High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature
Abstract
We present the synthesis and characterization of a new class of high temperature thermoplastic elastomers composed of polybenzofulvene–polyisoprene–polybenzofulvene (FIF) triblock copolymers. All copolymers were prepared by living anionic polymerization in benzene at room temperature. Homopolymerization and effects of additives on the glass transition temperature (Tg) of polybenzofulvene (PBF) were also investigated. Among all triblock copolymers studied, FIF with 14 vol % of PBF exhibited a maximum stress of 14.3 ± 1.3 MPa and strain at break of 1390 ± 66% from tensile tests. The stress–strain curves of FIF-10 and 14 were analyzed by a statistical molecular approach using a nonaffine tube model to estimate the thermoplastic elastomer behavior. Dynamic mechanical analysis showed that the softening temperature of PBF in FIF was 145 °C, much higher than that of thermoplastic elastomers with polystyrene hard blocks. Microphase separation of FIF triblock copolymers was observed by small-angle X-ray scattering, even though long-range order was not achieved under the annealing conditions employed. Additionally, the microphase separation of the resulting triblock copolymers was examined by atomic force microscopy.
- Authors:
-
- Fraunhofer-Institut fur Mikrostruktur con Werkstoffen und Systemen IMWS, Halle (Germany)
- Univ. of Massachusetts, Amherst, MA (United States)
- Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Tennessee, Knoxville, TN (United States)
- Fraunhofer-Institut fur Werkstoffmechanik (Fraunhofer IWM), Germany
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1253243
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 49; Journal Issue: 7; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Schlegel, Ralf, Williams, Katherine, Voyloy, Dimitry, Steren, Carlos A., Goodwin, Andrew, Coughlin, E. Bryan, Gido, Samuel, Beiner, Mario, Hong, Kunlun, Kang, Nam -Goo, Mays, Jimmy, Wang, Weiyu, and White, Benjamin T. High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature. United States: N. p., 2016.
Web. doi:10.1021/acs.macromol.5b02642.
Schlegel, Ralf, Williams, Katherine, Voyloy, Dimitry, Steren, Carlos A., Goodwin, Andrew, Coughlin, E. Bryan, Gido, Samuel, Beiner, Mario, Hong, Kunlun, Kang, Nam -Goo, Mays, Jimmy, Wang, Weiyu, & White, Benjamin T. High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature. United States. https://doi.org/10.1021/acs.macromol.5b02642
Schlegel, Ralf, Williams, Katherine, Voyloy, Dimitry, Steren, Carlos A., Goodwin, Andrew, Coughlin, E. Bryan, Gido, Samuel, Beiner, Mario, Hong, Kunlun, Kang, Nam -Goo, Mays, Jimmy, Wang, Weiyu, and White, Benjamin T. Wed .
"High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature". United States. https://doi.org/10.1021/acs.macromol.5b02642. https://www.osti.gov/servlets/purl/1253243.
@article{osti_1253243,
title = {High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature},
author = {Schlegel, Ralf and Williams, Katherine and Voyloy, Dimitry and Steren, Carlos A. and Goodwin, Andrew and Coughlin, E. Bryan and Gido, Samuel and Beiner, Mario and Hong, Kunlun and Kang, Nam -Goo and Mays, Jimmy and Wang, Weiyu and White, Benjamin T.},
abstractNote = {We present the synthesis and characterization of a new class of high temperature thermoplastic elastomers composed of polybenzofulvene–polyisoprene–polybenzofulvene (FIF) triblock copolymers. All copolymers were prepared by living anionic polymerization in benzene at room temperature. Homopolymerization and effects of additives on the glass transition temperature (Tg) of polybenzofulvene (PBF) were also investigated. Among all triblock copolymers studied, FIF with 14 vol % of PBF exhibited a maximum stress of 14.3 ± 1.3 MPa and strain at break of 1390 ± 66% from tensile tests. The stress–strain curves of FIF-10 and 14 were analyzed by a statistical molecular approach using a nonaffine tube model to estimate the thermoplastic elastomer behavior. Dynamic mechanical analysis showed that the softening temperature of PBF in FIF was 145 °C, much higher than that of thermoplastic elastomers with polystyrene hard blocks. Microphase separation of FIF triblock copolymers was observed by small-angle X-ray scattering, even though long-range order was not achieved under the annealing conditions employed. Additionally, the microphase separation of the resulting triblock copolymers was examined by atomic force microscopy.},
doi = {10.1021/acs.macromol.5b02642},
journal = {Macromolecules},
number = 7,
volume = 49,
place = {United States},
year = {Wed Mar 30 00:00:00 EDT 2016},
month = {Wed Mar 30 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Poly[poly(isobornyl methacrylate- co -methyl methacrylate) (poly(IBMA- co -MMA))- b -polybutadiene- b -poly(IBMA- co -MMA)] Copolymers: Synthesis, Morphology, and Properties
journal, October 1997
- Yu, J. M.; Dubois, Ph.; Jérôme, R.
