples easily crystallized in the cooling run from the melt state, decreasing the crystallization peak temperature (i.e., from 212/218 °C to 196 °C) and enthalpy (i.e., from 69.2 to 39.3 J/g for fA > 0.15) with the comonomer content. Logically, the presence of structural foreign units hindered the crystallization process.
- (g)
- A single glass transition temperature was always detected as evidence that phase separation did not occur in the amorphous fraction. In any case the Tg varied in a narrow interval (e.g., between 50 and 71 °C) being difficult to deduce a specific trend since both composition and molecular weight played a significant influence. Logically the homopolymer derived from glutaric acid was slightly more rigid than that constituted by azelaic acid (i.e., 71 °C with respect to 50 °C).
3.3. Equilibrium Melting Point of Nylon 4,5+9_X Copolymers
3.4. Melting Point Depression
3.5. Morphology of Nylon 4,5+9 Single Crystals
3.6. Morphology of Nylon 4,5+9_X Spherulites Obtained from Melt Crystallization
3.7. X-ray Diffraction Patterns of Solution Crystallized Samples
3.8. Structural Transitions During the Heating Process of Solution Crystallized Homopolymer Samples
3.9. Structural Transitions During the Heating Process of Solution Crystallized Copolymer Samples
3.10. Structural Transitions During the Cooling and Reheating Process of Nylon 4,5+9 Samples
4. Conclusions
Supplementary Materials
Author Contributions
Acknowledgments
Conflicts of Interest
References
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Sample | Yield (%) | fA | Mn (g/mol) | Mw (g/mol) | PDI |
---|---|---|---|---|---|
Nylon 4,5+9_0 | 50 | 0 | 16,000 | 40,000 | 2.5 |
Nylon 4,5+9_15 | 54 | 0.15 | 18,000 | 43,000 | 2.4 |
Nylon 4,5+9_40 | 53 | 0.45 | 17,000 | 41,000 | 2.4 |
Nylon 4,5+9_50 | 60 | 0.55 | 22,000 | 51,000 | 2.3 |
Nylon 4,5+9_60 | 58 | 0.73 | 20,000 | 44,000 | 2.2 |
Nylon 4,5+9_85 | 57 | 0.90 | 21,000 | 47,000 | 2.2 |
Nylon 4,5+9_100 | 63 | 1 | 20,000 | 46,000 | 2.3 |
Sample | 1st Heating Scan | Cooling Scan | |||||
Tf (°C) | ΔHf (J/g) | Tc (°C) | ΔHc (J/g) | ||||
Nylon 4,5+9_0 | 233,249 | 56.8 | 212 | 30.1 | |||
Nylon 4,5+9_15 | 207,225,237 | 50.3 | 203 | 29.4 | |||
Nylon 4,5+9_40 | 205,224,239 | 57.2 | 199 | 39.3 | |||
Nylon 4,5+9_50 | 206,224,234 | 65.0 | 196 | 38.9 | |||
Nylon 4,5+9_60 | 207,225,236 | 72.0 | 200 | 48.6 | |||
Nylon 4,5+9_85 | 213,229,239 | 82.2 | 209 | 56.0 | |||
Nylon 4,5+9_100 | 215,233,244 | 104 | 218 | 69.2 | |||
Sample | 2nd Heating Scan | 3rd Heating Scan | |||||
Tf (°C) | ΔHf (J/g) | Tg (°C) | Tf (°C) | Thc (°C) | ΔHhc (J/g) | ΔHf (J/g) | |
Nylon 4,5+9_0 | 221,244 | 35.9 | 71.2 | 239 | - | - | 36.6 |
Nylon 4,5+9_15 | 205,224,228 | 31.0 | 54.9 | 188,209 | - | - | 208 |
Nylon 4,5+9_40 | 175,201,222 | 43.5 | 50.2 | 178,218 | 197 | 2.7 | 5.5,32.3 |
Nylon 4,5+9_50 | 178,198,220 | 45.3 | 50.6 | 178,220,228 | 199 | 0.6 | 5.6,32.1 |
Nylon 4,5+9_60 | 177,201,224,234 | 59.9 | 52.6 | 177,222,232 | 200 | 3.1 | 5.6,45.7 |
Nylon 4,5+9_85 | 185,212,228,237 | 64.4 | 52.6 | 183,227,237 | 207 | 3.5 | 1.9,54.4 |
Nylon 4,5+9_100 | 195,233,244 | 86.6 | 50.0 | 195,231,243 | 236 | 0.4 | 39.9,39.2 |
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Olmo, C.; Casas, M.T.; Martínez, J.C.; Franco, L.; Puiggalí, J. Crystalline Structures and Structural Transitions of Copolyamides Derived from 1,4-Diaminobutane and Different Ratios of Glutaric and Azelaic Acids. Polymers 2019, 11, 572. https://doi.org/10.3390/polym11040572
Olmo C, Casas MT, Martínez JC, Franco L, Puiggalí J. Crystalline Structures and Structural Transitions of Copolyamides Derived from 1,4-Diaminobutane and Different Ratios of Glutaric and Azelaic Acids. Polymers. 2019; 11(4):572. https://doi.org/10.3390/polym11040572
Chicago/Turabian StyleOlmo, Cristian, María T. Casas, Juan C. Martínez, Lourdes Franco, and Jordi Puiggalí. 2019. "Crystalline Structures and Structural Transitions of Copolyamides Derived from 1,4-Diaminobutane and Different Ratios of Glutaric and Azelaic Acids" Polymers 11, no. 4: 572. https://doi.org/10.3390/polym11040572
APA StyleOlmo, C., Casas, M. T., Martínez, J. C., Franco, L., & Puiggalí, J. (2019). Crystalline Structures and Structural Transitions of Copolyamides Derived from 1,4-Diaminobutane and Different Ratios of Glutaric and Azelaic Acids. Polymers, 11(4), 572. https://doi.org/10.3390/polym11040572