Abstract
Novel phenylethynyl-terminated addition-type imide oligomers (degree of polymerization, n=4) derived from 1,2,4,5-benzenetetracarboxylic dianhydride, 2-phenyl-4,4′-diaminodiphenyl ether (p-ODA), which has an asymmetric and nonplanar structure, and 9,9-bis(4-aminophenoxy)fluorene were synthesized for use as the matrix resin of fiber-reinforced composites with high heat resistance. The uncured imide oligomers showed good solubility (>30 wt%) in aprotic solvents such as N-methyl-2-pyrrolidone and very low minimum melt viscosity. These excellent properties were achieved using steric hindrance of the pendant phenyl group of p-ODA in a solution or a melted state to prevent the intramolecular/intermolecular interactions of imide oligomer chains. The imide oligomers were converted to crosslinked structures after curing at 370 °C for 1 h. Thermal and rheological properties of the cured resins were characterized by differential scanning calorimetry, thermogravimetric analysis and dynamic rheometry. The glass transition temperature and elongation-at-break of the cured imide resin were found to be almost >350 °C and >15%, respectively. These excellent properties of pyromellitic dianhydride-based and p-ODA-based addition-type aromatic polyimides are promising for applications in highly heat-resistant composites.
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References
Ghosh, M. K. & Mittal, K. L. (eds). Polyimides: Fundamental and Applications, (Marcel Dekker, New York, 1996).
Bessonov, M. I. & Zubkov, V. A. (eds). Polyamic Acids and Polyimides: Synthesis, Transformations and Structure, (CRC Press, Boca Raton, 1993).
Feger, C., Khojasteh, M. M. & Molis, S. E. (eds). Polyimides: trends in Materials and Applications, (Society of Plastic Engineers, Mid Hudson Section, New York, 1996).
Serafini, T. T. Polyimides; Synthesis, Characterization, and Applications vol. 2 ed. K. L. Mittal 957 (New York, Plenum, 1984).
Cano, R. J. & Jensen, B. J. Effect of molecular weight on processing and adhesive properties of the phenylethynyl-terminated polyimide LARC™-PETI-5. J. Adhesion 60, 113–123 (1997).
Hergenrother, P. M. & Smith, J. G. Chemistry and properties of imide oligomers end-capped with phenylethynylphthalic anhydrides. Polymer 35, 4857–4864 (1994).
Hergenrother, P. M., Connell, J. W. & Smith, J. G. Phenylethynyl containing imide oligomers. Polymer 41, 5073–5081 (2000).
Meyer, G. W., Tan, B. & McGrath, J. E. Solvent-resistant polyetherimide network systems via phenylethynylphthalic anhydride endcapping. High Perform. Polym. 6, 423–435 (1994).
Holland, T. V., Glass, T. E. & McGrath, J. E. . Investigation of the thermal curing chemistry of the phenylethynyl group. Using a model aryl ether imide. Polymer 41, 4965–4990 (2000).
Takekoshi, T. & Terry, J. M. High-temperature thermoset polyimides containing disubstituted acetylene end groups. Polymer 35, 4874 (1994).
Yokota, R. Structure and Design of Photosensitive Polyimides eds. K. Horie, T. Yamashita Ch. 3, 49 (1996).
Yokota, R. in Proc. 7th Japan Polyimide Conference eds. T. Takeichi, M. Kochi 21 (Reitec, Tokyo, 1998).
Hasegawa, M., Sensui, N., Shindo, Y. & Yokota, R. Structure and properties of asymmetric biphenyl type polyimides. Homo- and copolymers and blends. Macromolecules 32, 387–396 (1999).
Kochi, M., Chen, C., Yokota, R., Hasegawa, M. & Hergenrother, P. M. Isomeric biphenyl polyimides. (II) glass transitions and secondary relaxation process. High Perform. Polym. 17, 335–347 (2005).
Zhou, H., Chen, C., Kanbara, R., Sakaki, T. & Yokota, R. Synthesis and properties of copolyimides derived from isometric biphenyltetracarboxylic dianhydrides (a-BPDA and i-BPDA) and oxydiphthalic dianhydride (ODPA) with 4,4′-oxydianiline (4,4′-ODA). High Perform. Polym. 17, 213–224 (2005).
