December 2010, Volume 1, No.

2
International Journal of Chemical and Environmental Engineering

Syntheses of High-Performance, Environmentally-

Degradable Polymers from Polyphenols
T. Kaneko*, T. Suzuki, S. Wang, D. Kaneko
Department of Materials Science, Japan Advanced Institute of Science and Techonology (JAIST)
Nomi, Ishikawa, Japan
*Corresponding author:kaneko@jaist.ac.jp

Abstract
Liquid crystalline (LC) polymers of rigid monomers based on phenolic acid were prepared by in-bulk polymerization in the presence
of appropriate catalysts. Coumaric acid derivatives such as [4-hydroxycinnamic acid (4HCA)] were selected as phytomonomers.
Various catalysts appropriate for transesterification polymerization of acetylated coumarates were tried to use and Na3PO4 was found
most appropriate. The 4HCA homopolymer adopting a rigid structure showed a thermotropic LC phase while 3,4-dihydroxycinnamic
acid (DHCA) adopting a hyperbranching architecture showed a transparent but brown colored resin which showed an elastomeric
behavior above its softening temperature. The copolymer P(4HCA-co-DHCA)s were also prepared successfully and showed high
molecular weight, high mechanical strength, high Young's modulus, and high softening temperature. The copolymers showed a
smooth hydrolysis, and in-soil degradation.
Keywords: Copolymers, Liquid Crystals, Degradation, High-Performance Polymers, Bio-Base Materials.

