LOW DIELECTRIC CONSTANT POLYIMIDES CONTAINING ALICYCLIC SEGMENTS

D. Popovici1, C. Hulubei1, V. E. Musteata1, V. Cozan1, M. Bruma1, A. Mller2

1

Petru Poni Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, Iasi, Romania dumitru.popovici@icmpp.ro 2 IMT Bucuresti, Erou Iancu Nicolae, 126A, Bucuresti, Romania

Abstract New polyimides have been synthesized by

reaction of 3,3,4,4-benzophenone tetracarboxylic dianhydride (BTDA) or/and 5-[2,5-(dioxotetrahydrofuryl)]3-methyl-3-cyclohexen-1,2-dicarboxylic anhydride (DOCDA) with 4,4-methylene dianiline (DDM). Polycondensation reactions were carried out in solution and resulting polyimides gave flexible free-standing films. The introduction of alicyclic moieties in the polyimide backbone improved their solubility, giving thermally stable films. The relative dielectric constant values was in range of 3.16 - 2.86 measured at 1kHz and room temperature, and decreased with increasing of the alicyclic units content.

Keywords: polyimide, dielectric constant, solubility, alicyclic, thermal behaviour

1. INTRODUCTION
Aromatic polyimides are well-known high performance polymers having excellent thermal, mechanical and electric properties, which make them useful in electronic, microelectronic and aerospace industry [1-4]. However, due to some drawbacks like poor solubility and infusibility, their processability is dramatically hindered. In view to avoid this disadvantage, some chemical strategies appeared like use of: flexible groups [1-8], alicyclic and/or asymmetric units [9,10], voluminous moieties [11,12]. One of the famous commercial polyimide is Kapton which is successfully used in aerospace industry, having dielectric constant = 3.4 and specific resistivity Rspec = 1.5 x 1017 ohm.cm. The purpose of our work is to present a synthetic procedure for the preparation of polyimides with improved processability and lowered dielectric constant. In this respect, DOCDA was used as an alicyclic, asymmetric and flexible structure.

2. EXPERIMENTAL
2.1 Methods. FTIR measurements have been performed on KBr pellets of powder sample by using a Bruker Vertex 70 Spectrometer. The

thermal behaviour was investigated under nitrogen atmosphere, in the range of 25C up to 900C by means of Mettler Toledo Instrument TGA/SDTA 851. The weight of the sample used was around 3-4 mg. The dielectric measurements were done on Novocontrol Dielectric Spectrometer Concept 40, in the range of 150C up to 250C at both 103 Hz and 106 Hz. The polymeric films (33-42 microns thick) were inserted into a plane capacitor having gold electrodes of 20 mm diameter. The amplitude of applied voltage was 1 V. 2.2 Synthesis. Two homopolymers (PI 1, PI 3) and a copolymer (PI 2) have been synthesized by the reaction of 3,3,4,4-benzophenone tetracarboxylic dianhydride (BTDA) or/and 5[2,5-(dioxotetrahydrofuryl)]-3-methyl-3-cyclo hexen-1,2-dicarboxylic anhydride (DOCDA) with stoechiometric amounts of 4,4-methylene dianiline (DDM) in NMP as solvent (see Figure 1). The reaction proceeded in two steps: first 24 h at room temperature under nitrogen atmosphere and second 6 h at 180 oC, using nitrogen flow for elimination of water vapours. The reaction mixture was precipitated in water and the resulting polymer was filtered, washed with water and methanol, then dried for 8 h at 100 C. Film preparation. The films for dielectric measurements have been prepared by casting the polyamic acid solutions (previously synthesized) on cleaned glass plates. After heating 8 h at 80oC, needed for solvent evaporation, a program of temperature treatment was applied by using a vacuum oven, each temperature step involving one hour: 1) 80C, 2) 120C, 3) 160C, 4) 200C, 5) 250C. After cooling, the films were removed from the glass plates by using boiling water, then were dried for 8 h at 100 oC.

containing alicyclic moieties, is completely soluble in all solvents while and the copolymer PI 2, having random structure with only 50% alicyclic moieties was partially soluble.
Table 1. Solubility behaviour of the polymers Solvent series Code NMP a DMAc DMSO THF PI 1 --b ---PI 2 ++++PI 3 ++ ++ ++ ++ a NMP: N-methyl-2-pyrrolidone; DMAc: N,Ndimethylacetamide; DMSO: dimethyl sulfoxide; THF: tetrahydrofuran b - - : insoluble; + - : partially soluble; + + : soluble

Figure 1. General structure of homopolymers PI 1, PI 3 and copolymer PI 2.

