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Title: Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers

Abstract

A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined in this paper by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (T ODT), for the first time for PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χ eff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. Finally, these copolymers exhibit well-ordered structures even at high temperatures (~260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [5]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [6]; ORCiD logo [7];  [3]; ORCiD logo [8]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Univ. of Ioannina (Greece). Dept. of Materials Science and Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
  3. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Computer Science and Mathematics Division
  5. Duke Univ., Durham, NC (United States). Shared Materials Instrumentation Facility
  6. Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
  7. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia). Physical Sciences and Engineering Division. KAUST Catalysis Center. Polymer Synthesis Lab.
  8. Univ. of Ioannina (Greece). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Florida State Univ., Tallahassee, FL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Ioannina (Greece)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); American Chemical Society Petroleum Research Fund (United States)
Contributing Org.:
Univ. of Tennessee, Knoxville, TN (United States); King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia); Duke Univ., Durham, NC (United States)
OSTI Identifier:
1376418
Grant/Contract Number:
AC05-00OR22725; 55378-DNI7
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 50; Journal Issue: 6; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Misichronis, Konstantinos, Chen, Jihua, Imel, Adam, Kumar, Rajeev, Thostenson, James, Hong, Kunlun, Dadmun, Mark, Sumpter, Bobby G., Kennemur, Justin G., Hadjichristidis, Nikos, Mays, Jimmy W., and Avgeropoulos, Apostolos. Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers. United States: N. p., 2017. Web. doi:10.1021/acs.macromol.7b00104.
Misichronis, Konstantinos, Chen, Jihua, Imel, Adam, Kumar, Rajeev, Thostenson, James, Hong, Kunlun, Dadmun, Mark, Sumpter, Bobby G., Kennemur, Justin G., Hadjichristidis, Nikos, Mays, Jimmy W., & Avgeropoulos, Apostolos. Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers. United States. doi:10.1021/acs.macromol.7b00104.
Misichronis, Konstantinos, Chen, Jihua, Imel, Adam, Kumar, Rajeev, Thostenson, James, Hong, Kunlun, Dadmun, Mark, Sumpter, Bobby G., Kennemur, Justin G., Hadjichristidis, Nikos, Mays, Jimmy W., and Avgeropoulos, Apostolos. Wed . "Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers". United States. doi:10.1021/acs.macromol.7b00104. https://www.osti.gov/servlets/purl/1376418.
@article{osti_1376418,
title = {Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers},
author = {Misichronis, Konstantinos and Chen, Jihua and Imel, Adam and Kumar, Rajeev and Thostenson, James and Hong, Kunlun and Dadmun, Mark and Sumpter, Bobby G. and Kennemur, Justin G. and Hadjichristidis, Nikos and Mays, Jimmy W. and Avgeropoulos, Apostolos},
abstractNote = {A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined in this paper by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (TODT), for the first time for PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χeff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. Finally, these copolymers exhibit well-ordered structures even at high temperatures (~260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.},
doi = {10.1021/acs.macromol.7b00104},
journal = {Macromolecules},
number = 6,
volume = 50,
place = {United States},
year = {Wed Mar 15 00:00:00 EDT 2017},
month = {Wed Mar 15 00:00:00 EDT 2017}
}

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  • Here, the synthesis and molecular characterization of a series of conformationally asymmetric polystyrene-block-poly(1,3-cyclohexadiene) (PS- b-PCHD) diblock copolymers (PCHD: ~90% 1,4 and ~10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27 ≤ Φ PS ≤ 0.91) was studied by transmission electron microscopy and small-angle X-ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD-1,4)–shell(PCHD-1,2) cylinders in PS matrix and three-phase (PS, PCHD-1,4, PCHD-1,2) four-layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strongmore » dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS- b-PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1564–1572« less
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  • Self-assembly and its influence on the photophysical properties of polystyrene-b-sulfonated poly (1,3-cyclohexadiene) (PS-b-sPCHD) were investigated using transmission electron microscopy (TEM), laser light scattering (LLS) technique, and fluorescence spectroscopy. The amphiphilic PS-b-sPCHD copolymers can associate to form micelles with insoluble PS segments as the core surrounded by soluble sPCHD segments in aqueous media. J-aggregation of the chromophores in sPCHD segments is significantly facilitated in the micellization, resulting in a remarkable change in the photophysical properties of PS-b-sPCHD.
  • The phase behavior of 44 poly(isoprene-b-styrene-b-ethylene oxide) (ISO) linear triblock copolymer melts was investigated at weak to intermediate segregation strengths and spanning a comprehensive range of compositions. Phases were characterized by a combination of experimental techniques, including small-angle X-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with our previous results, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O{sup 70}), double gyroid (Q{sup 230}), alternating gyroid (Q{sup 214}), hexagonal (HEX), and body-centered cubic (BCC). The phase map of ISO specimens was found to be somewhat asymmetric around the f{sub I}more » = f{sub O} isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation.« less