Tetracrystalline Tetrablock Quarterpolymers: Four Different Crystallites under the Same Roof
Abstract
Multicrystalline block polymers having three or more crystalline segments are essential materials for the advancement of physics in the field of crystallinity. The challenging synthesis of multicrystalline polymers has resulted in only a limited number of tricrystalline terpolymers having been reported to date. We report, for the first time, the synthesis of polyethylene‐ b ‐poly(ethylene oxide)‐ b ‐poly(ϵ‐caprolactone)‐ b ‐poly( l ‐lactide) (PE‐ b ‐PEO‐ b ‐PCL‐ b ‐PLLA), a tetracrystalline tetrablock quarterpolymer, by combining polyhomologation, ring‐opening polymerization, and an organic/metal “catalyst switch” strategy. 1 H NMR spectroscopy and gel‐permeation chromatography confirmed the formation of the tetrablock quarterpolymer, while differential scanning calorimetry, X‐ray diffraction, and wide‐line separation solid‐state NMR spectroscopy revealed the existence of four different crystalline domains.
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The formation of tetracrystalline quarterpolymers was confirmed by 1H NMR spectroscopy and gel-permeation chromatography.
“The formation of tetracrystalline quarterpolymers was confirmed by 1H NMR spectroscopy and gel-permeation chromatography.54”
From Sequential Crystallization and Multicrystalline Morphology in PE- <i>b</i> -PEO- <i>b</i> -PCL- <i>b</i> -PLLA Tetrablock Quarterpolymers (2021) · cites this paper as [54]
The organic/metal catalyst switch using Sn(Oct)2 was applied to obtain S,S-lactide monomeric units.
“Therefore, an organic/metal t-BuP4/DPP/Sn(Oct)2 ″catalyst switch″ strategy was applied, which consists of using tin(II) 2-ethylhexanoate [Sn(Oct)2] to obtain S,S-lactide monomeric units.54”
From Sequential Crystallization and Multicrystalline Morphology in PE- <i>b</i> -PEO- <i>b</i> -PCL- <i>b</i> -PLLA Tetrablock Quarterpolymers (2021) · cites this paper as [54]
Cites
Controlled Ring-Opening Polymerization of Lactide and Glycolide
Dechy-Cabaret, O., Martin-Vaca, B., & Bourissou, D. (2004) · Chemical Reviews · doi:10.1021/cr040002s · Cited by 2,257 · see citing works
Handbook of thermal analysis and calorimetry
GALLAGHER, P. K. (1998) · Handbook of thermal analysis and calorimetry · Cited by 823 · see citing works
Peacock, A. (2000) · CRC Press eBooks · doi:10.1201/9781482295467 · Cited by 688 · see citing works
Schmidt‐Rohr, K., Clauss, J., & Spiess, H. W. (1992) · Macromolecules · doi:10.1021/ma00038a037 · Cited by 488 · see citing works
Toughening of polylactide by melt blending with linear low‐density polyethylene
Anderson, K. S., Lim, S., & Hillmyer, M. A. (2003) · Journal of Applied Polymer Science · doi:10.1002/app.12462 · Cited by 362 · see citing works
Castillo, R. V., & Müller, A. J. (2009) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2009.03.002 · Cited by 253 · see citing works
Nojima, S., Kato, K., Yamamoto, S., & Ashida, T. (1992) · Macromolecules · doi:10.1021/ma00034a027 · Cited by 248 · see citing works
Wang, Y., & Hillmyer, M. A. (2001) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1254 · Cited by 214 · see citing works
Dong, C., Qiu, K., Gu, Z., & Feng, X. (2001) · Macromolecules · doi:10.1021/ma010005w · Cited by 160 · see citing works
Synthesis and crystallization behavior of poly( l -lactide)- block -poly(ϵ-caprolactone) copolymer
Kim, J. K., Park, D.-J., Lee, M.-S., & Ihn, K. J. (2001) · Polymer · doi:10.1016/s0032-3861(01)00217-8 · Cited by 147 · see citing works
Zhang, Z., Ortiz, O., Goyal, R., & Kohn, J. (2013) · Elsevier eBooks · doi:10.1016/b978-0-323-22805-3.00013-x · Cited by 136 · see citing works
