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

Title: Design of Graft Block Polymer Thermoplastics

Abstract

Graft block polymers are defined by several architectural parameters, including backbone flexibility, graft density, backbone length, side-chain composition, and side-chain length. In this work we probe the impacts of each of these parameters on the phase behavior, rheological properties, and mechanical performance of these materials. Specifically, we examine two sets of materials prepared from backbones of different inherent flexibility. One set was prepared from poly[(n-butyl acrylate)-co-(2-hydroxyethyl acrylate)] (B$$_x$$E$$_y$$) copolymers; the other was prepared from hydroxypropyl methyl cellulose (HPMC) samples. Sequential ring-opening transesterification polymerization from these hydroxyl-functionalized macroinitiatiors yielded a diblock graft architecture containing a rubbery interior block and semicrystalline exterior blocks tethered to a flexible (B$$_x$$E$$_y$$) or rigid (HPMC) backbone. Good control over side-chain molar mass and composition and judicious choice of the graft block segments enabled the preparation of materials that were either ordered or disordered in the melt state. In the former case, crystallization destroys existing order in the material; in the latter case crystallization induces new microphase separation in the bulk. Many of the structure–mechanical property relationships observed for graft block copolymers with rigid backbones are maintained for graft block polymers with semiflexible backbones, including the tendency for samples to remain transparent when stretched. However, interestingly, wemore » note the effects of graft density and backbone length are quite different depending on the rigidity of the backbone.« less

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]
  1. Southeast Univ., Nanjing (China); Univ. of Minnesota, Minneapolis, MN (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
National Science Foundation (NSF); National Natural Science Foundation of China (NSFC); E.I. DuPont de Nemours & Co.; The Dow Chemical Company; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1340733
Alternate Identifier(s):
OSTI ID: 1418560
Grant/Contract Number:  
DMR-1420013; 21504013; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 23; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; Hydroxyls; Plastics; Materials; Polymers; Copolymers

Citation Formats

Zhang, Jiuyang, Schneiderman, Deborah K., Li, Tuoqi, Hillmyer, Marc A., and Bates, Frank S. Design of Graft Block Polymer Thermoplastics. United States: N. p., 2016. Web. doi:10.1021/acs.macromol.6b02033.
Zhang, Jiuyang, Schneiderman, Deborah K., Li, Tuoqi, Hillmyer, Marc A., & Bates, Frank S. Design of Graft Block Polymer Thermoplastics. United States. https://doi.org/10.1021/acs.macromol.6b02033
Zhang, Jiuyang, Schneiderman, Deborah K., Li, Tuoqi, Hillmyer, Marc A., and Bates, Frank S. 2016. "Design of Graft Block Polymer Thermoplastics". United States. https://doi.org/10.1021/acs.macromol.6b02033. https://www.osti.gov/servlets/purl/1340733.
@article{osti_1340733,
title = {Design of Graft Block Polymer Thermoplastics},
author = {Zhang, Jiuyang and Schneiderman, Deborah K. and Li, Tuoqi and Hillmyer, Marc A. and Bates, Frank S.},
abstractNote = {Graft block polymers are defined by several architectural parameters, including backbone flexibility, graft density, backbone length, side-chain composition, and side-chain length. In this work we probe the impacts of each of these parameters on the phase behavior, rheological properties, and mechanical performance of these materials. Specifically, we examine two sets of materials prepared from backbones of different inherent flexibility. One set was prepared from poly[(n-butyl acrylate)-co-(2-hydroxyethyl acrylate)] (B$_x$E$_y$) copolymers; the other was prepared from hydroxypropyl methyl cellulose (HPMC) samples. Sequential ring-opening transesterification polymerization from these hydroxyl-functionalized macroinitiatiors yielded a diblock graft architecture containing a rubbery interior block and semicrystalline exterior blocks tethered to a flexible (B$_x$E$_y$) or rigid (HPMC) backbone. Good control over side-chain molar mass and composition and judicious choice of the graft block segments enabled the preparation of materials that were either ordered or disordered in the melt state. In the former case, crystallization destroys existing order in the material; in the latter case crystallization induces new microphase separation in the bulk. Many of the structure–mechanical property relationships observed for graft block copolymers with rigid backbones are maintained for graft block polymers with semiflexible backbones, including the tendency for samples to remain transparent when stretched. However, interestingly, we note the effects of graft density and backbone length are quite different depending on the rigidity of the backbone.},
doi = {10.1021/acs.macromol.6b02033},
url = {https://www.osti.gov/biblio/1340733}, journal = {Macromolecules},
issn = {0024-9297},
number = 23,
volume = 49,
place = {United States},
year = {Thu Dec 01 00:00:00 EST 2016},
month = {Thu Dec 01 00:00:00 EST 2016}
}

