Macromolecules
Article
imation (GGA). The basis set was set to DZP, which is in accord with
the accuracy requirement.
Differential scanning calorimeter (DSC1, Mettler-Toledo, Switzer-
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properties of bio-based epoxy networks derived from isosorbide
diglycidyl ether. Polymer 2011, 52, 3611−3620.
land) was used to determine the T and the melting temperature. The
(5) Hong, J.; Radojcic, D.; Ionescu, M.; Petrovic, Z. S.; Eastwood, E.
̌ ́ ́
g
samples (5−10 mg) were sealed in 40 μL aluminum crucibles and
scanned at a heating rate of 10 K min− under a nitrogen atmosphere.
Thermal stability was measured using a TGA/DSC1 thermogravi-
metric analyzer (TGA, Mettler-Toledo, Switzerland). Samples (10−
Advanced materials from corn: isosorbide-based epoxy resins. Polym.
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1
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of polymers from renewable resources: furans, vegetable oils, and
polysaccharides. Chem. Rev. 2016, 116, 1637−1669.
1
5
5 mg) were loaded into 70 μL alumina crucibles and scanned from
0 to 800 °C at a heating rate of 10 K min under a nitrogen
−
1
(7) Hu, F.; La Scala, J. J.; Sadler, J. M.; Palmese, G. R. Synthesis and
atmosphere. Prior to testing, all samples were dried in a vacuum oven
at 80 °C to remove the volatiles. The viscosity as a function of
temperature was characterized using a rheometer (Discovery HR-2,
TA Instruments) with 25 mm parallel plates at a fixed frequency of 10
rad/s. Dynamic mechanical properties as a function of temperature
were characterized using a dynamic mechanical analyzer (DMA)
characterization of thermosetting furan-based epoxy systems. Macro-
molecules 2014, 47, 3332−3342.
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8) Qin, J.; Liu, H.; Zhang, P.; Wolcott, M.; Zhang, J. Use of eugenol
and rosin as feedstocks for biobased epoxy resins and study of curing
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(
Q800, TA Instruments) in the film tension mode. The dimensions of
to functional additive: toughening epoxy resin with lignin. ACS Appl.
3
the sample were about 10.0 × 5.0 × 0.3 mm . The frequency was set
at 1 Hz, and the oscillating amplitude was set at 5 μm. The samples
were scanned from room temperature to 250 °C at a heating rate of 3
K min .
Stress relaxation was measured using a rheometer (Discovery HR-
, TA Instruments) with 8 mm parallel plates. The sample with
Mater. Interfaces 2014, 6, 5810−5817.
(10) Liu, X.; Zhang, J. High-performance biobased epoxy derived
from rosin. Polym. Int. 2010, 59, 607−609.
−
1
(11) Huang, K.; Zhang, J.; Li, M.; Xia, J.; Zhou, Y. Exploration of the
complementary properties of biobased epoxies derived from rosin
diacid and dimer fatty acid for balanced performance. Ind. Crops Prod.
2
uniform thickness was heated to 220 °C and equilibrated for 10 min.
Subsequently, a constant normal force of 2 N was applied to obtain a
good contact of sample with the parallel plate. During the test, a 1.5%
or 2.5% strain was applied and maintained, and the relaxation
modulus or torque value as a function of time was recorded. After test,
The tensile strengths of the cured samples were measured by an
Instron 1185 test machine according to ISO 527:1993, and type 1BA
specimens were used. The crosshead speed was set at 1 mm/min. At
least five repeats were performed for each composition.
2
(
013, 49, 497−506.
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M.; Andrady, A.; Narayan, R.; Law, K. L. Marine pollution. Plastic
waste inputs from land into the ocean. Science 2015, 347, 768−771.
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for new materials production. Nat. Rev. Chem. 2017, 1, 0046.
14) Liu, T.; Guo, X.; Liu, W.; Hao, C.; Wang, L.; Hiscox, W. C.;
(
Liu, C.; Xin, J.; Zhang, J. Selective cleavage of ester linkages of
anhydride-cured epoxy using a benign method and reuse of the
decomposed polymer in new epoxy preparation. Green Chem. 2017,
1
(
9, 4364−4372.
15) Denissen, W.; Winne, J. M.; Du Prez, F. E. Vitrimers:
permanent organic networks with glass-like fluidity. Chem. Sci. 2016,
, 30−38.
16) Rottger, M.; Domenech, T.; van der Weegen, R.; Breuillac, A.;
Nicolay, R.; Leibler, L. High-performance vitrimers from commodity
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ASSOCIATED CONTENT
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Supporting Information
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6
2−65.
Table S1 and Figures S1−S15 (PDF)
(17) Brutman, J. P.; Delgado, P. A.; Hillmyer, M. A. Polylactide
vitrimers. ACS Macro Lett. 2014, 3, 607−610.
(
18) Snyder, R. L.; Fortman, D. J.; De Hoe, G. X.; Hillmyer, M. A.;
AUTHOR INFORMATION
Dichtel, W. R. Reprocessable Acid-Degradable Polycarbonate
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Vitrimers. Macromolecules 2018, 51, 389−397.
(19) Taynton, P.; Ni, H.; Zhu, C.; Yu, K.; Loob, S.; Jin, Y.; Qi, H. J.;
*
Zhang, W. Repairable woven carbon fiber composites with full
ORCID
recyclability enabled by malleable polyimine networks. Adv. Mater.
2
016, 28, 2904−2909.
20) Jin, Y.; Yu, C.; Denman, R. J.; Zhang, W. Recent advances in
dynamic covalent chemistry. Chem. Soc. Rev. 2013, 42, 6634−6654.
21) Montarnal, D.; Capelot, M.; Tournilhac, F.; Leibler, L. Silica-
Like Malleable Materials from Permanent Organic Networks. Science
011, 334, 965−968.
22) Capelot, M.; Montarnal, D.; Tournilhac, F.; Leibler, L. Metal-
(
(
2
(
Notes
The authors declare no competing financial interest.
catalyzed transesterification for healing and assembling of thermosets.
J. Am. Chem. Soc. 2012, 134, 7664−7667.
(23) Shi, Q.; Yu, K.; Kuang, X.; Mu, X.; Dunn, C. K.; Dunn, M. L.;
Wang, T.; Qi, H. J. Recyclable 3D printing of vitrimer epoxy. Mater.
Horiz. 2017, 4, 598−607.
(24) Altuna, F. I.; Pettarin, V.; Williams, R. J. J. Self-healable
polymer networks based on the cross-linking of epoxidised soybean
oil by an aqueous citric acid solution. Green Chem. 2013, 15, 3360−
3366.
(25) Dahlke, J.; Zechel, S.; Hager, M. D.; Schubert, U. S. How to
Design a Self-Healing Polymer: General Concepts of Dynamic
Covalent Bonds and Their Application for Intrinsic Healable
Materials. Adv. Mater. Interfaces 2018, 1800051.
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