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

Goodwin, Andrew; Wang, Weiyu; Kang, Nam -Goo; Wang, Yangyang; Hong, Kunlun; Mays, Jimmy

doi:10.1021/acs.iecr.5b02560

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

Journal Article · Fri Aug 21 00:00:00 EDT 2015 · Industrial and Engineering Chemistry Research

DOI:https://doi.org/10.1021/acs.iecr.5b02560· OSTI ID:1245351

Goodwin, Andrew ^[1]; Wang, Weiyu ^[1]; Kang, Nam -Goo ^[1]; Wang, Yangyang ^[2]; Hong, Kunlun ^[2]; Mays, Jimmy ^[3]

Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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.

View Accepted Manuscript (DOE)

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:: 1245351

Journal Information:: Industrial and Engineering Chemistry Research, Journal Name: Industrial and Engineering Chemistry Research Journal Issue: 39 Vol. 54; ISSN 0888-5885

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers Misichronis, Konstantinos; Wang, Weiyu; Cheng, Shiwang RSC Advances, Vol. 8, Issue 10 https://doi.org/10.1039/c7ra08641e	journal	January 2018
Reversible-addition fragmentation chain transfer (RAFT) mediated depolymerization of brush polymers Flanders, Michael J.; Gramlich, William M. Polymer Chemistry, Vol. 9, Issue 17 https://doi.org/10.1039/c8py00446c	journal	January 2018

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