Sustainable Polyesters Derived from Glucose and Castor
Oil: Building Block Structure Impacts Properties
William
C. Shearouse
Leon M. Lillie
Theresa M. Reineke
William B. Tolman
10.1021/acsmacrolett.5b00099.s001
https://acs.figshare.com/articles/journal_contribution/Sustainable_Polyesters_Derived_from_Glucose_and_Castor_Oil_Building_Block_Structure_Impacts_Properties/2186074
Using the glucose derivatives isosorbide
and glucarodilactone along
with a castor oil derivative, 10-undecenoyl chloride, two monomers
were synthesized: glucarodilactone undecenoate (GDLU) and isosorbide
undecenoate (IU). These monomers were polymerized via acyclic diene
metathesis (ADMET) polymerization to yield two homopolymers, P(GDLU)
and P(IU), and two copolymers, P<sub>1</sub>(GDLU<i>-<i>co</i>-</i>IU) and P<sub>2</sub>(GDLU<i>-<i>co</i>-</i>IU), of similar number-averaged molecular weight and relative
composition (51 and 61 kDa, <i>Đ</i> = 1.8 and 1.4,
46:54 and 52:48 mol percent). Comparison of the physical properties
and degradation behavior of these polymers revealed divergent characteristics
arising from differences in the nature of the carbohydrate building
blocks. P(IU) is more thermally stable and has a lower glass transition
temperature (<i>T</i><sub>d</sub> = 369 °C, <i>T</i><sub>g</sub> = −10 °C) than P(GDLU) (<i>T</i><sub>d</sub> = 206 °C, <i>T</i><sub>g</sub> = 32 °C) and P<sub>1,2</sub>(GDLU<i>-<i>co</i>-</i>IU) (<i>T</i><sub>d</sub> = 210 and 203 °C, <i>T</i><sub>g</sub> = 1 and 7 °C). While all of the polymers
were stable in acidic and neutral aqueous conditions, the two analogs
containing GDLU hydrolytically degraded in the presence of base. Tensile
testing of the systems revealed that both homopolymers are brittle
materials while the P(GDLU-<i>co</i>-IU) is more tough.
Notably, P<sub>1,2</sub>(GDLU<i>-<i>co</i>-</i>IU) was found to be a rubbery material with a low Young’s
modulus (0.020 and 0.002 GPa, respectively), displaying an average
elongation at break of 480 and 640%, and shape memory properties.
2015-03-17 00:00:00
monomer
Castor Oil
glucose derivatives isosorbide
homopolymers
Tensile testing
acyclic diene metathesis
GDLU hydrolytically
material
ADMET
61 kDa
glucarodilactone undecenoate
0.002 GPa
carbohydrate building blocks
Sustainable Polyesters Derived
Building Block Structure Impacts PropertiesUsing
glass transition temperature
castor oil
isosorbide undecenoate
polymer
Tg
Td
degradation behavior
IU
shape memory properties