High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature

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.

doi:10.1021/acs.macromol.5b02642

Title: High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature

Journal Article · Wed Mar 30 00:00:00 EDT 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5b02642· OSTI ID:1253243

Schlegel, Ralf ^[1]; Williams, Katherine ^[2]; Voyloy, Dimitry ^[3]; Steren, Carlos A. ^[4]; Goodwin, Andrew ^[4]; Coughlin, E. Bryan ^[2]; Gido, Samuel ^[2]; Beiner, Mario ^[5]; Hong, Kunlun ^[6]; Kang, Nam -Goo ^[4]; Mays, Jimmy ^[7]; Wang, Weiyu ^[4]; White, Benjamin T. ^[4]

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)

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 (T_g) 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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1253243

Journal Information:: Macromolecules, Vol. 49, Issue 7; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 31 works

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References (41)

Poly[poly(isobornyl methacrylate- co -methyl methacrylate) (poly(IBMA- co -MMA))- b -polybutadiene- b -poly(IBMA- co -MMA)] Copolymers: Synthesis, Morphology, and Properties Yu, J. M.; Dubois, Ph.; Jérôme, R. Macromolecules, Vol. 30, Issue 21 https://doi.org/10.1021/ma961849w	journal	October 1997
Synthesis and Properties of Block Copolymers. 4. Poly(p-tert-butylstyrene-diene-p-tert-butylstyrene) and Poly(p-tert-butylstyrene-isoprene-styrene) Fetters, L. J.; Firer, E. M.; Dafauti, M. Macromolecules, Vol. 10, Issue 6 https://doi.org/10.1021/ma60060a008	journal	November 1977
Reinforcement of elastomers Heinrich, Gert; Klüppel, Manfred; Vilgis, Thomas A. Current Opinion in Solid State and Materials Science, Vol. 6, Issue 3 https://doi.org/10.1016/S1359-0286(02)00030-X	journal	June 2002
Synthesis and Characterization of an ABC Miktoarm Star Terpolymer of Cyclohexadiene, Styrene, and 2-Vinylpyridine Uhrig, David; Hong, Kunlun; Mays, Jimmy W. Macromolecules, Vol. 41, Issue 23 https://doi.org/10.1021/ma801852t	journal	November 2008
Applications of Anionic Polymerization Research Quirk, Roderic P. ACS Symposium Series https://doi.org/10.1021/bk-1998-0696	book	June 1998
Synthesis and Properties of New Thermoplastic Elastomers Containing Poly[4-(1-adamantyl)styrene] Hard Segments Kobayashi, Shingo; Kataoka, Hiroshi; Ishizone, Takashi Macromolecules, Vol. 41, Issue 14 https://doi.org/10.1021/ma7028743	journal	July 2008
Polyisobutylene-containing block polymers by sequential monomer addition. IV. New triblock thermoplastic elastomers comprising high Tg styrenic glassy segments: Synthesis, characterization and physical properties Puskas, J. E.; Kaszas, G.; Kennedy, J. P. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 30, Issue 1 https://doi.org/10.1002/pola.1992.080300105	journal	January 1992
Measurement of living polybutadienyllithium anion concentrations in the presence of complexing agents by u.v.-visible spectroscopy Poshyachinda, S.; Edwards, H. G. M.; Johnson, A. F. Polymer, Vol. 38, Issue 3 https://doi.org/10.1016/S0032-3861(96)00544-7	journal	February 1997
Anionic Polymerization: Principles and Practical Applications Hsieh, Henry; Quirk, Roderic P. CRC Press https://doi.org/10.1201/9780585139401	reference-book	March 1996
Are n -BuLi/TMEDA-Mediated Arene Ortholithiations Directed? Substituent-Dependent Rates, Substituent-Independent Mechanisms Chadwick, Scott T.; Rennels, Roger A.; Rutherford, Jennifer L. Journal of the American Chemical Society, Vol. 122, Issue 36 https://doi.org/10.1021/ja001471o	journal	September 2000
Synthesis and Characterization of Elastomeric Heptablock Terpolymers Structured by Crystallization Alfonzo, C. Guillermo; Fleury, Guillaume; Chaffin, Kimberly A. Macromolecules, Vol. 43, Issue 12 https://doi.org/10.1021/ma100347k	journal	June 2010
