Scattering Function and Spinodal Transition of Linear and Nonlinear Block Copolymers Based on a Unified Molecular Model

Weichao Shi

doi:10.1007/s10118-021-2544-9

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Scattering Function and Spinodal Transition of Linear and Nonlinear Block Copolymers Based on a Unified Molecular Model

ARTICLE | Updated：2021-02-10

- Scattering Function and Spinodal Transition of Linear and Nonlinear Block Copolymers Based on a Unified Molecular Model
- Chinese Journal of Polymer Science Vol. 39, Issue 6, Pages: 779-788(2021)
- Affiliations：
  
  Key Laboratory of Functional Polymer Materials of Ministry of Education; Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
- Author bio：
  
  weichaoshi@nankai.edu.cn
- Funds：
- DOI：10.1007/s10118-021-2544-9
  CLC：
- Received：29 November 2020，
  
  Revised：2020-12-28，
  
  Accepted：30 December 2020，
  
  Online First：10 February 2021，
  
  Published：15 April 2021
- Accepted：
Scan QR Code
Shi, W. Scattering function and spinodal transition of linear and nonlinear block copolymers based on a unified molecular model. Chinese J. Polym. Sci. 2021, 39, 779–788

Weichao Shi. Scattering Function and Spinodal Transition of Linear and Nonlinear Block Copolymers Based on a Unified Molecular Model[J]. Chinese Journal of Polymer Science, 2021, 39(6): 779-788.
Shi, W. Scattering function and spinodal transition of linear and nonlinear block copolymers based on a unified molecular model. Chinese J. Polym. Sci. 2021, 39, 779–788 DOI： 10.1007/s10118-021-2544-9.

Weichao Shi. Scattering Function and Spinodal Transition of Linear and Nonlinear Block Copolymers Based on a Unified Molecular Model[J]. Chinese Journal of Polymer Science, 2021, 39(6): 779-788. DOI： 10.1007/s10118-021-2544-9.

摘要

Abstract

This work uses a block copolymer architecture [(A’B)

]

to unify the scattering function and spinodal transition of typical AB-type block copolymers. The key roles of block number

junction points and asymmetry ratios of block length are (1) to determine the form factor of each block copolymer at the molecular scale; (2) to affect the entropy loss across the spinodal transition and may result in deflection of spinodal curves. The common features are validated in typical linear and nonlinear block copolymers

including AB diblock

asymmetric A’BA triblock

miktoarm stars of AB

(AB)

(A’B)

A’BA

and multi-graft combs of (B

)

and [(A’B)

]

. The explicit scattering functions and form factors of various block copolymers can be directly applied in radiation experiments (

i.e

. neutron or X-ray scattering) to unravel the effect of molecular architecture in solution and microphase separation in disordered melt. The molecular model used in this study is also helpful to guide the chemical synthesis to explore more potentially interesting block copolymers.

关键词

Keywords

references

Bates, F. S.; Fredrickson, G. H. . Block copolymer thermodynamics: theory and experiment . Annu. Rev. Phys. Chem. , 1990 . 41 525 - 557 . DOI: 10.1146/annurev.pc.41.100190.002521 http://doi.org/10.1146/annurev.pc.41.100190.002521 .

Leibler, L. . Theory of microphase separation in block copolymers . Macromolecules , 1980 . 13 1602 - 1617 . DOI: 10.1021/ma60078a047 http://doi.org/10.1021/ma60078a047 .

Matsen, M. W.; Bates, F. S. . Unifying weak- and strong-segregation block copolymer theories . Macromolecules , 1996 . 29 1091 - 1098 . DOI: 10.1021/ma951138i http://doi.org/10.1021/ma951138i .

Fredrickson, G. H. The equilibrium theory of inhomogeneous polymers. Oxford University Press: New York, 2006 .

Olvera de la Cruz, M.; Sanchez, I. C. . Theory of microphase separation in graft and star copolymers . Macromolecules , 1986 . 19 2501 - 2508 . DOI: 10.1021/ma00164a008 http://doi.org/10.1021/ma00164a008 .

Milner, S. T. . Chain architecture and asymmetry in copolymer microphases . Macromolecules , 1994 . 27 2333 - 2335 . DOI: 10.1021/ma00086a057 http://doi.org/10.1021/ma00086a057 .