- Macromolecules, Vol. 30, Issue 21
Synthesis and Properties of Block Copolymers. 4. Poly(p-tert-butylstyrene-diene-p-tert-butylstyrene) and Poly(p-tert-butylstyrene-isoprene-styrene)
journal, November 1977
- Fetters, L. J.; Firer, E. M.; Dafauti, M.
- Macromolecules, Vol. 10, Issue 6
Reinforcement of elastomers
journal, June 2002
- Heinrich, Gert; Klüppel, Manfred; Vilgis, Thomas A.
- Current Opinion in Solid State and Materials Science, Vol. 6, Issue 3
Synthesis and Characterization of an ABC Miktoarm Star Terpolymer of Cyclohexadiene, Styrene, and 2-Vinylpyridine
journal, November 2008
- Uhrig, David; Hong, Kunlun; Mays, Jimmy W.
- Macromolecules, Vol. 41, Issue 23
Applications of Anionic Polymerization Research
book, June 1998
- Quirk, Roderic P.
- ACS Symposium Series
Synthesis and Properties of New Thermoplastic Elastomers Containing Poly[4-(1-adamantyl)styrene] Hard Segments
journal, July 2008
- Kobayashi, Shingo; Kataoka, Hiroshi; Ishizone, Takashi
- Macromolecules, Vol. 41, Issue 14
Polyisobutylene-containing block polymers by sequential monomer addition. IV. New triblock thermoplastic elastomers comprising high Tg styrenic glassy segments: Synthesis, characterization and physical properties
journal, January 1992
- Puskas, J. E.; Kaszas, G.; Kennedy, J. P.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 30, Issue 1
Measurement of living polybutadienyllithium anion concentrations in the presence of complexing agents by u.v.-visible spectroscopy
journal, February 1997
- Poshyachinda, S.; Edwards, H. G. M.; Johnson, A. F.
- Polymer, Vol. 38, Issue 3
Anionic Polymerization: Principles and Practical Applications
reference-book, March 1996
- Hsieh, Henry; Quirk, Roderic P.
- CRC Press
Are n -BuLi/TMEDA-Mediated Arene Ortholithiations Directed? Substituent-Dependent Rates, Substituent-Independent Mechanisms
journal, September 2000
- Chadwick, Scott T.; Rennels, Roger A.; Rutherford, Jennifer L.
- Journal of the American Chemical Society, Vol. 122, Issue 36
Synthesis and Characterization of Elastomeric Heptablock Terpolymers Structured by Crystallization
journal, June 2010
- Alfonzo, C. Guillermo; Fleury, Guillaume; Chaffin, Kimberly A.
- Macromolecules, Vol. 43, Issue 12
High Anionic Polymerizability of Benzofulvene: New Exo-Methylene Hydrocarbon Monomer
journal, June 2015
- Kosaka, Yuki; Kawauchi, Susumu; Goseki, Raita
- Macromolecules, Vol. 48, Issue 13
Synthesis and Properties of Block Polymers. I. Poly-α-methylstyrene-Polyisoprene-Poly-α-methylstyrene
journal, September 1969
- Fetters, Lewis J.; Morton, Maurice
- Macromolecules, Vol. 2, Issue 5
Synthesis of ABA-triblock and star-diblock copolymers with poly(2-adamantyl vinyl ether) and poly( n -butyl vinyl ether) segments: New thermoplastic elastomers composed solely of poly(vinyl ether) backbones
journal, January 2013
- Imaeda, Tsuguto; Hashimoto, Tamotsu; Irie, Satoshi
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 51, Issue 8
Living Anionic Polymerization of Benzofulvene in Hydrocarbon Solvent
journal, April 2015
- Kosaka, Yuki; Goseki, Raita; Kawauchi, Susumu
- Macromolecular Symposia, Vol. 350, Issue 1
High-Strain-Induced Deformation Mechanisms in Block–Graft and Multigraft Copolymers
journal, December 2011
- Schlegel, R.; Duan, Y. X.; Weidisch, R.