High Anionic Polymerizability of Benzofulvene: New Exo-Methylene Hydrocarbon Monomer Kosaka, Yuki; Kawauchi, Susumu; Goseki, Raita Macromolecules, Vol. 48, Issue 13 https://doi.org/10.1021/acs.macromol.5b00944	journal	June 2015
Synthesis and Properties of Block Polymers. I. Poly-α-methylstyrene-Polyisoprene-Poly-α-methylstyrene Fetters, Lewis J.; Morton, Maurice Macromolecules, Vol. 2, Issue 5 https://doi.org/10.1021/ma60011a002	journal	September 1969
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 Imaeda, Tsuguto; Hashimoto, Tamotsu; Irie, Satoshi Journal of Polymer Science Part A: Polymer Chemistry, Vol. 51, Issue 8 https://doi.org/10.1002/pola.26561	journal	January 2013
Living Anionic Polymerization of Benzofulvene in Hydrocarbon Solvent Kosaka, Yuki; Goseki, Raita; Kawauchi, Susumu Macromolecular Symposia, Vol. 350, Issue 1 https://doi.org/10.1002/masy.201400024	journal	April 2015
High-Strain-Induced Deformation Mechanisms in Block–Graft and Multigraft Copolymers Schlegel, R.; Duan, Y. X.; Weidisch, R. Macromolecules, Vol. 44, Issue 23 https://doi.org/10.1021/ma201353w	journal	December 2011
Polyisobutylene-Based Thermoplastic Elastomers. 3. Synthesis, Characterization, and Properties of Poly(.alpha.-methylstyrene-b-isobutylene-b-.alpha.-methylstyrene) Triblock Copolymers Li, Dawei; Faust, Rudolf Macromolecules, Vol. 28, Issue 14 https://doi.org/10.1021/ma00118a015	journal	July 1995
Polymers with Complex Architecture by Living Anionic Polymerization Hadjichristidis, Nikos; Pitsikalis, Marinos; Pispas, Stergios Chemical Reviews, Vol. 101, Issue 12 https://doi.org/10.1021/cr9901337	journal	December 2001
Synthesis and Properties of Poly[isobornyl methacrylate (IBMA)- b -butadiene (BD)- b -IBMA] Copolymers: New Thermoplastic Elastomers of a Large Service Temperature Range Yu, Jian Ming; Dubois, Philippe; Jérôme, Robert Macromolecules, Vol. 29, Issue 23 https://doi.org/10.1021/ma960710i	journal	January 1996
A generalized tube model of rubber elasticity and stress softening of filler reinforced elastomer systems Klüppel, Manfred; Schramm, Joachim Macromolecular Theory and Simulations, Vol. 9, Issue 9 https://doi.org/10.1002/1521-3919(20001201)9:9<742::AID-MATS742>3.0.CO;2-4	journal	December 2000
‘Living’ Polymers Szwarc, M. Nature, Vol. 178, Issue 4543 https://doi.org/10.1038/1781168a0	journal	November 1956
Anionic Polymerization of 1,3-Cyclohexadiene with Alkyllithium/Amine Systems. Characteristics of n -Butyllithium/ N , N , N ‘, N ‘-Tetramethylethylenediamine System for Living Anionic Polymerization Natori, Itaru; Inoue, Shohei Macromolecules, Vol. 31, Issue 15 https://doi.org/10.1021/ma9718661	journal	July 1998
Sustainable Thermoplastic Elastomers from Terpene-Derived Monomers Bolton, Justin M.; Hillmyer, Marc A.; Hoye, Thomas R. ACS Macro Letters, Vol. 3, Issue 8 https://doi.org/10.1021/mz500339h	journal	July 2014
Difunctional Initiator Based on 1,3-Diisopropenylbenzene. 6. Synthesis of Methyl Methacrylate−Butadiene−Methyl Methacrylate Triblock Copolymers Yu, Y.; Dubois, Ph.; Teyssié, Ph. Macromolecules, Vol. 30, Issue 15 https://doi.org/10.1021/ma961819t	journal	July 1997
Poly[alkyl methacrylate- b -butadiene- b -alkyl methacrylate] Triblock Copolymers: Synthesis, Morphology, and Mechanical Properties at High Temperatures Yu, Jian Ming; Dubois, Philippe; Jérôme, Robert Macromolecules, Vol. 29, Issue 26 https://doi.org/10.1021/ma960886k	journal	January 1996
Modelling of stress and strain amplification effects in filled polymer melts Domurath, Jan; Saphiannikova, Marina; Ausias, Gilles Journal of Non-Newtonian Fluid Mechanics, Vol. 171-172 https://doi.org/10.1016/j.jnnfm.2012.01.001	journal	March 2012
