Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers

Fei, Huafeng; Yavitt, Benjamin M.; Kopanati, Gayathri; Watkins, James J.

doi:10.1002/polb.24824

Title: Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers

Abstract

ABSTRACT We report the synthesis of polystyrene‐block‐poly(dimethyl siloxane) (PS‐ b ‐PDMS) brush block copolymers (BBCPs) through sequential ROMP of norbornene‐modified macromonomers (‐NB) and explore the effect of side chain length (N _sc ) and total backbone degree of polymerization (N _bb ) on the self‐assembly of lamellar morphologies. Group I (PS‐NB M _n = 2.9 kg/mol, PDMS‐NB M _n = 4.8 kg/mol) exhibits asymmetric side chains, while Group II (PS‐NB M _n = 4.7 kg/mol, PDMS‐NB M _n = 4.8 kg/mol) possess a more symmetric arrangement. Both families rapidly self‐assemble into well‐ordered lamellar morphologies with domain spacings (d ₀ ) ranging from d ₀ = 54 to 140 nm. The scaling relationship between d ₀ and N _bb (d ₀ ~N _bb ^α ) was determined as the measure of backbone flexibility. Exponents of α = 0.71 and α = 0.81 are observed for Groups I and II, respectively, indicating the BBCPs adopt an extended backbone conformation. The presence of a low T _g side chain such as PDMS increases apparent flexibility of the backbone. The interplay between contrasting characteristics of the side chains is discussed and reveals the importance of understanding the physical consequences of block architecture on controlling BBCP assembly. These findingsmore »« less

Authors:

^[1]; Yavitt, Benjamin M. ^[1]; Kopanati, Gayathri ^[1]; Watkins, James J. ^[1]

Department of Polymer Science and Engineering University of Massachusetts Amherst 120 Governors Drive, Amherst Massachusetts, 01003

Publication Date:: Wed Apr 10 00:00:00 EDT 2019

Sponsoring Org.:: USDOE

OSTI Identifier:: 1506159

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Journal of Polymer Science. Part B, Polymer Physics

Additional Journal Information:: Journal Name: Journal of Polymer Science. Part B, Polymer Physics Journal Volume: 57 Journal Issue: 11; Journal ID: ISSN 0887-6266

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: United States

Language:: English

Citation Formats


                    Fei, Huafeng, Yavitt, Benjamin M., Kopanati, Gayathri, and Watkins, James J. Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers.  United States: N. p., 2019. 
Web.  doi:10.1002/polb.24824.

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                    Fei, Huafeng, Yavitt, Benjamin M., Kopanati, Gayathri, & Watkins, James J. Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers.  United States.  https://doi.org/10.1002/polb.24824

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                    Fei, Huafeng, Yavitt, Benjamin M., Kopanati, Gayathri, and Watkins, James J. Wed .  
"Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers".  United States.  https://doi.org/10.1002/polb.24824.

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@article{osti_1506159,

  title        = {Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers},

  author       = {Fei, Huafeng and Yavitt, Benjamin M. and Kopanati, Gayathri and Watkins, James J.},

  abstractNote = {ABSTRACT We report the synthesis of polystyrene‐block‐poly(dimethyl siloxane) (PS‐ b ‐PDMS) brush block copolymers (BBCPs) through sequential ROMP of norbornene‐modified macromonomers (‐NB) and explore the effect of side chain length (N sc ) and total backbone degree of polymerization (N bb ) on the self‐assembly of lamellar morphologies. Group I (PS‐NB M n = 2.9 kg/mol, PDMS‐NB M n = 4.8 kg/mol) exhibits asymmetric side chains, while Group II (PS‐NB M n = 4.7 kg/mol, PDMS‐NB M n = 4.8 kg/mol) possess a more symmetric arrangement. Both families rapidly self‐assemble into well‐ordered lamellar morphologies with domain spacings (d 0 ) ranging from d 0 = 54 to 140 nm. The scaling relationship between d 0 and N bb (d 0 ~N bb α ) was determined as the measure of backbone flexibility. Exponents of α = 0.71 and α = 0.81 are observed for Groups I and II, respectively, indicating the BBCPs adopt an extended backbone conformation. The presence of a low T g side chain such as PDMS increases apparent flexibility of the backbone. The interplay between contrasting characteristics of the side chains is discussed and reveals the importance of understanding the physical consequences of block architecture on controlling BBCP assembly. These findings provide necessary information for future investigations of complex phases and well‐defined nanostructures fabricated using the brush architecture. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57 , 691–699},

  doi          = {10.1002/polb.24824},

  journal      = {Journal of Polymer Science. Part B, Polymer Physics},

  number       = 11,

  volume       = 57,

  place        = {United States},

  year         = {Wed Apr 10 00:00:00 EDT 2019},

  month        = {Wed Apr 10 00:00:00 EDT 2019}

}

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Title: Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers

Abstract

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Linear Rheology of Polyolefin-Based Bottlebrush Polymers
journal, June 2015