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

Citation Metrics:
Cited by: 55 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Polymer blends and composites from renewable resources
journal, June 2006


Thermoplastic Elastomers
journal, July 1987


Multiblock Polymers: Panacea or Pandora's Box?
journal, April 2012


Consequences of Molecular Bridging in Lamellae-Forming Triblock/Pentablock Copolymer Blends
journal, November 2003


Sustainable Poly(lactide- b -butadiene) Multiblock Copolymers with Enhanced Mechanical Properties
journal, September 2013


Effect of Architecture on the Phase Behavior of AB-Type Block Copolymer Melts
journal, February 2012


Polylactide. II. Viscosity–molecular weight relationships and unperturbed chain dimensions
journal, August 1979


Hyperbranched and Highly Branched Polymer Architectures—Synthetic Strategies and Major Characterization Aspects
journal, November 2009


Block copolymers in tomorrow's plastics
journal, January 2005


Well-Defined, Model Long Chain Branched Polyethylene. 1. Synthesis and Characterization
journal, April 2000


Solvent-free, supersoft and superelastic bottlebrush melts and networks
journal, November 2015


Tough and Sustainable Graft Block Copolymer Thermoplastics
journal, March 2016


Tetrafunctional Multigraft Copolymers as Novel Thermoplastic Elastomers
journal, August 2001


Polar Three-Arm Star Block Copolymer Thermoplastic Elastomers Based on Polyacrylonitrile
journal, April 2008


A Novel Architecture toward Third-Generation Thermoplastic Elastomers by a Grafting Strategy
journal, June 2013


All-Acrylic Multigraft Copolymers: Effect of Side Chain Molecular Weight and Volume Fraction on Mechanical Behavior
journal, September 2015


Correlations between chain parameters and the plateau modulus of polymers
journal, February 1986


Heterogeneous polymer systems. I. Torsional modulus studies
journal, September 1961


Estimation of the Persistence Length of Polymers by MD Simulations on Small Fragments in Solution. Application to Cellulose
journal, October 1997

  • Kroon-Batenburg, Loes M. J.; Kruiskamp, Peter H.; Vliegenthart, Johannes F. G.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 42
  • https://doi.org/10.1021/jp971717k

Activators Regenerated by Electron Transfer for Atom-Transfer Radical Polymerization of (Meth)acrylates and Related Block Copolymers
journal, July 2006


Controlled Ring-Opening Polymerization of Lactide and Glycolide
journal, December 2004


Formation of interfacial network structure via photo-crosslinking in carbon fiber/epoxy composites
journal, January 2014


Polylactones 48. SnOct 2 -Initiated Polymerizations of Lactide:  A Mechanistic Study
journal, February 2000


Synthesis and Crystallization of Poly(vinyl acetate)- g -Poly( l -lactide) Graft Copolymer with Controllable Graft Density
journal, August 2013


Crystallization and thermal properties of PLLA comb polymer
journal, March 2008


ε-Decalactone: A Thermoresilient and Toughening Comonomer to Poly( l -lactide)
journal, July 2013


Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990


Synthesis and Melt Processing of Sustainable Poly(ε-decalactone)- block -Poly(lactide) Multiblock Thermoplastic Elastomers
journal, October 2014


Crystallization Behavior of Crystalline‐Amorphous Diblock Copolymers Consisting of a Rubbery Amorphous Block
journal, September 2006


Thermoplastic Elastomers with Composite Crystalline−Glassy Hard Domains and Single-Phase Melts
journal, May 2010


Structure and Properties of Semicrystalline−Rubbery Multiblock Copolymers
journal, December 2005


Crystallization behavior of poly(ε-caprolactone) chains confined in lamellar nanodomains
journal, August 2014


Unifying Weak- and Strong-Segregation Block Copolymer Theories
journal, January 1996


Aliphatic Polyester Block Polymer Design
journal, March 2016


Chain structure, phase morphology, and toughness relationships in polymers and blends
journal, July 1990


Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties
journal, August 1994


Linear Rheology of Polyolefin-Based Bottlebrush Polymers
journal, June 2015


Works referencing / citing this record:

Field-theoretic simulations of bottlebrush copolymers
journal, November 2018


Photocross‐linked polymers based on plant‐derived monomers for potential application in optical 3D printing
journal, November 2019


Mimicking biological stress–strain behaviour with synthetic elastomers
journal, September 2017


Natural Polymers from Biomass Resources as Feedstocks for Thermoplastic Materials
journal, February 2019