Experimental techniques in high-vacuum anionic polymerization Uhrig, David; Mays, Jimmy W. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, Issue 24 https://doi.org/10.1002/pola.21016	journal	January 2005
Living Anionic Polymerization of Benzofulvene: Highly Reactive Fixed Transoid 1,3-Diene Kosaka, Yuki; Kitazawa, Keita; Inomata, Sotaro ACS Macro Letters, Vol. 2, Issue 2 https://doi.org/10.1021/mz4000078	journal	January 2013
A new semi-phenomenological approach to predict the stress relaxation behavior of thermoplastic elastomers Baeurle, Stephan A.; Hotta, Atsushi; Gusev, Andrei A. Polymer, Vol. 46, Issue 12 https://doi.org/10.1016/j.polymer.2004.07.034	journal	May 2005
POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERS ¹ Szwarc, M.; Levy, M.; Milkovich, R. Journal of the American Chemical Society, Vol. 78, Issue 11 https://doi.org/10.1021/ja01592a101	journal	June 1956
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 Iatrou, Hermis; Mays, Jimmy W.; Hadjichristidis, Nikos Macromolecules, Vol. 31, Issue 19 https://doi.org/10.1021/ma980738p	journal	September 1998
1,3-Cyclohexadiene Polymers. 1. Anionic Polymerization Hong, Kunlun; Mays, Jimmy W. Macromolecules, Vol. 34, Issue 4 https://doi.org/10.1021/ma0015626	journal	February 2001
Synthesis, morphology and mechanical properties of linear triblock copolymers based on poly(α-methylene-γ-butyrolactone) Mosnáček, Jaroslav; Yoon, Jeong Ae; Juhari, Azhar Polymer, Vol. 50, Issue 9 https://doi.org/10.1016/j.polymer.2009.02.037	journal	April 2009
Polyisobutylene-containing block polymers by sequential monomer addition: IX. Poly(acenaphthylene-b-isobutylene-b-acenaphthylene) Fodor, Zs.; Kennedy, J. P. Polymer Bulletin, Vol. 29, Issue 6 https://doi.org/10.1007/BF01041157	journal	December 1992
Catalytic Hydrogenation of Polystyrene Hucul, D. A.; Hahn, S. F. Advanced Materials, Vol. 12, Issue 23 https://doi.org/10.1002/1521-4095(200012)12:23<1855::AID-ADMA1855>3.0.CO;2-P	journal	December 2000
Star-like poly (n-butyl acrylate)-b-poly (α-methylene-γ-butyrolactone) block copolymers for high temperature thermoplastic elastomers applications Juhari, Azhar; Mosnáček, Jaroslav; Yoon, Jeong Ae Polymer, Vol. 51, Issue 21 https://doi.org/10.1016/j.polymer.2010.08.017	journal	October 2010
Graft Copolymers with Regularly Spaced, Tetrafunctional Branch Points: Morphology and Grain Structure Beyer, Frederick L.; Gido, Samuel P.; Büschl, Christine Macromolecules, Vol. 33, Issue 6 https://doi.org/10.1021/ma991141s	journal	March 2000
Anionic polymerization to high vinyl polybutadiene Halasa, Adel F.; Lohr, D. F.; Hall, J. E. Journal of Polymer Science: Polymer Chemistry Edition, Vol. 19, Issue 6 https://doi.org/10.1002/pol.1981.170190608	journal	June 1981
Free Radical Polymerization of 7-Methyl-1-methylene-3-phenylindene. Copoly(methylene/7-methyl-3-phenyl-1,1-indenylene)−Excimer Photoluminescence Londergan, Timothy M.; Teng, Conan J.; Weber, William P. Macromolecules, Vol. 32, Issue 4 https://doi.org/10.1021/ma9816113	journal	January 1999
Advances in Living Anionic Polymerization: From Functional Monomers, Polymerization Systems, to Macromolecular Architectures Hirao, Akira; Goseki, Raita; Ishizone, Takashi Macromolecules, Vol. 47, Issue 6 https://doi.org/10.1021/ma401175m	journal	February 2014
Preparation and stress–strain properties of SBS and SIS block polymers made with dilithium initiators Cunningham, Robert E.; Auerbach, Melvin; Floyd, Walter J. Journal of Applied Polymer Science, Vol. 16, Issue 1 https://doi.org/10.1002/app.1972.070160115	journal	January 1972

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Title: High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature

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