Chain Architecture and Hydrogen Bonding Induced Co-Ordering and Segregation of Block Copolymer/Graft Copolymer Blends

Chia Chen Wang, Kuang Hsin Wu, Chieh-Tsung Lo

Research output: Contribution to journalArticle

Abstract

We investigated the effects of chain architecture and hydrogen-bonding interaction on the phase behavior of binary mixtures containing nearly symmetric polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer and highly asymmetric polystyrene-graft-poly(acrylic acid) (PS-g-PAA) graft copolymer. When PS-g-PAA was added to PS-b-P2VP, hydrogen bonds between PAA and P2VP chains improved the miscibility of the copolymers and facilitated localization of PS-g-PAA at the PS-b-P2VP interface, which reduced the interfacial free energy of the blends. However, positioning PS-g-PAA with one PS main chain and two PAA grafted chains at the PS-b-P2VP interface increased the stretching free energy of PS-b-P2VP. Consequently, the interfacial coverage of PS-g-PAA reached saturation. Residual PS-g-PAA was segregated into the PS microdomains formed by PS-b-P2VP to regain translational entropy and reduce the stretching free energy. When the molecular weight ratio of PS-b-P2VP to PS-g-PAA (R) was smaller than 8, PS-g-PAA could not swell the PS microdomains formed by PS-b-P2VP. Therefore, the morphology of PS-b-P2VP/PS-g-PAA blends remained lamellar. By contrast, when R > 8, PS-g-PAA effectively swelled the PS microdomains formed by PS-b-P2VP. This behavior amplified the asymmetry effect caused by the branched-chain architecture of PS-g-PAA on altering the interfacial curvature of PS-b-P2VP. Consequently, the morphology of the blends transformed into a cylindrical structure.

Original languageEnglish
Pages (from-to)3210-3221
Number of pages12
JournalMacromolecules
Volume52
Issue number9
DOIs
Publication statusPublished - 2019 May 14

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carbopol 940
Graft copolymers
Polystyrenes
Grafts
Block copolymers
Hydrogen bonds
Acrylics
Acids
Free energy
Stretching
polystyrene-block-poly(2-vinylpyridine)

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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title = "Chain Architecture and Hydrogen Bonding Induced Co-Ordering and Segregation of Block Copolymer/Graft Copolymer Blends",
abstract = "We investigated the effects of chain architecture and hydrogen-bonding interaction on the phase behavior of binary mixtures containing nearly symmetric polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer and highly asymmetric polystyrene-graft-poly(acrylic acid) (PS-g-PAA) graft copolymer. When PS-g-PAA was added to PS-b-P2VP, hydrogen bonds between PAA and P2VP chains improved the miscibility of the copolymers and facilitated localization of PS-g-PAA at the PS-b-P2VP interface, which reduced the interfacial free energy of the blends. However, positioning PS-g-PAA with one PS main chain and two PAA grafted chains at the PS-b-P2VP interface increased the stretching free energy of PS-b-P2VP. Consequently, the interfacial coverage of PS-g-PAA reached saturation. Residual PS-g-PAA was segregated into the PS microdomains formed by PS-b-P2VP to regain translational entropy and reduce the stretching free energy. When the molecular weight ratio of PS-b-P2VP to PS-g-PAA (R) was smaller than 8, PS-g-PAA could not swell the PS microdomains formed by PS-b-P2VP. Therefore, the morphology of PS-b-P2VP/PS-g-PAA blends remained lamellar. By contrast, when R > 8, PS-g-PAA effectively swelled the PS microdomains formed by PS-b-P2VP. This behavior amplified the asymmetry effect caused by the branched-chain architecture of PS-g-PAA on altering the interfacial curvature of PS-b-P2VP. Consequently, the morphology of the blends transformed into a cylindrical structure.",
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Chain Architecture and Hydrogen Bonding Induced Co-Ordering and Segregation of Block Copolymer/Graft Copolymer Blends. / Wang, Chia Chen; Wu, Kuang Hsin; Lo, Chieh-Tsung.

In: Macromolecules, Vol. 52, No. 9, 14.05.2019, p. 3210-3221.

Research output: Contribution to journalArticle

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