The Effect of the Cooling Rate on the Morphology and Crystallization of Triple Crystalline PE -b- PEO -b- PLLA and PE -b- PCL -b- PLLA Triblock Terpolymers
Abstract
We study the non-isothermal crystallization and morphology of two triblock terpolymers of practically perfect linear polyethylene (PE), poly(ethylene oxide) (PEO) or poly(ε-caprolactone) (PCL), and poly( l -lactide) (PLLA) with three crystallizable blocks. The two triblock terpolymers PE 21 2.6 -b- PEO 32 4.0 -b- PLLA 47 5.9 and PE 21 7.1 -b- PCL 12 4.2 -b- PLLA 67 23.0 (subscripts indicate the composition in wt %, and superscripts refer to the number average molecular weights in kg/mol) were synthesized by a combination of polyhomologation and ring-opening polymerization techniques, using a “catalyst-switch” strategy. We have applied cooling ramps from the melt at 20 and 1 °C/min while simultaneously performing in situ SAXS/WAXS (small-angle X-ray scattering/wide-angle X-ray scattering) measurements. Parallel experiments performed by differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM) at identical rates allowed us to unequivocally identify the crystallization sequence of the three blocks from the melt, as well as their superstructural morphology. SAXS indicated that the samples are weakly segregated in the melt as breakout occurs upon crystallization. WAXS and DSC results demonstrated that when the crystallization occurs at 20 °C/min, the blocks crystallize in the following peculiar sequence: PE first, then PLLA, and finally PEO or PCL depending on the triblock terpolymer. The faster crystallization kinetics of the PE block, in comparison with the PLLA block, is responsible for this crystallization sequence. Only when the cooling rate is reduced to 1 °C/min can the PLLA block crystallize first and only for the terpolymer with the highest amount of PLLA. The cooling conditions determine the morphology and properties of these fascinating materials.
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50th Anniversary Perspective : Block Polymers─Pure Potential
Bates, C. M., & Bates, F. S. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b02355 · Cited by 792 · see citing works
Modes of Crystallization in Block Copolymer Microdomains: Breakout, Templated, and Confined
Loo, Y., Register, R. A., & Ryan, A. J. (2002) · Macromolecules · doi:10.1021/ma011824j · Cited by 453 · see citing works
Polymer spherulites: A critical review
Crist, B., & Schultz, J. M. (2015) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2015.11.006 · Cited by 437 · see citing works
Crystallization assisted self-assembly of semicrystalline block copolymers
He, W., & Xu, J. (2012) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2012.05.002 · Cited by 381 · see citing works
Phase Behaviour and Morphologies of Block Copolymers
Abetz, V., & Simon, P. F. W. (2005) · Springer eBooks · doi:10.1007/12_004 · Cited by 369 · see citing works
Nucleation and Crystallization in Diblock and Triblock Copolymers
Müller, A. J., Balsamo, V., & Arnal, M. L. (2005) · Advances in Polymer Science · doi:10.1007/12_001 · Cited by 294 · see citing works
Self-citationCastillo, R. V., & Müller, A. J. (2009) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2009.03.002 · Cited by 253 · see citing works
Self-citationStructure Development in Semicrystalline Diblock Copolymers Crystallizing from the Ordered Melt
Ryan, A. J., Hamley, I. W., Bras, W., & Bates, F. S. (1995) · Macromolecules · doi:10.1021/ma00115a016 · Cited by 233 · see citing works
Hadjichristidis, N., Pitsikalis, M., & Iatrou, H. (2005) · Springer eBooks · doi:10.1007/12_005 · Cited by 209 · see citing works
Self-citationCastillo, R. V., Müller, A. J., Raquez, J.-M., & Dubois, P. (2010) · Macromolecules · doi:10.1021/ma100201g · Cited by 175 · see citing works
Self-citationHamley, I. W., Castelletto, V., Castillo, R. V., Müller, A. J., Martin, C. M., Pollet, E., & Dubois, P. (2005) · Macromolecules · doi:10.1021/ma0481499 · Cited by 160 · see citing works