Matsen, M. W.; Schick, M. . Microphase separation in starblock copolymer melts . Macromolecules , 1994 . 27 6761 - 6767 . DOI: 10.1021/ma00101a014 http://doi.org/10.1021/ma00101a014 .

Shinozaki, A.; Jasnow, D.; Balazs, A. C. . Microphase separation in comb copolymers . Macromolecules , 1994 . 27 2496 - 2502 . DOI: 10.1021/ma00087a018 http://doi.org/10.1021/ma00087a018 .

Matsen, M. W. . Effect of architecture on the phase behavior of AB-type block copolymer melts . Macromolecules , 2012 . 45 2161 - 2165 . DOI: 10.1021/ma202782s http://doi.org/10.1021/ma202782s .

Polymeropoulos, G.; Zapsas, G.; Ntetsikas, K.; Bilalis, P.; Gnanou, Y.; Hadjichristidis, N. . 50 th Anniversary perspective: polymers with complex architectures . Macromolecules , 2017 . 50 1253 - 1290 . DOI: 10.1021/acs.macromol.6b02569 http://doi.org/10.1021/acs.macromol.6b02569 .

Zhulina, E. B.; Borisov, O. V. . Effect of block copolymer architecture on morphology of self-assembled aggregates in solution . ACS Macro Lett. , 2013 . 2 292 - 295 . DOI: 10.1021/mz400035k http://doi.org/10.1021/mz400035k .

Augustine, D.; Hadjichristidis, N.; Gnanou, Y.; Feng, X. . Hydrophilic stars, amphiphilic star block copolymers, and miktoarm stars with degradable polycarbonate cores . Macromolecules , 2020 . 53 895 - 904 . DOI: 10.1021/acs.macromol.9b02658 http://doi.org/10.1021/acs.macromol.9b02658 .

Huang, C. I.; Yu, H. T. . Microphase separation and molecular conformation of AB 2 miktoarm star copolymers by dissipative particle dynamics . Polymer , 2007 . 48 4537 - 4546 . DOI: 10.1016/j.polymer.2007.06.002 http://doi.org/10.1016/j.polymer.2007.06.002 .

Teng, X.; Zhang, P.; Liu, T.; Xin, J.; Zhang, J. . Biobased miktoarm star copolymer from soybean oil, isosorbide, and caprolactone . J. Appl. Polym. Sci. , 2020 . 137 48281 DOI: 10.1002/app.48281 http://doi.org/10.1002/app.48281 .

Zhou, F., Zhou, Q., Tian, H.; Li, C.; Zhang, Y.; Fan, X.; Shen, Z. . Synthesis and self-assembly of a triarm star-shaped rod-rod block copolymer . Chinese J. Polym. Sci. , 2015 . 33 709 - 720 . DOI: 10.1007/s10118-015-1621-3 http://doi.org/10.1007/s10118-015-1621-3 .

Bates, M. W.; Barbon, S. M.; Levi, A. E.; Lewis III, R. M.; Beech, H. K.; Vonk, K. M.; Zhang, C.; Fredrickson, G. H.; Hawker, C. J.; Bates, C. M. . Synthesis and self-assembly of AB n miktoarm star polymers . ACS Macro Lett. , 2020 . 9 396 - 403 . DOI: 10.1021/acsmacrolett.0c00061 http://doi.org/10.1021/acsmacrolett.0c00061 .

Shi, W.; Tateishi, Y. C.; Li, W.; Hawker, C. J.; Fredrickson, G. H.; Kramer, E. J. . Producing small domain features using miktoarm block copolymers with large interaction parameters . ACS Macro Lett. , 2015 . 4 1287 - 1292 . DOI: 10.1021/acsmacrolett.5b00712 http://doi.org/10.1021/acsmacrolett.5b00712 .

Ji, S. X.; Wan, L.; Liu, C. C.; Nealey, P. F. . Directed self-assembly of block copolymers on chemical patterns: a platform for nanofabrication . Prog. Polym. Sci. , 2016 . 76 - 127 . .

Pang, Y. Y.; Jin, X. S.; Huang, G. C.; Wan, L.; Ji, S. X. . Directed Self-assembly of styrene-methyl acrylate block copolymers with sub-7 nm features via thermal annealing . Macromolecules , 2019 . 52 2987 - 2994 . DOI: 10.1021/acs.macromol.9b00174 http://doi.org/10.1021/acs.macromol.9b00174 .