Study 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
Polyhomologation. A Living C1 Polymerization
Luo, J., & Shea, K. J. (2010) · Accounts of Chemical Research · doi:10.1021/ar100062a · Cited by 112 · see citing works
Castillo, R. V., Müller, A. J., Lin, M.-C., Chen, H., Jeng, U., & Hillmyer, M. A. (2008) · Macromolecules · doi:10.1021/ma800859y · Cited by 111 · see citing works
Holland, G. P., Lewis, R. V., & Yarger, J. L. (2004) · Journal of the American Chemical Society · doi:10.1021/ja031930w · Cited by 111 · see citing works
Effect of the molecular weight on the crystallinity of PCL-b-PLLA di-block copolymers
Peponi, L., Navarro-Baena, I., Báez, J. E., Kenny, J. M., & Marcos-Fernández, A. (2012) · Polymer · doi:10.1016/j.polymer.2012.07.066 · Cited by 109 · see citing works
Busch, B. B., Paz, M. M., Shea, K. J., et al. (2002) · Journal of the American Chemical Society · doi:10.1021/ja017376c · Cited by 102 · see citing works
He, C., Sun, J., Zhao, T., Hong, Z., Zhuang, X., Chen, X., & Jing, X. (2005) · Biomacromolecules · doi:10.1021/bm050627f · Cited by 97 · see citing works
Horn, R. M. V., Zheng, J. X., Sun, H., Hsiao, M.-S., Zhang, W., Dong, X., Xu, J., Thomas, E. L., Lotz, B., & Cheng, S. Z. D. (2010) · Macromolecules · doi:10.1021/ma1010793 · Cited by 93 · see citing works
Zhao, J., Pahovnik, D., Gnanou, Y., & Hadjichristidis, N. (2014) · Macromolecules · doi:10.1021/ma500830v · Cited by 92 · see citing works
Self-citationHe, C., Sun, J., Ma, J., Chen, X., & Jing, X. (2006) · Biomacromolecules · doi:10.1021/bm060578m · Cited by 85 · see citing works
Zhao, J., Pahovnik, D., Gnanou, Y., & Hadjichristidis, N. (2014) · Polym. Chem. · doi:10.1039/c4py00429a · Cited by 79 · see citing works
Self-citationWang, J., & Dong, C. (2006) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200500546 · Cited by 76 · see citing works
Wang, Y., & Hillmyer, M. A. (2000) · Macromolecules · doi:10.1021/ma0007177 · Cited by 72 · see citing works
Nojima, S., Nakano, H., Takahashi, Y., & Ashida, T. (1994) · Polymer · doi:10.1016/0032-3861(94)90912-1 · Cited by 72 · 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
Morphology of melt-quenched poly(ε-caprolactone)-block-polyethylene copolymers
Nojima, S., Akutsu, Y., Washino, A., & Tanimoto, S. (2004) · Polymer · doi:10.1016/j.polymer.2004.08.044 · Cited by 62 · see citing works
Yang, J., Zhao, T., Zhou, Y., Liu, L., Li, G., Zhou, E., & Chen, X. (2007) · Macromolecules · doi:10.1021/ma062727z · Cited by 61 · see citing works
Li, Q., Zhang, G., Chen, J., et al. (2010) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.24464 · Cited by 51 · see citing works
Lü, Y., Hu, Y., & Chung, T. C. M. (2005) · Polymer · doi:10.1016/j.polymer.2005.07.094 · Cited by 48 · see citing works
Single crystals morphology of biodegradable double crystalline PLLA-b-PCL diblock copolymers
Casas, M. T., Puiggalí, J., Raquez, J.-M., Dubois, P., Córdova, M. E., & Müller, A. J. (2011) · Polymer · doi:10.1016/j.polymer.2011.08.057 · Cited by 44 · see citing works
Nojima, S., Kiji, T., & Ohguma, Y. (2007) · Macromolecules · doi:10.1021/ma0627830 · Cited by 44 · see citing works
Ring, J., Thomann, R., Mülhaupt, R., Raquez, J., Degée, P., & Dúbois, P. (2007) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200600640 · Cited by 44 · 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
Well-Defined Polyethylene-Based Random, Block, and Bilayered Molecular Cobrushes
Zhang, H., Zhang, Z., Gnanou, Y., et al. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b00713 · Cited by 41 · see citing works
Self-citationC1 polymerization: a unique tool towards polyethylene-based complex macromolecular architectures
