Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers

Junliang Zhang, Robert Deubler, Matthias Hartlieb, Liam Martin, Joji Tanaka, Elena Patyukova, Paul D. Topham, Felix H. Schacher, Sébastien Perrier

Research output: Contribution to journalArticle

Abstract

Multiblock copolymers (MBCPs) are an emerging class of materials that are becoming more accessible in recent years. However, to date there is still a lack of fundamental understanding of their physical properties. In particular, the glass transition temperature (Tg) which is known to be affected by the phase separation has not been well characterized experimentally. To this end, we report the first experimental study on the evolution of the Tgs and the corresponding phase separation of linear MBCPs with increasing number of blocks while keeping the overall degree of polymerization (DP) constant (DP = 200). Ethylene glycol methyl ether acrylate (EGMEA) and tert-butyl acrylate (tBA) were chosen as monomers for reversible addition-fragmentation chain transfer polymerization to synthesize MBCPs. We found the Tgs (as measured by differential scanning calorimetry) of EGMEA and tBA segments within the MCBPs to converge with increasing number of blocks and decreasing block length, correlating with the loss of the heterogeneity as observed from small-angle X-ray scattering (SAXS) analysis. The Tgs of the multiblock copolymers were also compared to the Tgs of the polymer blends of the corresponding homopolymers, and we found that Tgs of the polymer blends were similar to those of the respective homopolymers, as expected. SAXS experiments further demonstrated microphase separation of multiblock copolymers. This work demonstrates the enormous potential of multiblock architectures to tune the physical properties of synthetic polymers, by changing their glass transition temperature and their morphologies obtained from microphase separation, with domain sizes reaching under 10 nm.

LanguageEnglish
Pages7380-7387
Number of pages8
JournalMacromolecules
Volume50
Issue number18
DOIs
Publication statusPublished - 14 Sep 2017

Fingerprint

Microphase separation
Copolymers
Methyl Ethers
Ethylene Glycol
Polymerization
Polymer blends
Ethylene glycol
Homopolymerization
X ray scattering
Phase separation
Ethers
Physical properties
Differential scanning calorimetry
Polymers
Monomers
Experiments

Bibliographical note

Copyright: 2017 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules , copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/acs.macromol.7b01831.

Funding: German Research Foundation (DFG, GZ: HA 7725/1-1) Thuringian Ministry of Science, Education, and Culture (TMBWK; Grant B515-11028).

Engineering and Physical Sciences Research Council (EPSRC) under Grant EP/F500378/1 through the Molecular Organisation and Assembly in Cells Doctoral Training Centre (MOAC-DTC).

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 704459.

Cite this

Zhang, J., Deubler, R., Hartlieb, M., Martin, L., Tanaka, J., Patyukova, E., ... Perrier, S. (2017). Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers. Macromolecules, 50(18), 7380-7387. https://doi.org/10.1021/acs.macromol.7b01831
Zhang, Junliang ; Deubler, Robert ; Hartlieb, Matthias ; Martin, Liam ; Tanaka, Joji ; Patyukova, Elena ; Topham, Paul D. ; Schacher, Felix H. ; Perrier, Sébastien. / Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers. In: Macromolecules. 2017 ; Vol. 50, No. 18. pp. 7380-7387.
@article{b506629712a24eda8066d0d87cfa292a,
title = "Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers",
abstract = "Multiblock copolymers (MBCPs) are an emerging class of materials that are becoming more accessible in recent years. However, to date there is still a lack of fundamental understanding of their physical properties. In particular, the glass transition temperature (Tg) which is known to be affected by the phase separation has not been well characterized experimentally. To this end, we report the first experimental study on the evolution of the Tgs and the corresponding phase separation of linear MBCPs with increasing number of blocks while keeping the overall degree of polymerization (DP) constant (DP = 200). Ethylene glycol methyl ether acrylate (EGMEA) and tert-butyl acrylate (tBA) were chosen as monomers for reversible addition-fragmentation chain transfer polymerization to synthesize MBCPs. We found the Tgs (as measured by differential scanning calorimetry) of EGMEA and tBA segments within the MCBPs to converge with increasing number of blocks and decreasing block length, correlating with the loss of the heterogeneity as observed from small-angle X-ray scattering (SAXS) analysis. The Tgs of the multiblock copolymers were also compared to the Tgs of the polymer blends of the corresponding homopolymers, and we found that Tgs of the polymer blends were similar to those of the respective homopolymers, as expected. SAXS experiments further demonstrated microphase separation of multiblock copolymers. This work demonstrates the enormous potential of multiblock architectures to tune the physical properties of synthetic polymers, by changing their glass transition temperature and their morphologies obtained from microphase separation, with domain sizes reaching under 10 nm.",
author = "Junliang Zhang and Robert Deubler and Matthias Hartlieb and Liam Martin and Joji Tanaka and Elena Patyukova and Topham, {Paul D.} and Schacher, {Felix H.} and S{\'e}bastien Perrier",
note = "Copyright: 2017 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules , copyright {\circledC} American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/acs.macromol.7b01831. Funding: German Research Foundation (DFG, GZ: HA 7725/1-1) Thuringian Ministry of Science, Education, and Culture (TMBWK; Grant B515-11028). Engineering and Physical Sciences Research Council (EPSRC) under Grant EP/F500378/1 through the Molecular Organisation and Assembly in Cells Doctoral Training Centre (MOAC-DTC). This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 704459.",
year = "2017",
month = "9",
day = "14",
doi = "10.1021/acs.macromol.7b01831",
language = "English",
volume = "50",
pages = "7380--7387",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "18",

