skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization

Abstract

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermal analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 105 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.

Authors:
 [1];  [2];  [1];  [2];  [3];  [2];  [1];  [2]
  1. Northwestern Polytechnical University, Xi'an (China)
  2. Univ. of Tennessee, Knoxville, TN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1265397
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 54; Journal Issue: 4; Journal ID: ISSN 0888-5885
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Wenwen, Wang, Weiyu, Li, Hui, Lu, Xinyi, Chen, Jihua, Kang, Nam-goo, Zhang, Qiuyu, and Mays, Jimmy. Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization. United States: N. p., 2015. Web. doi:10.1021/ie504457e.
Wang, Wenwen, Wang, Weiyu, Li, Hui, Lu, Xinyi, Chen, Jihua, Kang, Nam-goo, Zhang, Qiuyu, & Mays, Jimmy. Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization. United States. https://doi.org/10.1021/ie504457e
Wang, Wenwen, Wang, Weiyu, Li, Hui, Lu, Xinyi, Chen, Jihua, Kang, Nam-goo, Zhang, Qiuyu, and Mays, Jimmy. 2015. "Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization". United States. https://doi.org/10.1021/ie504457e. https://www.osti.gov/servlets/purl/1265397.
@article{osti_1265397,
title = {Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization},
author = {Wang, Wenwen and Wang, Weiyu and Li, Hui and Lu, Xinyi and Chen, Jihua and Kang, Nam-goo and Zhang, Qiuyu and Mays, Jimmy},
abstractNote = {In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermal analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 105 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.},
doi = {10.1021/ie504457e},
url = {https://www.osti.gov/biblio/1265397}, journal = {Industrial and Engineering Chemistry Research},
issn = {0888-5885},
number = 4,
volume = 54,
place = {United States},
year = {Wed Jan 14 00:00:00 EST 2015},
month = {Wed Jan 14 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Block and Graft Copolymers
book, January 1989


Macromolecular architectures by living and controlled/living polymerizations
journal, December 2006


Copolymerization of isoprene and hydroxyl containing monomers by controlled radical and emulsion methods
journal, January 2012


Well-defined graft copolymers: from controlled synthesis to multipurpose applications
journal, January 2011


Tough Polylactide Graft Copolymers
journal, September 2010


Synthesis and Structure– Property Relationships for Regular Multigraft Copolymers
journal, August 2004


Multigraft copolymer superelastomers: Synthesis morphology, and properties
journal, April 2011


Mechanical Properties and Hysteresis Behaviour of Multigraft Copolymers
journal, February 2006


Synthesis of well-defined multigraft copolymers
journal, January 2011


Anionic homo- and copolymerization of double-tailed macromonomers: A route to novel macromolecular architectures
journal, January 2005


Anionic homo- and copolymerization of styrenic triple-tailed polybutadiene macromonomers
journal, January 2007


Anionic polymerization: High vacuum techniques
journal, January 2000


Experimental techniques in high-vacuum anionic polymerization
journal, January 2005


Tetrafunctional Multigraft Copolymers as Novel Thermoplastic Elastomers
journal, August 2001


Synthesis of styrene- g -polyisoprene nanoparticles by emulsion polymerization and its effect on properties of polyisoprene composites: STYRENE-G-POLYISOPRENE NANOPARTICLES AND ITS COMPOSITES
journal, December 2011


The analysis of organolithium compounds
journal, December 1964


Synthetic Rubber Production. Chelating Agents in Sulfoxylate Polymerization
journal, March 1960


Simple Method for the Esterification of Carboxylic Acids
journal, July 1978


Synthesis and cross-linking of polyisoprene latexes
journal, February 2004


Synthesis of nanosized ethylene-propylene rubber latex via polyisoprene hydrogenation
journal, May 2012


Styrene–Butadiene–Styrene Triblock Copolymer Latex via Reversible Addition–Fragmentation Chain Transfer Miniemulsion Polymerization
journal, November 2012


Microphase Separation of Block Copolymer Thin Films
journal, April 2010


Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition
journal, December 1995


Theory of microphase separation in graft and star copolymers
journal, October 1986


Methyl Group Dynamics in Glassy Polyisoprene: A Neutron Backscattering Investigation
journal, July 1994


Effect of Molecular Architecture on Dynamics of Multigraft Copolymers:  Combs, Centipedes, and Barbwires
journal, October 2003


Deformation Behavior of Sphere-Forming Trifunctional Multigraft Copolymer
journal, July 2008


Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes
journal, June 2007


Study on the influence of electron beam irradiation on the thermal, mechanical, and rheological properties of ethylene-octene copolymer with high comonomer content
journal, September 2012


Works referencing / citing this record:

Superstretchable, Self-Healing Polymeric Elastomers with Tunable Properties
journal, April 2018


Rheological and thermal degradation properties of hyperbranched polyisoprene prepared by anionic polymerization
journal, November 2019


The Microscopic Structure–Property Relationship of Metal–Organic Polyhedron Nanocomposites
journal, November 2019


Block Copolymers: Synthesis, Self-Assembly, and Applications
journal, October 2017


The Microscopic Structure–Property Relationship of Metal–Organic Polyhedron Nanocomposites
journal, November 2019


Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers
journal, January 2018


Rheological and thermal degradation properties of hyperbranched polyisoprene prepared by anionic polymerization
journal, November 2019


Block Copolymers: Synthesis, Self-Assembly, and Applications
journal, October 2017