Jiang, Y., Hadjichristidis, N. . pH-Responsive AIE-active polyethylene-based block copolymers . Chinese J. Polym. Sci. , 2019 . 37 930 - 935 . DOI: 10.1007/s10118-019-2330-0 http://doi.org/10.1007/s10118-019-2330-0 .

Bai, Y.; Xie, F.; Tian, W. . Controlled self-assembly of thermo-responsive amphiphilic H-shaped polymer for adjustable drug release . Chinese J. Polym. Sci. , 2018 . 36 406 - 416 . DOI: 10.1007/s10118-018-2086-y http://doi.org/10.1007/s10118-018-2086-y .

Liu, Z.; Zhang, G. . Preparation of Janus hybrid gold nanoparticles based on asymmetric star polymers . J. Funct. Polym. , 2020 . 33 342 - 349 . .

Shin, J. J.; Kim, E. J.; Ku, K. H.; Lee, Y. J.; Hawker, C. J.; Kim, B. J. . 100 th Anniversary of macromolecular science viewpoint: block copolymer particles: tuning shape, interfaces, and morphology . ACS Macro Lett. , 2020 . 9 306 - 317 . DOI: 10.1021/acsmacrolett.0c00020 http://doi.org/10.1021/acsmacrolett.0c00020 .

Zhu, Y.; Burgaz, E.; Gido, S. P.; Staudinger, U.; Weidisch, R.; Uhrig, D.; Mays, J. W. . Morphology and tensile properties of multigraft copolymers with regularly spaced tri-, tetra-, and hexafunctional junction points . Macromolecules , 2006 . 39 4428 - 4436 . DOI: 10.1021/ma060067s http://doi.org/10.1021/ma060067s .

Burns, A. B.; Register, R. A. . Mechanical properties of star block polymer thermoplastic elastomers with glassy and crystalline end blocks . Macromolecules , 2016 . 49 9521 - 9530 . DOI: 10.1021/acs.macromol.6b02175 http://doi.org/10.1021/acs.macromol.6b02175 .

Lynd, N. A.; Oyerokun, F. T.; O’Donoghue, D. L.; Handlin, D. L. Jr.; Fredrickson, G. H. . Design of soft and strong thermoplastic elastomers based on nonlinear block copolymer architectures using self-consistent-field theory . Macromolecules , 2010 . 43 3479 - 3486 . DOI: 10.1021/ma902517v http://doi.org/10.1021/ma902517v .

Shi, W.; Lynd, N. A.; Montarnal, D.; Luo, Y.; Fredrickson, G. H.; Kramer, E. J.; Ntaras, C.; Avgeropoulos, A.; Hexemer, A. . Toward strong thermoplastic elastomers with asymmetric miktoarm block copolymer architectures . Macromolecules , 2014 . 47 2037 - 2043 . DOI: 10.1021/ma402566g http://doi.org/10.1021/ma402566g .

Shi, W.; Hamilton, A. L.; Delaney, K. T.; Fredrickson, G. H.; Kramer, E. J.; Ntaras, C.; Avgeropoulos, A.; Lynd, N. A.; Demassieux, Q.; Creton, C. . Aperiodic “bricks and mortar” mesophase: a new equilibrium state of soft matter and application as a stiff thermoplastic elastomer . Macromolecules , 2015 . 48 5378 - 5384 . DOI: 10.1021/acs.macromol.5b01210 http://doi.org/10.1021/acs.macromol.5b01210 .

Liu, Y. X.; Delaney, K. T.; Fredrickson, G. H. . Field-theoretic simulations of fluctuation-stabilized aperiodic “bricks-and-mortar” mesophase in miktoarm star block copolymer/homopolymer blends . Macromolecules , 2017 . 50 6263 - 6272 . DOI: 10.1021/acs.macromol.7b01106 http://doi.org/10.1021/acs.macromol.7b01106 .

Lequieu, J.; Koeper, T.; Delaney, K. T.; Fredrickson, G. H. . Extreme deflection of phase boundaries and chain bridging in A(BA′) n miktoarm star polymers . Macromolecules , 2020 . 53 513 - 522 . DOI: 10.1021/acs.macromol.9b02254 http://doi.org/10.1021/acs.macromol.9b02254 .