Self-citationStudy on crystalline morphology of poly(L-lactide)-poly(ethylene glycol) diblock copolymer
Sun, J., Hong, Z., Yang, L., Tang, Z., Chen, X., & Jing, X. (2004) · Polymer · doi:10.1016/j.polymer.2004.06.026 · Cited by 117 · see citing works
Hamley, I. W., Parras, P., Castelletto, V., Castillo, R. V., Müller, A. J., Pollet, E., Dubois, P., & Martin, C. M. (2006) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200600085 · Cited by 108 · see citing works
Self-citationCrystallization in block copolymers with more than one crystallizable block
Müller, A. J., Arnal, M. L., & Balsamo, V. (2007) · Lecture Notes in Physics · doi:10.1007/3-540-47307-6_13 · Cited by 78 · see citing works
Self-citationCrystallization and higher-order structure of multicomponent polymeric systems
Takeshita, H., Shiomi, T., Takenaka, K., & Arai, F. (2013) · Polymer · doi:10.1016/j.polymer.2013.06.031 · Cited by 72 · see citing works
Nojima, S., Akutsu, Y., Akaba, M., & Tanimoto, S. (2005) · Polymer · doi:10.1016/j.polymer.2005.02.075 · Cited by 72 · see citing works
Crystalline and Spherulitic Morphology of Polymers Crystallized in Confined Systems
Yu, C., Xie, Q. M., Bao, Y., Shan, G., & Pan, P. (2017) · Crystals · doi:10.3390/cryst7050147 · Cited by 66 · see citing works
Huang, S., Jiang, S., An, L., & Chen, X. (2008) · Journal of Polymer Science Part B: Polymer Physics · doi:10.1002/polb.21474 · Cited by 65 · see citing works
Yang, J., Zhao, T., Cui, J., Liu, L., Zhou, Y., Li, G., Zhou, E., & Chen, X. (2006) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/polb.20886 · Cited by 63 · see citing works
Crystallization of polymer chains confined in nanodomains
Nakagawa, S., Marubayashi, H., & Nojima, S. (2015) · European Polymer Journal · doi:10.1016/j.eurpolymj.2015.07.018 · Cited by 61 · see citing works
Jiang, S., He, C., An, L., Chen, X., & Jiang, B. (2004) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200400204 · Cited by 58 · see citing works
Li, Y., Huang, H., Wang, Z., & He, T. (2014) · Macromolecules · doi:10.1021/ma402579d · Cited by 56 · see citing works
Recent progress in block copolymer crystallization
Horn, R. M. V., Steffen, M. R., & O’Connor, D. (2018) · Polymer Crystallization · doi:10.1002/pcr2.10039 · Cited by 49 · see citing works
Arnal, M. L., López‐Carrasquero, F., Laredo, E., & Müller, A. J. (2004) · European Polymer Journal · doi:10.1016/j.eurpolymj.2004.02.023 · Cited by 47 · see citing works
Self-citationYang, J., Liang, Y., & Han, C. C.-C. (2015) · Polymer · doi:10.1016/j.polymer.2015.09.067 · Cited by 45 · see citing works
Structures and morphologies of biocompatible and biodegradable block copolymers
Huang, S., & Jiang, S. (2014) · RSC Advances · doi:10.1039/c4ra03043e · Cited by 43 · see citing works
Chiang, Y., Hu, Y.-Y., Li, J.-N., Huang, S.-H., & Kuo, S. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b02042 · Cited by 42 · see citing works
Palacios, J. K., Zhao, J., Hadjichristidis, N., & Müller, A. J. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b02148 · Cited by 41 · see citing works
Self-citationLi, L., Meng, F., Zhong, Z., Белов, Д. В., de Jeu, W. H., & Feijén, J. (2007) · The Journal of Chemical Physics · doi:10.1063/1.2405357 · Cited by 40 · see citing works
Trilayered morphology of an ABC triple crystalline triblock terpolymer
Palacios, J. K., Tercjak, A., Liu, G., Wang, D., Zhao, J., Hadjichristidis, N., & Müller, A. J. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b01576 · Cited by 37 · see citing works
Self-citationNucleation and Crystallization of PLDA‐ b ‐PE and PLLA‐ b ‐PE Diblock Copolymers
Müller, A. J., Castillo, R. V., & Hillmyer, M. A. (2006) · Macromolecular Symposia · doi:10.1002/masy.200651025 · Cited by 36 · see citing works
Self-citationZhou, D., Sun, J., Shao, J., Bian, X., Huang, S., Li, G., & Chen, X. (2015) · Polymer · doi:10.1016/j.polymer.2015.10.066 · Cited by 31 · see citing works
