Molecular Architecture Directs Linear–Bottlebrush–Linear Triblock Copolymers to Self-Assemble to Soft Reprocessable Elastomers

Nian, Shifeng; Lian, Huada; Gong, Zihao; Zhernenkov, Mikhail; Qin, Jian; Cai, Li -Heng

doi:10.1021/acsmacrolett.9b00721

Title: Molecular Architecture Directs Linear–Bottlebrush–Linear Triblock Copolymers to Self-Assemble to Soft Reprocessable Elastomers

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Abstract

Linear–bottlebrush–linear (LBBL) triblock copolymers represent an emerging system for creating multifunctional nanostructures. Their self-assembly depends on molecular architecture but remains poorly explored. We synthesize polystyrene-block-bottlebrush polydimethylsiloxane-block-polystyrene triblock copolymers with controlled molecular architecture and use them as a model system to study the self-assembly of LBBL polymers. Unlike classical stiff rod-flexible linear block copolymers that are prone to form highly ordered nanostructures such as lamellae, at small weight fractions of the linear blocks, LBBL polymers self-assemble to a disordered sphere phase, regardless of the bottlebrush stiffness. Microscopically, characteristic lengths increase with the bottlebrush stiffness by a power of 2/3, which is captured by a scaling analysis. Macroscopically, the formed nanostructures are ultrasoft, reprocessable elastomers with shear moduli of about 1 kPa, two orders of magnitude lower than that of conventional polydimethylsiloxane elastomers. Our results provide insights on exploiting the self-assembly of LBBL polymers to create soft functional nanostructures.

Authors:

Nian, Shifeng ^[1]; Lian, Huada ^[2]; Gong, Zihao ^[1];

^[3];

^[2];

^[1]

Univ. of Virginia, Charlottesville, VA (United States)
Stanford Univ., Stanford, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: Fri Nov 01 00:00:00 EDT 2019

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

OSTI Identifier:: 1580235

Report Number(s):: BNL-212460-2019-JAAM
Journal ID: ISSN 2161-1653

Grant/Contract Number:: SC0012704

Resource Type:: Accepted Manuscript

Journal Name:: ACS Macro Letters

Additional Journal Information:: Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2161-1653

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Nian, Shifeng, Lian, Huada, Gong, Zihao, Zhernenkov, Mikhail, Qin, Jian, and Cai, Li -Heng. Molecular Architecture Directs Linear–Bottlebrush–Linear Triblock Copolymers to Self-Assemble to Soft Reprocessable Elastomers.  United States: N. p., 2019. 
Web.  doi:10.1021/acsmacrolett.9b00721.

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                    Nian, Shifeng, Lian, Huada, Gong, Zihao, Zhernenkov, Mikhail, Qin, Jian, & Cai, Li -Heng. Molecular Architecture Directs Linear–Bottlebrush–Linear Triblock Copolymers to Self-Assemble to Soft Reprocessable Elastomers.  United States.  https://doi.org/10.1021/acsmacrolett.9b00721

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                    Nian, Shifeng, Lian, Huada, Gong, Zihao, Zhernenkov, Mikhail, Qin, Jian, and Cai, Li -Heng. Fri .  
"Molecular Architecture Directs Linear–Bottlebrush–Linear Triblock Copolymers to Self-Assemble to Soft Reprocessable Elastomers".  United States.  https://doi.org/10.1021/acsmacrolett.9b00721.  https://www.osti.gov/servlets/purl/1580235.

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@article{osti_1580235,

  title        = {Molecular Architecture Directs Linear–Bottlebrush–Linear Triblock Copolymers to Self-Assemble to Soft Reprocessable Elastomers},

  author       = {Nian, Shifeng and Lian, Huada and Gong, Zihao and Zhernenkov, Mikhail and Qin, Jian and Cai, Li -Heng},

  abstractNote = {Linear–bottlebrush–linear (LBBL) triblock copolymers represent an emerging system for creating multifunctional nanostructures. Their self-assembly depends on molecular architecture but remains poorly explored. We synthesize polystyrene-block-bottlebrush polydimethylsiloxane-block-polystyrene triblock copolymers with controlled molecular architecture and use them as a model system to study the self-assembly of LBBL polymers. Unlike classical stiff rod-flexible linear block copolymers that are prone to form highly ordered nanostructures such as lamellae, at small weight fractions of the linear blocks, LBBL polymers self-assemble to a disordered sphere phase, regardless of the bottlebrush stiffness. Microscopically, characteristic lengths increase with the bottlebrush stiffness by a power of 2/3, which is captured by a scaling analysis. Macroscopically, the formed nanostructures are ultrasoft, reprocessable elastomers with shear moduli of about 1 kPa, two orders of magnitude lower than that of conventional polydimethylsiloxane elastomers. Our results provide insights on exploiting the self-assembly of LBBL polymers to create soft functional nanostructures.},

  doi          = {10.1021/acsmacrolett.9b00721},

  journal      = {ACS Macro Letters},

  number       = 11,

  volume       = 8,

  place        = {United States},

  year         = {Fri Nov 01 00:00:00 EDT 2019},

  month        = {Fri Nov 01 00:00:00 EDT 2019}

}

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