1. Introduction
Development of environmentally-benign polymers,
which are derived from naturally occurring molecules
degrade into environmentally is one effective method for
solving environmental problems. Bio-base polyesters
exhibiting smooth degradation have been widely studied
as environmentally friendly polymeric materials [1].
However, aliphatic bio-base polyesters such as
poly(hydroxyalkanoate)s, poly(butylene succinate), and
so on [2] degrade too rapidly to actually be used.
EcoflexTM and BiomaxTM are more durable and show
greater performance levels than do the aliphatic bio-base
polymers but the problems of environmental toxicity and
availability of terephthalic acid are serious. Poly(lactic
acid)s (PLA) have been remarkably well developed
because of their high mechanical strength. However, it
was estimated that these polyesters will become
substitutes for only a small percentage of non degradable
plastics currently in use since application of the aliphatic
polyesters is limited due to their poor level of
thermoresistance in applications as an engineering plastic.
Non degradable engineering plastics have a rigid
component of a benzene ring and super engineering
plastics have a continuous structure of benzene and hetero
rings. The introduction of an aromatic component into a
thermoplastic polymer backbone is an efficient method
for intrinsically improving material performance [3].
Additionally, the continuous sequence of aromatic rings
can be a mesogenic group. Molding in the thermotropic
liquid crystalline (LC) state can induce molecular
orientation giving anisotropy to the mechanical
performance, which sometimes dramatically increases
mechanical strength and Young’s modulus. Coumarate
phytochemicals was polymerized in the presence of
sodium acetate as a catalysts [4] but the side reaction
could not be excluded.
Here, we report on the advanced preparation method
of biopolyarylates derived mainly from polymerizable
phytochemicals—in other words, “phytomonomers”
widely present as lignin biosynthetic precursors [5]. One
series of polyarylates showed environmental degradability
and a performance level as high as an engineering plastic.
2. Materials and Method
2.1 Selection of Phytomonomers
The phenolic phytochemical family with the p-
coumaryloyl group having a photosensitive
phenylenevinylene and a polymerizable
hydroxycarboxylic acid group, such as p-coumaric acid
(4-hydroxycinnamic acid; 4HCA), m-coumaric acid (3-
hydroxycinnamic acid; 3HCA), ferulic acid (3-methoxy-
4-hydroxycinnamic acid; MHCA), and caffeic acid (3,4-
dihydroxycinnamic acid; DHCA), has been selected as
biomonomers (polymer structures, Fig. 1). These
molecules are widely available in various plants with an
essential pathway of lignin biosynthesis. 4HCA
derivatives are used as allelopathic chemicals in plants
and widely exist in soil. 4HCA is also available in
 several photosynthetic bacteria as a protein component.
Rhodobacter capsulatus, Rhodobacter sphaeroides, and
so on have photoactive yellow protein containing a 4HCA
component. Furthermore, since their enzymatic synthetic
roots from amino acids were well defined as being very
simple, it is possible to mass-produce these
phytomonomers. These phytomonomers were
biodegraded by microbial action.
Figure 1. Polyester structures prepared by coumarate
phytomonomers
2.2. Polymerization Procedures
P4HCA was obtained by a thermal
polycondensation of 4HCA as follows. 4HCA was heated
at 220°C for 24 h in the presence of anhydride acetic acid
as a condensation reagent and an alkaline salt as a catalyst
for transesterification. The molten mixture gradually
became viscous during the reaction period. After cooling,
the product was dissolved in pentafluorophenol and
purified by reprecipitation over methanol, then was
washed with methanol by the Soxhlet extraction method
for 24 h (yield: 90%). Other coumarates were
polymerized by analogous procedures with 4HCA (yield:
more than 80 %)
3. Results and discussion
3.1 Polymerization in the presence of alkaline catalysts
The coumarate monomers were homopolymerized by
one-pot polymerization using an acetic anhydride as well
as various alkaline catalysts. Acetylated 3HCA monomer
was used since the corresponding polymer showed a high
solubility to investigate the structures such as molecular
weight by GPC. In Table 1, the molecular weights (GPC;
poly(methyl methacrylate) standard) of P3HCA were
prepared using various catalysts (1 mol% to monomers)
summarized, and the weight-average molecular weight
attained reached 28 000 the polymerization was made
with sodium phosphate, to work as an alkaline catalyst as
well as a condensation reagent. IR and 1H NMR
spectroscopy demonstrated the formation of a polyester
structure of any polymers derived from these coumarates.
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Table 1.Molecular Weights of Poly(m-coumaric acid) prepared
under Various Catalysts
3.2. Polymer properties
P3HCA showed no liquid crystalline behavior
presumably due to the bend structure by m-substitution.
Then the p-substituted rigid-rod structure of the polymers
P4HCA, PMHCA, and DHCA was prepared using the
sodium phosphate catalysts. These polymerizations were
also successful. In order to investigate the thermotropic
properties of P4HCA, crossed polarizing microscopic
observations of samples was conducted sandwiched
between two glass plates as the temperature was changed.
The sample was a birefringent powder at 20°C. When the
sample was heated at a rate of 10°C min-1, the sample
melted at 215°C while maintaining its birefringence. In
the temperature range of 215–280°C, a schlieren texture
was observed with two and four brushes. Therefore,
P4HCA exhibits a nematic phase where the polymer
chains are autonomously oriented but randomly located.
On the other hand, PMHCA showed a similar behavior of
P4HCA but no clear liquid crystalline behavior while
PDHCA showed no liquid crystalline but an elastomeric
behavior above its softening temperature (Tc~120 oC)
presumably due to hyperbranching architecture.
The focus was on the combination of liquid crystalline
behavior and hyperbranching architecture and then
prepared the copolymers P(4HCA-co-DHCA)s. The
copolymerization was also successful to create very hard
resins. The weight-average molecular weight ranged more
than 3x104 -1x105. All of the copolymers were soluble in
DMF, thus denying the cross-linked network formation. If
the poly(4HCA-co-DHCA)s were heated, they melted at
specific temperatures to exhibit a thermotropic LC phase,
where the schlieren texture was observed by crossed
polarizing microscopy. Tc ranged between 115–160°C,
which were much higher than the values of the degradable
bio-based polymers reported so far and high enough for
engineering use {Tg of poly(bisphenol A carbonate), PC,
is 145°C}. The copolymer was processed into oriented
resin shown in Fig. 2.

Figure 2. Processed resin of P(4HCA-co-DHCA) copolymer. Inset:
photo of in-soil degraded resin.
4. Conclusion
A mechanical bending test of the oriented samples
showed the mechanical strength, , Young’s modulus, E,
and maximal strain, e, ranging between 25–63MPa, 7.6–
16 GPa, and 1.2–1.3, respectively. The  values of the
poly(4HCA-co-DHCA)s with 4HCA composition of 25–
50mol% were comparable to those of PC and all the
conventional environmentally degradable polymers
reported so far whereas E was much higher than they
were. Further P(4HCA-co-DHCA)s showed a smooth
hydrolysis, in-soil degradation as shown in the inset photo
of Fig.2. Thus, P(4HCA-co-DHCA)s might be applied as
135
an environmentally-degradable plastic with extremely
high performance.
ACKNOWLEDGMENT
This research was mainly supported by a Grant-in-
Aid for JST (Practical application research, Kaneko
Project).
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