}

Zhang, J, Deubler, R, Hartlieb, M, Martin, L, Tanaka, J, Patyukova, E, Topham, PD, Schacher, FH & Perrier, S 2017, 'Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers' Macromolecules, vol. 50, no. 18, pp. 7380-7387. https://doi.org/10.1021/acs.macromol.7b01831

Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers. / Zhang, Junliang; Deubler, Robert; Hartlieb, Matthias; Martin, Liam; Tanaka, Joji; Patyukova, Elena; Topham, Paul D.; Schacher, Felix H.; Perrier, Sébastien.

In: Macromolecules, Vol. 50, No. 18, 14.09.2017, p. 7380-7387.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers

AU - Zhang, Junliang

AU - Deubler, Robert

AU - Hartlieb, Matthias

AU - Martin, Liam

AU - Tanaka, Joji

AU - Patyukova, Elena

AU - Topham, Paul D.

AU - Schacher, Felix H.

AU - Perrier, Sébastien

N1 - Copyright: 2017 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules , copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/acs.macromol.7b01831. Funding: German Research Foundation (DFG, GZ: HA 7725/1-1) Thuringian Ministry of Science, Education, and Culture (TMBWK; Grant B515-11028). Engineering and Physical Sciences Research Council (EPSRC) under Grant EP/F500378/1 through the Molecular Organisation and Assembly in Cells Doctoral Training Centre (MOAC-DTC). This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 704459.

PY - 2017/9/14

Y1 - 2017/9/14

N2 - Multiblock copolymers (MBCPs) are an emerging class of materials that are becoming more accessible in recent years. However, to date there is still a lack of fundamental understanding of their physical properties. In particular, the glass transition temperature (Tg) which is known to be affected by the phase separation has not been well characterized experimentally. To this end, we report the first experimental study on the evolution of the Tgs and the corresponding phase separation of linear MBCPs with increasing number of blocks while keeping the overall degree of polymerization (DP) constant (DP = 200). Ethylene glycol methyl ether acrylate (EGMEA) and tert-butyl acrylate (tBA) were chosen as monomers for reversible addition-fragmentation chain transfer polymerization to synthesize MBCPs. We found the Tgs (as measured by differential scanning calorimetry) of EGMEA and tBA segments within the MCBPs to converge with increasing number of blocks and decreasing block length, correlating with the loss of the heterogeneity as observed from small-angle X-ray scattering (SAXS) analysis. The Tgs of the multiblock copolymers were also compared to the Tgs of the polymer blends of the corresponding homopolymers, and we found that Tgs of the polymer blends were similar to those of the respective homopolymers, as expected. SAXS experiments further demonstrated microphase separation of multiblock copolymers. This work demonstrates the enormous potential of multiblock architectures to tune the physical properties of synthetic polymers, by changing their glass transition temperature and their morphologies obtained from microphase separation, with domain sizes reaching under 10 nm.

AB - Multiblock copolymers (MBCPs) are an emerging class of materials that are becoming more accessible in recent years. However, to date there is still a lack of fundamental understanding of their physical properties. In particular, the glass transition temperature (Tg) which is known to be affected by the phase separation has not been well characterized experimentally. To this end, we report the first experimental study on the evolution of the Tgs and the corresponding phase separation of linear MBCPs with increasing number of blocks while keeping the overall degree of polymerization (DP) constant (DP = 200). Ethylene glycol methyl ether acrylate (EGMEA) and tert-butyl acrylate (tBA) were chosen as monomers for reversible addition-fragmentation chain transfer polymerization to synthesize MBCPs. We found the Tgs (as measured by differential scanning calorimetry) of EGMEA and tBA segments within the MCBPs to converge with increasing number of blocks and decreasing block length, correlating with the loss of the heterogeneity as observed from small-angle X-ray scattering (SAXS) analysis. The Tgs of the multiblock copolymers were also compared to the Tgs of the polymer blends of the corresponding homopolymers, and we found that Tgs of the polymer blends were similar to those of the respective homopolymers, as expected. SAXS experiments further demonstrated microphase separation of multiblock copolymers. This work demonstrates the enormous potential of multiblock architectures to tune the physical properties of synthetic polymers, by changing their glass transition temperature and their morphologies obtained from microphase separation, with domain sizes reaching under 10 nm.

UR - http://www.scopus.com/inward/record.url?scp=85029944213&partnerID=8YFLogxK

UR - http://pubs.acs.org/doi/abs/10.1021/acs.macromol.7b01831

U2 - 10.1021/acs.macromol.7b01831

DO - 10.1021/acs.macromol.7b01831

M3 - Article

VL - 50

SP - 7380

EP - 7387

JO - Macromolecules

T2 - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 18

ER -