Liénard, R., Zaldua, N., Josse, T., Winter, J. D., Zubitur, M., Múgica, A., Iturrospe, A., Arbe, A., Coulembier, O., & Müller, A. J. (2016) · Macromolecular Rapid Communications · doi:10.1002/marc.201600309 · Cited by 31 · see citing works
Self-citationArnal, M. L., Boissé, S., Müller, A. J., Meyer, F., Raquez, J., Dúbois, P., & Prud'homme, R. E. (2016) · CrystEngComm · doi:10.1039/c6ce00330c · Cited by 26 · see citing works
Self-citationPoly(vinylidene fluoride)/Polymethylene-Based Block Copolymers and Terpolymers
Zapsas, G., Patil, Y., Bilalis, P., et al. (2019) · Macromolecules · doi:10.1021/acs.macromol.8b02663 · Cited by 25 · see citing works
Self-citationTetracrystalline Tetrablock Quarterpolymers: Four Different Crystallites under the Same Roof
Ladelta, V., Zapsas, G., Abou‐hamad, E., Gnanou, Y., & Hadjichristidis, N. (2019) · Angewandte Chemie International Edition · doi:10.1002/anie.201908688 · Cited by 22 · see citing works
Self-citationHuang, S., Li, H., Jiang, S., Chen, X., & An, L. (2011) · Polymer Bulletin · doi:10.1007/s00289-011-0518-8 · Cited by 21 · see citing works
Ponjavic, M., Nikolic, M. S., Jevtic, S., Rogan, J., Stevanovic, S., & Djonlagic, J. (2016) · Macromolecular Research · doi:10.1007/s13233-016-4048-y · Cited by 20 · see citing works
Li, S., & Register, R. A. (2013) · doi:10.1002/9781118541838.ch11 · Cited by 19 · see citing works
Vivas, M., Contreras, J., López‐Carrasquero, F., Lorenzo, A. T., Arnal, M. L., Balsamo, V., Müller, A. J., Laredo, E., Schmalz, H., & Abetz, V. (2006) · Macromolecular Symposia · doi:10.1002/masy.200690110 · Cited by 19 · see citing works
Self-citationPalacios, J. K., Mugica, A., Zubitur, M., & Müller, A. J. (2018) · Crystallization in Multiphase Polymer Systems · doi:10.1016/b978-0-12-809453-2.00006-2 · Cited by 18 · see citing works
Self-citationPalacios, J. K., Liu, G., Wang, D., Hadjichristidis, N., & Müller, A. J. (2019) · Macromolecular Chemistry and Physics · doi:10.1002/macp.201900292 · Cited by 15 · see citing works
Self-citationLadelta, V., Zapsas, G., Gnanou, Y., & Hadjichristidis, N. (2019) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.29492 · Cited by 9 · see citing works
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Matxinandiarena, E., Múgica, A., Tercjak, A., Ladelta, V., Zapsas, G., Hadjichristidis, N., Cavallo, D., Flores, A., & Müller, A. J. (2021) · Macromolecules · doi:10.1021/acs.macromol.1c01186 · Cited by 16 · see citing works
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- Authors
- Matxinandiarena, E., Múgica, A., Zubitur, M., Zhang, B., Ladelta, V., Zapsas, G., Hadjichristidis, N., & Müller, A. J.
- Affiliations
- University of the Basque Country (ES)
- Zhengzhou University (CN)
- King Abdullah University of Science and Technology (SA)
- Ikerbasque (ES)
- Corresponding author
- Hadjichristidis, Nikos
- Müller, Alejandro J.
- ORCID
- Venue
- ACS Applied Polymer Materials
- Publisher
- American Chemical Society (ACS)
- Published
- 2020-10-14
- Volume
- 2
- Issue
- 11
- Pages
- 4952-4963
- ISSN
- 2637-6105 (ISSN-L)
- OpenAlex
- W3097821303
- Cited by
- 16
- References
- 43
- Citations by year
- 2026: 2 · 2025: 6 · 2024: 1 · 2023: 3 · 2022: 2 · 2021: 2
- FWCI
- 0.66
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- ACS Applied Polymer Materials (publishedVersion)
- King Abdullah University of Science and Technology Repository (King Abdullah University of Science and Technology) (submittedVersion)
- Funders
- Ministerio de Econom?a y Competitividad (MAT2017-83014-C2-1-P)
- Eusko Jaurlaritza (IT1309-19)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Keywords
- triblock terpolymers, non-isothermal crystallization, cooling rate, crystallization sequence, block copolymer morphology, superstructure, crystallization kinetics, polycaprolactone, poly(ethylene oxide), poly(L-lactic acid), ring-opening polymerization, melt segregation, in situ SAXS/WAXS
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