Wang, D., Zhang, Z., & Hadjichristidis, N. (2017) · Polymer Chemistry · doi:10.1039/c7py00581d · Cited by 41 · see citing works
Self-citationPalacios, J. K., Zhao, J., Hadjichristidis, N., & Müller, A. J. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b02148 · Cited by 41 · see citing works
Self-citationLadelta, V., Kim, J. D., Bilalis, P., Gnanou, Y., & Hadjichristidis, N. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b00153 · Cited by 40 · see citing works
Self-citationTrilayered 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-citationAjami, D., Rodríguez-Silva, M., Sabino, M. A., Castillo, R. V., Müller, A. J., Boschetti‐de‐Fierro, A., Abetz, C., Abetz, V., & Dúbois, P. (2008) · Journal of Biomedical Materials Research Part A · doi:10.1002/jbm.a.31796 · Cited by 36 · see citing works
Nucleation 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
Guillerm, B., Lemaur, V., Ernould, B., Cornil, J., Lazzaroni, R., Gohy, J., Dúbois, P., & Coulembier, O. (2014) · RSC Advances · doi:10.1039/c3ra47204c · Cited by 34 · see citing works
Synthesis, characterization, and degradation of poly(ethylene‐b‐ε‐caprolactone) diblock copolymer
Báez, J. E., Ramírez‐Hernández, A., & Marcos-Fernández, Á. A. (2009) · Polymers for Advanced Technologies · doi:10.1002/pat.1399 · Cited by 26 · see citing works
WIM/WISE NMR Studies of Chain Dynamics in Solid Polymers and Blends
Qiu, X., & Mirau, P. A. (2000) · Journal of Magnetic Resonance · doi:10.1006/jmre.1999.1934 · Cited by 25 · see citing works
Palacios, J. K., Mugica, A., Zubitur, M., Iturrospe, A., Arbe, A., Liu, G., Wang, D., Zhao, J., Hadjichristidis, N., & Müller, A. J. (2016) · RSC Advances · doi:10.1039/c5ra25812j · Cited by 23 · see citing works
Self-citationAlamri, H., & Hadjichristidis, N. (2016) · Polymer Chemistry · doi:10.1039/c6py00314a · Cited by 21 · see citing works
Self-citationPolyethylene‐block‐poly(ε‐caprolactone) diblock copolymers: synthesis and compatibility
Mu, J., Yang, F., Liu, Z., et al. (2014) · Polymer International · doi:10.1002/pi.4754 · Cited by 12 · see citing works
Báez, J. E., Zhao, R., & Shea, K. J. (2017) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.7b02596 · Cited by 12 · see citing works
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Michell, R. M., Ladelta, V., Da Silva, E., Müller, A. J., & Hadjichristidis, N. (2023) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2023.101742 · Cited by 77 · see citing works
Self-citationMatxinandiarena, 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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Self-citation
- Authors
- Ladelta, V., Zapsas, G., Abou‐hamad, E., Gnanou, Y., & Hadjichristidis, N.
- Affiliations
- King Abdullah University of Science and Technology (SA)
- Corresponding author
- Hadjichristidis, Nikos
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2019-09-18
- Volume
- 58
- Issue
- 45
- Pages
- 16267-16274
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W2971184783
- Cited by
- 22
- References
- 50
- Citations by year
- 2026: 3 · 2025: 4 · 2024: 3 · 2023: 3 · 2022: 4 · 2021: 2 · 2020: 3
- FWCI
- 0.15
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Angewandte Chemie International Edition (publishedVersion)
- PubMed (publishedVersion)
- King Abdullah University of Science and Technology Repository (King Abdullah University of Science and Technology) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Keywords
- poly(ethylene oxide), polycaprolactone, poly(L-lactic acid), polyethylene, crystalline domains, ring-opening polymerization, crystallinity
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