- Macromolecules, Vol. 44, Issue 23
Polyisobutylene-Based Thermoplastic Elastomers. 3. Synthesis, Characterization, and Properties of Poly(.alpha.-methylstyrene-b-isobutylene-b-.alpha.-methylstyrene) Triblock Copolymers
journal, July 1995
- Li, Dawei; Faust, Rudolf
- Macromolecules, Vol. 28, Issue 14
Polymers with Complex Architecture by Living Anionic Polymerization
journal, December 2001
- Hadjichristidis, Nikos; Pitsikalis, Marinos; Pispas, Stergios
- Chemical Reviews, Vol. 101, Issue 12
Synthesis and Properties of Poly[isobornyl methacrylate (IBMA)- b -butadiene (BD)- b -IBMA] Copolymers: New Thermoplastic Elastomers of a Large Service Temperature Range
journal, January 1996
- Yu, Jian Ming; Dubois, Philippe; Jérôme, Robert
- Macromolecules, Vol. 29, Issue 23
A generalized tube model of rubber elasticity and stress softening of filler reinforced elastomer systems
journal, December 2000
- Klüppel, Manfred; Schramm, Joachim
- Macromolecular Theory and Simulations, Vol. 9, Issue 9
Anionic Polymerization of 1,3-Cyclohexadiene with Alkyllithium/Amine Systems. Characteristics of n -Butyllithium/ N , N , N ‘, N ‘-Tetramethylethylenediamine System for Living Anionic Polymerization
journal, July 1998
- Natori, Itaru; Inoue, Shohei
- Macromolecules, Vol. 31, Issue 15
Sustainable Thermoplastic Elastomers from Terpene-Derived Monomers
journal, July 2014
- Bolton, Justin M.; Hillmyer, Marc A.; Hoye, Thomas R.
- ACS Macro Letters, Vol. 3, Issue 8
Difunctional Initiator Based on 1,3-Diisopropenylbenzene. 6. Synthesis of Methyl Methacrylate−Butadiene−Methyl Methacrylate Triblock Copolymers
journal, July 1997
- Yu, Y.; Dubois, Ph.; Teyssié, Ph.
- Macromolecules, Vol. 30, Issue 15
Poly[alkyl methacrylate- b -butadiene- b -alkyl methacrylate] Triblock Copolymers: Synthesis, Morphology, and Mechanical Properties at High Temperatures
journal, January 1996
- Yu, Jian Ming; Dubois, Philippe; Jérôme, Robert
- Macromolecules, Vol. 29, Issue 26
Modelling of stress and strain amplification effects in filled polymer melts
journal, March 2012
- Domurath, Jan; Saphiannikova, Marina; Ausias, Gilles
- Journal of Non-Newtonian Fluid Mechanics, Vol. 171-172
Experimental techniques in high-vacuum anionic polymerization
journal, January 2005
- Uhrig, David; Mays, Jimmy W.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, Issue 24
Living Anionic Polymerization of Benzofulvene: Highly Reactive Fixed Transoid 1,3-Diene
journal, January 2013
- Kosaka, Yuki; Kitazawa, Keita; Inomata, Sotaro
- ACS Macro Letters, Vol. 2, Issue 2
A new semi-phenomenological approach to predict the stress relaxation behavior of thermoplastic elastomers
journal, May 2005
- Baeurle, Stephan A.; Hotta, Atsushi; Gusev, Andrei A.
- Polymer, Vol. 46, Issue 12
POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERS 1
journal, June 1956
- Szwarc, M.; Levy, M.; Milkovich, R.
- Journal of the American Chemical Society, Vol. 78, Issue 11
Regular Comb Polystyrenes and Graft Polyisoprene/Polystyrene Copolymers with Double Branches (“Centipedes”). Quality of (1,3-Phenylene)bis(3-methyl-1-phenylpentylidene)dilithium Initiator in the Presence of Polar Additives
journal, September 1998
- Iatrou, Hermis; Mays, Jimmy W.; Hadjichristidis, Nikos
- Macromolecules, Vol. 31, Issue 19
1,3-Cyclohexadiene Polymers. 1. Anionic Polymerization
journal, February 2001
- Hong, Kunlun; Mays, Jimmy W.
- Macromolecules, Vol. 34, Issue 4
Synthesis, morphology and mechanical properties of linear triblock copolymers based on poly(α-methylene-γ-butyrolactone)
journal, April 2009
- Mosnáček, Jaroslav; Yoon, Jeong Ae; Juhari, Azhar
- Polymer, Vol. 50, Issue 9
Polyisobutylene-containing block polymers by sequential monomer addition: IX. Poly(acenaphthylene-b-isobutylene-b-acenaphthylene)
journal, December 1992
- Fodor, Zs.; Kennedy, J. P.