3. RESULTS AND DISCUSSION

The chemical structure of the obtained polymers and copolymer was confirmed by FT-IR spectroscopy (Figure 2). Characteristic absorption bands due to specific imide moieties have been observed: 1770-1780 cm-1 and 1710 1720 cm-1 (imide I, asymmetrical C=O imide stretching), 1370 - 1380 cm-1 (imide II, C-N imide stretching), 720 - 740 cm-1 (imide IV, imide ring deformation).

This improvement of the solubility in the case of polymer PI 3 could be explained by an increase of the free volume induced by the presence of the voluminous alicyclic units, leading to a poor chain packing. The thermal stability of the PI 1 and PI 3 polymers and PI 2 copolymer was investigated by thermogravimetric analysis in nitrogen atmosphere (Figure 3).

Figure 3. TGA curves of polymers PI 1, PI 3 and copolymer PI 2

Some characteristic parameters which monitor the thermal stability of the samples are presented in Table 2. The data showed a decreasing tendency of the thermal stability of the samples with the increase of alicyclic contents, as expected.
Figure 2. FT-IR spectra of polymers PI 1, PI 3 and copolymer PI 2 Table 2. Thermogravimetric data of polymers Code IDT a T10 Td Yc (C) (C) (C) (%) PI 1 504 540 575 60.28 PI 2 407 447 474 572 51.35 PI 3 431 453 490 26.02 a IDT: onset temperature of thermal degradation; T10: temperature corresponding to the 10% weight loss; Td: temperature of maximum decomposition step from DTG; Yc: characteristic yield at 700C

The solubility of the polyimides containing alicyclic moieties in some common organic solvents at room temperature (Table 1) showed an improvement effect due to the presence of alicyclic units. As can be seen from Table 1, while the polymer PI 1 was insoluble in the solvent series used for test, the polymer PI 3,

This different behaviour, which is due to the lower thermal stability of the alicyclic units in comparison with the aromatic ones, however, do not cause any problem - the thermal decomposition starting over 400C in all cases. The presence of alicyclic units in the polymer backbone led to the appearance of an additional decomposition peak in DTG curves at 474C (sample PI 2). During the thermal decomposition one can also observe that the increasing of alicyclic content led to a decreasing of the characteristic yield. The dielectric behaviour of the polyimides PI 1, PI 3 and copolyimide PI 2 was investigated in the temperature range of -150C up to 250C, at 103 Hz and 106 Hz. The obtained results are presented in Table 3. The insulator properties of the samples were evaluated by means of dielectric constant (*) * = ' i'' where: ' : relative dielectric constant '' : relative dielectric loss factor (1)

3.16, the sample PI 3 showed ' value of 2.86. Frequency dependent dielectric constant, measured at room temperature, is shown in Figure 4. The dielectric constant of polymers decreases gradually with increasing frequency because the response of the electronic, atomic and dipolar polarisable units vary with frequency [14]. This decreasing effect of dielectric constant could be due, on one hand, to the interruption of extended conjugation along the macromolecular chain which lowers the dipole size [15] and, on the other hand, to the increasing of the free volume of macromolecule [16].

Their ratio is known as dissipation factor or loss tangent: tan = '' / ', where is the phase angle between the applied voltage and the current response [13].
Table 3. Dielectric behaviour at 25C of the polymers 103 Hz 106 Hz Code tan Rspec tan Rspec ' ' x 10-3 x 1011 x 10-3 x 109 PI 1 3.16 1.57 3.61 3.14 0.55 1.04 PI 2 2.97 1.64 3.7 2.94 1.70 0.37 PI 3 2.86 1.32 7.77 2.83 0.17 3.82

Figure 4. Frequency dependent dielectric constant

As can be seen from Table 3, the value of the relative dielectric constant (') showed a decreasing tendency at both 103 Hz and 106 Hz, with the increasing of alicyclic units contents. For example, while sample PI 1 has ' value of

Figure 5 Graphs for the relative permittivity, dissipation factor and volume resistivity of polyimides at 1 kHz

Also, one can observe that the values of the internal specific resistivity (Rspec) of the sample increase with the increasing of cycloaliphatic

units content. The graphs for the relative dielectric constant, dissipation and specific internal resistance depending on temperature at 1kHz, are shown in Figure 5.