Yokota, R., Yamamoto, S., Yano, S., Sawaguchi, T., Hasegawa, M., Yamaguchi, H., Ozawa, H. & Sato, R. Molecular design of resistant polyimides having excellent processability and glass transition temperature. High Perform. Polym. 13, S61–S72 (2001).
Ogasawara, T., Ishikawa, T., Yokota, R., Ozawa, H., Taguchi, M., Sato, R., Shigenari, Y. & Miyagawa, K. Processing and properties of carbon fiber reinforced triple-A polyimide (Tri-A PI) matrix composites. Adv. Composite Mater. 11, 277 (2003).
Yang, C. P. & Chen, R. S. Polyimides based on 2,5-bis(4-aminophenoxy)biphenyl. J. Polym. Sci. Part A; Polym. Chem. 40, 429–438 (2002).
Fang, X. Z., Yang, Z. H., Zhang, S. B., Gao, L. X. & Ding, M. X. Polyimides derived from mellophanic dianhydride. Macromolecules 35, 8708–8717 (2002).
Morikawa, A., Furukawa, T. & Moriyama, Y. Synthesis and characterization of novel aromatic polyimides from Bis(4-amino-2-biphenyl) ether and aromatic tetracarboxylic dianhydrides. High Perform. Polym. 18, 593–602 (2006).
Morikawa, A., Furukawa, T. & Moriyama, Y. Synthesis and characterization of novel aromatic polyimides from bis(4-amino-2-biphenyl)ether and aromatic tetracarboxylic dianhydrides. Polym. J. 37, 759–766 (2005).
Morikawa, A. in Recent Advances in Polyimides 2008 eds. M. Hasegawa, Y. Ishida, M. Kochi, R. Yokota 1–6 (Meibunsha Co., Chiba, 2008).
Miyauchi, M., Kazama, K., Sawaguchi, T. & Yokota, R. Dynamic tensile properties of a novel Kapton-type asymmetric polyimide derived from 2-phenyl-4,4′-diaminodiphenyl ether. Polym. J. 43, 866–868 (2011).
Coburn, J. C. & Pottiger, M. T. Advances in Polyimide Science and Technology eds. C. Feger, M. M. Khojasteh, M. S. Htoo 360 (Technomic, New York, 1993).
Isoda, S., Shimada, H., Kochi, M. & Kambe, H. Molecular aggregation of solid aromatic polymers. I. Small-angle X-ray scattering from aromatic polyimide film. J. Polym. Sci. Polym. Phys. Ed. 19, 1293–1312 (1981).
Ishida, Y., Ogasawara, T. & Yokota, R. Development of highly soluble addition-type imide oligomers for matrix of carbon fiber composite (I): Imide oligomers based on asymmetric biphenyltetracarboxylic dianhydride and 9,9-Bis(4-aminophenyl) fluorene. High Perform. Polym. 18, 727–737 (2006).
Miyauchi, M., Ishida, Y., Ogasawara, T. & Yokota, R. In Recent Advances in Polyimides 2009 (eds. T. Takeichi, T. Kawauchi, K. Akahori 139–141 (Meibunsha Co., Aichi, 2009).
Miyauchi, M., Ishida, Y., Ogasawara, T. & Yokota, R. in Proc. of 14th European Conference on Composite Materials ID:754 ( (Budapest, Hungary, 2010).
Miyauchi, M., Ishida, Y., Ogasawara, T. & Yokota, R. in Proc. of Society for the Advancement of Material and Process Engineering, (Long Beach, USA, 2011).
Acknowledgements
This report is part of a series of studies entitled ‘Development of Novel Asymmetric Polyimides for Fiber Reinforced Composite Materials with High Heat Resistance,’ for which M Miyauchi received an Award for Encouragement of Research in Polymer Science from The Society of Polymer Science, Japan (2011). We thank Dr A Tamaki and Dr M Takeda at Seika for kindly supplying the monomer. Furthermore, we thank Professor M Kochi and Assistant Professor A Morikawa for fruitful discussions.
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Miyauchi, M., Ishida, Y., Ogasawara, T. et al. Novel phenylethynyl-terminated PMDA-type polyimides based on KAPTON backbone structures derived from 2-phenyl-4,4′-diaminodiphenyl ether. Polym J 44, 959–965 (2012). https://doi.org/10.1038/pj.2012.19
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DOI: https://doi.org/10.1038/pj.2012.19
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