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Title: All-acrylic multigraft copolymers: Effect of side chain molecular weight and volume fraction on mechanical behavior

Abstract

We present in this paper the synthesis of poly(n-butyl acrylate)-g-poly(methyl methacrylate) (PnBA-g-PMMA) multigraft copolymers via a grafting-through (macromonomer) approach. The synthesis was performed using two controlled polymerization techniques. The PMMA macromonomer was obtained by high-vacuum anionic polymerization followed by the copolymerization of n-butyl acrylate and PMMA macromonomer using reversible addition–fragmentation chain transfer (RAFT) polymerization to yield the desired all-acrylic multigraft structures. The PnBA-g-PMMA multigraft structures exhibit randomly spaced branch points with various PMMA contents, ranging from 15 to 40 vol %, allowing an investigation into how physical properties vary with differences in the number of branch points and molecular weight of grafted side chains. The determination of molecular weight and polydispersity indices of both the PMMA macromonomer and the graft copolymers was carried out using size exclusion chromatography with triple detection, and the structural characteristics of both the macromonomer and PnBA-g-PMMA graft materials were characterized by 1H and 13C NMR. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was employed for monitoring the macromonomer synthesis. Thermal characteristics of the materials were analyzed using differential scanning calorimetry and thermogravimetric analysis. The mechanical performance of the graft materials was characterized by rheology and dynamic mechanical analysis, revealing that samples with PMMA content of 25–40more » vol % exhibit superior elastomeric properties as compared to materials containing short PMMA side chains or <25 vol % PMMA. In conclusion, atomic force microscopy showed a varying degree of microphase separation between the glassy and rubbery components that is strongly dependent on PMMA side chain molecular weight.« less

Authors:
 [1];  [1];  [1];  [2];  [2];  [3]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, 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:
1245351
Grant/Contract Number:  
AC05-00OR22725; 1237787
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 54; Journal Issue: 39; Journal ID: ISSN 0888-5885
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Goodwin, Andrew, Wang, Weiyu, Kang, Nam -Goo, Wang, Yangyang, Hong, Kunlun, and Mays, Jimmy. All-acrylic multigraft copolymers: Effect of side chain molecular weight and volume fraction on mechanical behavior. United States: N. p., 2015. Web. doi:10.1021/acs.iecr.5b02560.
Goodwin, Andrew, Wang, Weiyu, Kang, Nam -Goo, Wang, Yangyang, Hong, Kunlun, & Mays, Jimmy. All-acrylic multigraft copolymers: Effect of side chain molecular weight and volume fraction on mechanical behavior. United States. https://doi.org/10.1021/acs.iecr.5b02560
Goodwin, Andrew, Wang, Weiyu, Kang, Nam -Goo, Wang, Yangyang, Hong, Kunlun, and Mays, Jimmy. 2015. "All-acrylic multigraft copolymers: Effect of side chain molecular weight and volume fraction on mechanical behavior". United States. https://doi.org/10.1021/acs.iecr.5b02560. https://www.osti.gov/servlets/purl/1245351.
@article{osti_1245351,
title = {All-acrylic multigraft copolymers: Effect of side chain molecular weight and volume fraction on mechanical behavior},
author = {Goodwin, Andrew and Wang, Weiyu and Kang, Nam -Goo and Wang, Yangyang and Hong, Kunlun and Mays, Jimmy},
abstractNote = {We present in this paper the synthesis of poly(n-butyl acrylate)-g-poly(methyl methacrylate) (PnBA-g-PMMA) multigraft copolymers via a grafting-through (macromonomer) approach. The synthesis was performed using two controlled polymerization techniques. The PMMA macromonomer was obtained by high-vacuum anionic polymerization followed by the copolymerization of n-butyl acrylate and PMMA macromonomer using reversible addition–fragmentation chain transfer (RAFT) polymerization to yield the desired all-acrylic multigraft structures. The PnBA-g-PMMA multigraft structures exhibit randomly spaced branch points with various PMMA contents, ranging from 15 to 40 vol %, allowing an investigation into how physical properties vary with differences in the number of branch points and molecular weight of grafted side chains. The determination of molecular weight and polydispersity indices of both the PMMA macromonomer and the graft copolymers was carried out using size exclusion chromatography with triple detection, and the structural characteristics of both the macromonomer and PnBA-g-PMMA graft materials were characterized by 1H and 13C NMR. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was employed for monitoring the macromonomer synthesis. Thermal characteristics of the materials were analyzed using differential scanning calorimetry and thermogravimetric analysis. The mechanical performance of the graft materials was characterized by rheology and dynamic mechanical analysis, revealing that samples with PMMA content of 25–40 vol % exhibit superior elastomeric properties as compared to materials containing short PMMA side chains or <25 vol % PMMA. In conclusion, atomic force microscopy showed a varying degree of microphase separation between the glassy and rubbery components that is strongly dependent on PMMA side chain molecular weight.},
doi = {10.1021/acs.iecr.5b02560},
url = {https://www.osti.gov/biblio/1245351}, journal = {Industrial and Engineering Chemistry Research},
issn = {0888-5885},
number = 39,
volume = 54,
place = {United States},
year = {Fri Aug 21 00:00:00 EDT 2015},
month = {Fri Aug 21 00:00:00 EDT 2015}
}

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Works referencing / citing this record:

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