Levi, A. E.; Fu, L.; Lequieu, J.; Horne, J. D.; Blankenship, J.; Mukherjee, S.; Zhang, T.; Fredrickson, G. H.; Gutekunst, W. R.; Bates, C. M. . Efficient synthesis of asymmetric miktoarm star polymers . Macromolecules , 2020 . 53 702 - 710 . DOI: 10.1021/acs.macromol.9b02380 http://doi.org/10.1021/acs.macromol.9b02380 .

Xie, Q.; Qiang, Y.; Chen, L.; Xia, Y.; Li, W. . Synergistic effect of stretched bridging block and released packing frustration leads to exotic nanostructures . ACS Macro Lett. , 2020 . 9 980 - 984 . DOI: 10.1021/acsmacrolett.0c00313 http://doi.org/10.1021/acsmacrolett.0c00313 .

Chen, L.; Qiang, Y.; Li, W. . Tuning arm architecture leads to unusual phase behaviors in a (BAB) 5 star copolymer melt . Macromolecules , 2018 . 51 9890 - 9900 . DOI: 10.1021/acs.macromol.8b01484 http://doi.org/10.1021/acs.macromol.8b01484 .

Xie, N.; Li, W. H.; Qiu, F.; Shi, A. C. . σ Phase formed in conformationally asymmetric AB-type block copolymers . ACS Macro Lett. , 2014 . 3 906 - 910 . DOI: 10.1021/mz500445v http://doi.org/10.1021/mz500445v .

Jiang, W.; Qiang, Y.; Li, W.; Qiu, F.; Shi, A. C. . Effects of chain topology on the self-assembly of AB-type block copolymers . Macromolecules , 2018 . 51 1529 - 1538 . DOI: 10.1021/acs.macromol.7b02389 http://doi.org/10.1021/acs.macromol.7b02389 .

Ji, X.; Li, W. . Effect of chain architectures on the domain spacing of block copolymers with equivalent segregation degrees . Phys. Chem. Chem. Phys. , 2020 . 22 17824 - 17832 . DOI: 10.1039/D0CP02104K http://doi.org/10.1039/D0CP02104K .

Qiang, Y.; Li, W.; Shi, A. C. . Stabilizing phases of block copolymers with gigantic spheres via designed chain architectures . ACS Macro Lett. , 2020 . 9 668 - 673 . DOI: 10.1021/acsmacrolett.0c00193 http://doi.org/10.1021/acsmacrolett.0c00193 .

Hamley, I. W.; Castelletto, V. . Small-angle scattering of block copolymers: in the melt, solution and crystal states . Prog. Polym. Sci. , 2004 . 29 909 - 948 . .

Mori, K.; Tanaka, H.; Hashimoto, T. . Scattering functions for disordered two-component polymer systems including block polymers . Macromolecules , 1987 . 20 381 - 393 . DOI: 10.1021/ma00168a026 http://doi.org/10.1021/ma00168a026 .

Yilmaz, G., Yagci, Y. . Mechanistic transformations involving radical and cationic polymerizations . Chinese J. Polym. Sci. , 2020 . 38 205 - 212 . DOI: 10.1007/s10118-020-2367-0 http://doi.org/10.1007/s10118-020-2367-0 .

Lynd, N. A.; Meuler, A. J.; Hillmyer, M. A. . Polydispersity and block copolymer self-assembly . Prog. Polym. Sci. , 2008 . 33 875 - 893 . DOI: 10.1016/j.progpolymsci.2008.07.003 http://doi.org/10.1016/j.progpolymsci.2008.07.003 .

Matsen, M. W.; Thompson, R. B. . Equilibrium behavior of symmetric ABA triblock copolymer melts . J. Chem. Phys. , 1999 . 111 7139 - 7146 . DOI: 10.1063/1.480006 http://doi.org/10.1063/1.480006 .

Matsen, M. W. . Equilibrium behavior of asymmetric ABA triblock copolymer melts . J. Chem. Phys. , 2000 . 113 5539 - 5544 . DOI: 10.1063/1.1289889 http://doi.org/10.1063/1.1289889 .

Wang, Y.; Zhong, M.; Park, J. V.; Zhukhovitskiy, A. V.; Shi, W.; Johnson, J. A. . Block co-polyMOCs by stepwise self-assembly . J. Am. Chem. Soc. , 2016 . 138 10708 - 10715 . DOI: 10.1021/jacs.6b06712 http://doi.org/10.1021/jacs.6b06712 .

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