- Polymer Bulletin, Vol. 29, Issue 6
Catalytic Hydrogenation of Polystyrene
journal, December 2000
- Hucul, D. A.; Hahn, S. F.
- Advanced Materials, Vol. 12, Issue 23
Star-like poly (n-butyl acrylate)-b-poly (α-methylene-γ-butyrolactone) block copolymers for high temperature thermoplastic elastomers applications
journal, October 2010
- Juhari, Azhar; Mosnáček, Jaroslav; Yoon, Jeong Ae
- Polymer, Vol. 51, Issue 21
Graft Copolymers with Regularly Spaced, Tetrafunctional Branch Points: Morphology and Grain Structure
journal, March 2000
- Beyer, Frederick L.; Gido, Samuel P.; Büschl, Christine
- Macromolecules, Vol. 33, Issue 6
Anionic polymerization to high vinyl polybutadiene
journal, June 1981
- Halasa, Adel F.; Lohr, D. F.; Hall, J. E.
- Journal of Polymer Science: Polymer Chemistry Edition, Vol. 19, Issue 6
Free Radical Polymerization of 7-Methyl-1-methylene-3-phenylindene. Copoly(methylene/7-methyl-3-phenyl-1,1-indenylene)−Excimer Photoluminescence
journal, January 1999
- Londergan, Timothy M.; Teng, Conan J.; Weber, William P.
- Macromolecules, Vol. 32, Issue 4
Advances in Living Anionic Polymerization: From Functional Monomers, Polymerization Systems, to Macromolecular Architectures
journal, February 2014
- Hirao, Akira; Goseki, Raita; Ishizone, Takashi
- Macromolecules, Vol. 47, Issue 6
Preparation and stress–strain properties of SBS and SIS block polymers made with dilithium initiators
journal, January 1972
- Cunningham, Robert E.; Auerbach, Melvin; Floyd, Walter J.
- Journal of Applied Polymer Science, Vol. 16, Issue 1
Works referencing / citing this record:
The Microscopic Structure–Property Relationship of Metal–Organic Polyhedron Nanocomposites
journal, November 2019
- Zhang, Mingxin; Lai, Yuyan; Li, Mu
- Angewandte Chemie International Edition, Vol. 58, Issue 48
Block Copolymers: Synthesis, Self-Assembly, and Applications
journal, October 2017
- Feng, Hongbo; Lu, Xinyi; Wang, Weiyu
- Polymers, Vol. 9, Issue 12
Initiating Mechanism of the Anionic Polymerization of Methacrylates with t ‐BuOK and the Synthesis of ABA Type Triblock Copolymers
journal, November 2019
- Zhang, Tongyuan; Zheng, Anna; Zou, Guijin
- Macromolecular Chemistry and Physics, Vol. 220, Issue 24
All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties
journal, January 2017
- Lu, Wei; Wang, Yangyang; Wang, Weiyu
- Polymer Chemistry, Vol. 8, Issue 37
Block Copolymers: Synthesis, Self-Assembly, and Applications
journal, October 2017
- Feng, Hongbo; Lu, Xinyi; Wang, Weiyu
- Polymers, Vol. 9, Issue 12
Elastomeric polyethylenes accessible via ethylene homo-polymerization using an unsymmetrical α-diimino-nickel catalyst
journal, January 2017
- Wang, Xinxin; Fan, Linlin; Ma, Yanping
- Polymer Chemistry, Vol. 8, Issue 18
Initiating Mechanism of the Anionic Polymerization of Methacrylates with t ‐BuOK and the Synthesis of ABA Type Triblock Copolymers
journal, November 2019
- Zhang, Tongyuan; Zheng, Anna; Zou, Guijin
- Macromolecular Chemistry and Physics, Vol. 220, Issue 24
Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants
journal, September 2017
- Huang, Caili; Forth, Joe; Wang, Weiyu
- Nature Nanotechnology, Vol. 12, Issue 11
The Microscopic Structure–Property Relationship of Metal–Organic Polyhedron Nanocomposites
journal, November 2019
- Zhang, Mingxin; Lai, Yuyan; Li, Mu
- Angewandte Chemie, Vol. 131, Issue 48
Highly branched and high‐molecular‐weight polyethylenes produced by 1‐[2,6‐bis(bis(4‐fluorophenyl)methyl)‐4‐MeOC 6 H 2 N]‐2‐aryliminoacenaphthylnickel(II) halides
journal, November 2018
- Wu, Ruikai; Wang, Yifan; Guo, Liwei
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 57, Issue 2