Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · Macromolecules
 [1];  [2];  [3];  [4];  [4];  [2];  [2];  [5];  [6];  [4];  [7];  [4];  [4]
  1. Fraunhofer-Institut fur Mikrostruktur con Werkstoffen und Systemen IMWS, Halle (Germany)
  2. Univ. of Massachusetts, Amherst, MA (United States)
  3. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Univ. of Tennessee, Knoxville, TN (United States)
  5. Fraunhofer-Institut fur Werkstoffmechanik (Fraunhofer IWM), Germany
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  7. 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 (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.

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, Journal Name: Macromolecules Journal Issue: 7 Vol. 49; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (42)

A generalized tube model of rubber elasticity and stress softening of filler reinforced elastomer systems journal December 2000
Catalytic Hydrogenation of Polystyrene journal December 2000
Applications of Thermoplastic Elastomers Based on Styrenic Block Copolymers book January 2007
Preparation and stress–strain properties of SBS and SIS block polymers made with dilithium initiators journal January 1972
Living Anionic Polymerization of Benzofulvene in Hydrocarbon Solvent journal April 2015
Anionic polymerization to high vinyl polybutadiene journal June 1981
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
Experimental techniques in high-vacuum anionic polymerization journal January 2005
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
Polyisobutylene-containing block polymers by sequential monomer addition: IX. Poly(acenaphthylene-b-isobutylene-b-acenaphthylene) journal December 1992
Measurement of living polybutadienyllithium anion concentrations in the presence of complexing agents by u.v.-visible spectroscopy journal February 1997
Reinforcement of elastomers journal June 2002
Modelling of stress and strain amplification effects in filled polymer melts journal March 2012
A new semi-phenomenological approach to predict the stress relaxation behavior of thermoplastic elastomers journal May 2005
Synthesis, morphology and mechanical properties of linear triblock copolymers based on poly(α-methylene-γ-butyrolactone) journal April 2009
Star-like poly (n-butyl acrylate)-b-poly (α-methylene-γ-butyrolactone) block copolymers for high temperature thermoplastic elastomers applications journal October 2010
High Anionic Polymerizability of Benzofulvene: New Exo-Methylene Hydrocarbon Monomer journal June 2015
Applications of Anionic Polymerization Research book June 1998
Polymers with Complex Architecture by Living Anionic Polymerization journal December 2001
Are n -BuLi/TMEDA-Mediated Arene Ortholithiations Directed? Substituent-Dependent Rates, Substituent-Independent Mechanisms journal September 2000
POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERS 1 journal June 1956
Polyisobutylene-Based Thermoplastic Elastomers. 3. Synthesis, Characterization, and Properties of Poly(.alpha.-methylstyrene-b-isobutylene-b-.alpha.-methylstyrene) Triblock Copolymers journal July 1995
1,3-Cyclohexadiene Polymers. 1. Anionic Polymerization journal February 2001
Synthesis and Characterization of Elastomeric Heptablock Terpolymers Structured by Crystallization journal June 2010
High-Strain-Induced Deformation Mechanisms in Block–Graft and Multigraft Copolymers journal December 2011
Advances in Living Anionic Polymerization: From Functional Monomers, Polymerization Systems, to Macromolecular Architectures journal February 2014
Synthesis and Properties of Block Polymers. I. Poly-α-methylstyrene-Polyisoprene-Poly-α-methylstyrene journal September 1969
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
Synthesis and Properties of New Thermoplastic Elastomers Containing Poly[4-(1-adamantyl)styrene] Hard Segments journal July 2008
Synthesis and Characterization of an ABC Miktoarm Star Terpolymer of Cyclohexadiene, Styrene, and 2-Vinylpyridine journal November 2008
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
Poly[alkyl methacrylate- b -butadiene- b -alkyl methacrylate] Triblock Copolymers:  Synthesis, Morphology, and Mechanical Properties at High Temperatures journal January 1996
Difunctional Initiator Based on 1,3-Diisopropenylbenzene. 6. Synthesis of Methyl Methacrylate−Butadiene−Methyl Methacrylate Triblock Copolymers journal July 1997
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
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
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
Free Radical Polymerization of 7-Methyl-1-methylene-3-phenylindene. Copoly(methylene/7-methyl-3-phenyl-1,1-indenylene)−Excimer Photoluminescence journal January 1999
Graft Copolymers with Regularly Spaced, Tetrafunctional Branch Points:  Morphology and Grain Structure journal March 2000
Living Anionic Polymerization of Benzofulvene: Highly Reactive Fixed Transoid 1,3-Diene journal January 2013
Sustainable Thermoplastic Elastomers from Terpene-Derived Monomers journal July 2014
‘Living’ Polymers journal November 1956
Anionic Polymerization: Principles and Practical Applications reference-book March 1996

Cited By (9)

Block Copolymers: Synthesis, Self-Assembly, and Applications journal October 2017
The Microscopic Structure–Property Relationship of Metal–Organic Polyhedron Nanocomposites journal November 2019
The Microscopic Structure–Property Relationship of Metal–Organic Polyhedron Nanocomposites journal November 2019
Initiating Mechanism of the Anionic Polymerization of Methacrylates with t ‐BuOK and the Synthesis of ABA Type Triblock Copolymers journal November 2019
Initiating Mechanism of the Anionic Polymerization of Methacrylates with t ‐BuOK and the Synthesis of ABA Type Triblock Copolymers journal November 2019
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
Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants journal September 2017
Elastomeric polyethylenes accessible via ethylene homo-polymerization using an unsymmetrical α-diimino-nickel catalyst journal January 2017
All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties journal January 2017

Similar Records

All-acrylic multigraft copolymer superelastomers
Patent · Tue May 10 00:00:00 EDT 2022 · OSTI ID:1892910

All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties
Journal Article · Fri Aug 25 00:00:00 EDT 2017 · Polymer Chemistry · OSTI ID:1407777

Recent advances in thermoplastic elastomers from living polymerizations: Macromolecular architectures and supramolecular chemistry
Journal Article · Thu Apr 25 00:00:00 EDT 2019 · Progress in Polymer Science · OSTI ID:1546540

Related Subjects