December 2010, Volume 1, No.

2 International Journal of Chemical and Environmental Engineering

Syntheses of High-Performance, EnvironmentallyDegradable 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 pcoumaryloyl group having a photosensitive phenylenevinylene and a polymerizable hydroxycarboxylic acid group, such as p-coumaric acid (4-hydroxycinnamic acid; 4HCA), m-coumaric acid (3hydroxycinnamic acid; 3HCA), ferulic acid (3-methoxy4-hydroxycinnamic acid; MHCA), and caffeic acid (3,4dihydroxycinnamic 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 were phytomonomers. These phytomonomers biodegraded by microbial action.

Table 1.Molecular Weights of Poly(m-coumaric acid) prepared under Various Catalysts

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.

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.

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an environmentally-degradable plastic with extremely high performance. ACKNOWLEDGMENT This research was mainly supported by a Grant-inAid for JST (Practical application research, Kaneko Project). REFERENCES
[1] E. S. Stevens, “Green Plastics: An Introduction to the New Science of Biodegradable Plastics;” Princeton University Press: New Jersey, 2002. Figure 2. Processed resin of P(4HCA-co-DHCA) copolymer. Inset: photo of in-soil degraded resin. [2] B.Saulnier, S. Ponsart, J. Coudane, H. Garreau, M. Vert, “Lactic Acid-Based Functionalized Polymers via Copolymerization and Chemical Modification” Macromol Biosci vol. 4, pp. 232-237, 2004 Y. Imai, “Synthesis of novel organic-soluble high-temperature aromatic polymers” High Perform Polym vol.7, pp.337-345, 1995 T.Kaneko, H.T.Tran, D.J.Shi, M.Akashi, “EnvironmentallyDegradable, High-performance Plastics from Phenolic Phytomonomers” Nature Mater. vol.5, pp.966-970, 2006 N. Ricarda, J. M. Anthony, M. Cathie “Engineering plants with increased levels of the antioxidant chlorogenic acid” Nat Biotechnol vol.22, pp. 746-754, 2004

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
[3] [4]

[5]

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