Ultra-Low CTE and Improved Toughness of PMDA/PDA Polyimide-based Molecular Composites Containing Asymmetric BPDA-type Polyimides

Abstract

A completely amorphous polyimide (PI) derived from 2,3,3^′,4^′-biphenyltetracarboxylic dianhydride (a-BPDA) with 4,4^′ -oxydianiline (4,4^′-ODA) (i.e. a-BPDA/ODA) was used as a matrix polymer for a rod-like polyimide structure derived from pyromellitic dianhydride (PMDA) with p-phenylenediamine (PDA) (i.e. PMDA/PDA) to improve the toughness without sacrificing its ultra-low coefficient of thermal expansion (CTE) characteristics. A matrix effect of a-BPDA/ODA was investigated by comparing with an isomer PI system, s-BPDA/ODA (s-BPDA: 3,3^′,4,4^′-biphenyltetracarboxylic dianhydride). Neither of the PMDA/PDA-based blend systems with a minor fraction of these flexible PIs showed any distinct glass transitions during dynamic mechanical thermal analysis. The unique fluorescence behavior of perylenetetracarboxydiimide (PEDI), which became almost non-fluorescent by intimate intermolecular contact with the PMDA/PDA chains, was applied to study the miscibility of the PMDA/PDA-based blend systems. For this purpose, a- and s-BPDA/ODA was labeled by copolymerization using a trace amount of difunctional PEDI. The results revealed that the a-BPDA/ODA-containing blend system was miscible over the entire blend composition whereas the s-BPDA/ODA-containing counterpart was essentially immiscible. The a-BPDA/ODA was much more effective as a flexible component than s-BPDA/ODA for reducing the crystallinity of PMDA/PDA and, as a result, significantly improved the film toughness. Blending of only small amounts of a-BPDA/ODA (5—10 wt.%) into PMDA/PDA caused an unexpected further decrease in the ultra-low CTE (2.8 ppm/K) of homo PMDA/PDA film. A mechanism is proposed to reasonably explain the results obtained in the present study. The blend system composed of PMDA/PDA (90 wt/%) and a-BPDA/ODA (10 wt.%) achieved an ultra-low CTE of 0.9 ppm K^—1 in addition to sufficient film flexibility.

Keywords

2,3,3′,4′ -biphenyltetracarboxylic dianhydride (a-BPDA)-type polyimides PMDA/PDA ultra-low CTE polyimide/polyimide blend miscibility

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References

Mittal, K. L. (ed) ( 1984 ). Polyimides: Synthesis, Characterization and Application , Plenum, New York.

Bessonov, M.I., Koton, M.M., Kudryavtsev, V.V. and Laius, L.A. (eds) (1987). Polyimide: Thermally Stable Polymers, Plenum, New York.

Feger, C., Khojasteh, M.M. and McGrath, J.E. (eds) (1989). Polyimides: Materials, Chemistry and Characterization , Elsevier, Amsterdam.

Feger, C., Khojasteh, M.M. and Htoo, M.S. (eds) (1993) Advances in Polyimide Science and Technology, Technomic, Lancaster.

Bessonov, M.I. and Zubkov, V.A. (eds) (1993) Polyamic Acid and Polyimides: Synthesis, Transformation and Structure, CRC Press, Boca Raton, FL.

Ghosh, M.K. and Mittal, K.L. (eds) (1996) Polyimides: Fundamentals and Applications, Marcel Dekker , New York.

Feger, C., Khojasteh, M.M. and Molis, S. E. (eds) (1996) Polyimides: Trends in Materials and Applications , Society of Plastic Engineers, New York.

Sachdev, H.S., Khojasteh, M.M. and Feger, C. (eds) (1999). Advances in Polyimides and Low Dielectric Polymers , Society of Plastic Engineers, New York.

Mittal, K.L. (ed) ( 2001). Polyimides and Other High Temperature Polymers: Synthesis , Characterization and Applications, vol. 1, VSP, Zeist, The Netherlands.

10.

Imai, Y. and Yokota, R. (eds) (2002). The Latest Polyimides: Fundamentals and Applications, NTS, Tokyo. (in Japanese)

11.

Numata, S. , Oohara, S. , Fujisaki, K. , Imaizumi, J. and Kinjyo, N. ( 1986). Thermal Expansion Behavior of Various Aromatic Polyimides , J. Appl. Polym. Sci., 31: 101-110.

12.

Numata, S. , Fujisaki, K. and Kinjyo, N. ( 1987). Reexamination of the Relationship Between Packing Coefficient and Thermal Expansion Coefficient for Aromatic Polyimides, Polymer, 28: 2282-2288.

13.

Coburn, J.C. and Pottiger, M.T. ( 1996). In: Ghosh, M.K. and Mittal, K.L. (eds), Thermal Curing in Polyimide Films and Coatings, Polyimides: Fundamentals and Applications, Marcel Dekker, New York, pp. 207-247.

14.

Hasegawa, M. , Matano, T. , Shindo, Y. and Sugimura, T. ( 1996). Spontaneous Molecular Orientation of Polyimides Induced by Thermal Imidization (2). In-plane Orientation, Macromolecules , 29: 7897-7909.

15.

Hasegawa, M. and Koyanaka, M. ( 2003). Polyimides Containing Trans-1,4-cyclohexane Unit: Polymerizability of their Precursors and Low-CTE and Low-K and High-Tg Properties, High Perform. Polym., 15: 47-64.

16.

Hasegawa, M. and Koseki, K. (2006). Poly(ester imide)s Possessing Low CTE and Low Water Absorption, High Perform. Polym., 18: 697-717.

17.

Hasegawa, M. , Horiuchi, M. and Wada, Y. (2007). Polyimides Containing Trans-1,4-cyclohexane unit (II). Low-K and Low-CTE Semi- and Wholly Cycloaliphatic Polyimides, High Perform. Polym. , 19: 175-193.

18.

Hasegawa, M. and Horii, S. (2007). Low-CTE Polyimides Derived from 2,3,6,7-Naphthalenetetracarboxylic Dianhydride, Polym. J., 39: 610-621.

19.

Hasegawa, M. , Tsujimura, Y. , Koseki , K. and Miyazaki, T. (2008). Poly(ester imide)s Possessing Low CTE and Low Water Absorption (II). Effect of Substituents, Polym. J., 40: 56-67.

20.

Hasegawa, M. , Sensui, N. , Shindo , Y. and Yokota, R. (1999). Structure and Properties of Novel Asymmetric Biphenyl Type Polyimides. Homo- and Copolymers and Blends, Macromolecules, 32: 387-396.

21.

Hasegawa, M. , Shi, Z. Yokota , R. , He , F. and Ozawa, H. (2001). Thermo-processable Polyimides with High Tg and High Thermo-oxidative Stability as Derived from 2,3,3′,4′-Biphenyltetracarboxylic Dianhydride , High Perform. Polym., 13: 355-364.

22.

Yokota, R. , Yamamoto, S. , Yano , S. , Sawaguchi, T. , Hasegawa, M. , Yamaguchi, H. , H.Ozawa , H. and Sato, R. (2001). Molecular Design of Heat Resistant Polyimides Having Excellent Processability and High Transition Temperature , High Perform. Polym., 13: 61-72.

23.

Hasegawa, M. , Sensui, N. , Shindo , Y. and Yokota, R. (1999). Improvement of Thermoplasticity for s-BPDA/PDA by Copolymerization and Blend with Novel Asymmetric BPDA-based Polyimides, J. Polym. Sci. Part B, 37: 2499-2511.

24.

Takayanagi, M. , Ogata, T. , Morikawa , M. and Kai , T. (1980). Polymer Composites of Rigid and Flexible Molecules: System of Wholly Aromatic and Aliphatic Polyamides , J. Macromol. Sci. Phys., B17: 591-615.

25.

Yokota R. , Horiuchi, H. , Kochi , R. , Soma, M. and Mita, I. (1988). High Strength and High Modulus Aromatic Polyimide/polyimide Molecular Composite Films, J. Polym. Sci. Part C, 26: 215-223.

26.

Iatatani, H. and Yoshimoto, H. (1973). Palladium-catalyzed Syntheses of Aromatic Coupling Compounds, J. Org. Chem., 38: 76-79.

27.

Hasegawa, M. , Ishii, J. and Shindo, Y. (1998). Unique Fluorescence Behavior of Perylenetetracarboxydiimides in Polyimide Systems, J. Polym. Sci.: Part B, 36: 827-840.

28.

Hasegawa, M. , Ishii, J. and Shindo, Y. (1999). Polyimide/Polyimide Blend Miscibility Probed by Perylenetetracarboxydiimide Fluorescence, Macromolecules, 32: 6111-6119.

29.

Hasegawa, M. , Mita, I. , Kochi , M. and Yokota, R. (1991). Miscibility of Polyimide/Polyimide Blends and Charge-transfer Fluorescence Spectra, Polymer, 32: 3225-3232.

30.

Ford, W.E. and Kamat, P.V. (1987). Photochemistry of 3,4,9,10-perylenetetracarboxylic Dianhydride Dyes. 3. Singlet and Triplet Excited-state Properties of the bis(2,5-di-tert-butylphenyl)imide Derivative , J. Phys. Chem., 91: 6373-6380.

31.

Hasegawa, M. , Shindo, Y. , Sugimura , T. , Horie, K. , Yokota, R. and Mita, I. (1991). On Amide Exchange Reaction of Polyimide Precursor, J. Polym. Sci. Part A, 29: 1515-1522.

32.

Hasegawa, M. , Okuda, K. , Horimoto , M. , Shindo, Y. , Yokota, R. and Kochi, M. (1997). Spontaneous Molecular Orientation of Polyimides Induced by Thermal Imidization (3). Component Chain Orientation in Binary Polyimide Blends, Macromolecules, 30, 5745-5752.