[5]

[6]

4. CONCLUSIONS
Two polymers and one copolymer containing BTDA and DOCDA units have been synthesized by using DDM as aromatic diamine. Polycondensations were carried out in solution and the resulting polyimides gave flexible freestanding films. The introduction of alicyclic moieties in the polyimide backbone improved their solubility in both aprotic dipolar solvents and tetrahydrofurane. The samples showed high thermal stability; the initial decomposition temperature being above 400C. Dielectric measurements showed a decreasing tendency of the value of dielectric constant with increasing of alicyclic units content. The polyimides based on equimolecular amount of alicyclic dianhydrides and methylene-dianiline showed a dielectric constant value of 2,86, which is significantly lower than that of commercial Kapton polyimide that is usually taken as a reference. These properties recommend the obtained polyimides as good candidates for RF electronics and microelectronics, both as interlayer substrate and insulator.

[7]

[8]

[9]

[10]

[11]

[12]

[13]

References
[1] M. K. Gosh, K. L. Mittal (eds.), Polyimides: Fundamentals and Applications; Marcel Dekker, New York, 1996. C. E., Sroog, "Polyimides", Prog. Polym. Sci., 16(4), pp. 561-694, 1991. S. Yu, T. K. S. Wong, X. Hu, K. Pita, "Synthesis and characterization of porous silsesquioxane dielectric films", Thin Solid Films, 473(2), pp. 191195, 2005. G. Maier, " Low dielectric constant polymers for microelectronics ", Prog. Polym. Sci., 26(1), pp. 3 65, 2001.

[14]

[15]

[2] [3]

[16]

[4]

M. Bruma, I. Sava, F. Mercer, I. Negulescu, W. Daly, J. Fitch, P. Cassidy," Synthesis and properties of fluorinated poly(ester-imide)s", High Perform. Polym., 7(4), p. 411-420, 1995 T. J. Murray, "Poly(amide-imides): Wire Enamels with Excellent Thermal and Chemical Properties", Macromol. Mater. Eng., 293(5), pp. 350-360, 2008. E. Hamciuc, I. Sava, M. Bruma, T. Kopnick, B. Schulz, B. Sapich, J. Wagner, J. Stumpe, "New poly(amide-imide)s containing cinnamoyl and azobenzene group", Polym. Adv. Technol., 17(9-10), pp. 641-646, 2006. R. D. Rusu, M. D. Damaceanu, M. Bruma, "Comparative Study of Soluble Poly(ketonaphthylimide)s", Rev. Roum. Chim., 54(11-12), pp. 1015-1022, 2009. Y. Tsuda, , R. Kuwahara, K. Fukuda, K. Ueno, J. M. Oh, "Soluble Polyimides and Copolyimides Based on Alicyclic Dianhydride Having Cyclohexene and Tetralin Moieties", Polymer Journal, 37(2), pp. 126 132, 2005. K,-Y. Choi, M. H. Yi, M. Y. Jin, "Synthesis and Characterization of Novel Polyimides from Alicyclic Dianhydride", Korea Polymer Journal, 4(2), pp 117124, 1996. E. Hamciuc, R. Lungu, C. Hulubei, M. Bruma, "New Poly(Imide-Ether-Amide)s Based on Epiclon", J. Macromol. Sci., Part A: Pure Appl. Chem., 43(2), , pp. 247-258, 2006 C., Hulubei, E. Hamciuc, M. Bruma, "New polyimides based on epiclon", Rev. Roum. Chim., 52(11), pp. 1063-1069, 2007. Feger, C.; Franke, H. "Polyimides in High Performance Electronics Packaging and Optoelectronic Applications", in M. K. Ghosh, K.L. Mittal, (eds.), Polyimides: Fundamentals and Applications, Marcel Dekker, New York, 1996. H. Deligoz, T. Yalcinyuva, S. Ozgumus, S. Yildirim, "Electrical Properties of Conventional Polyimide Films: Effects of Chemical Structure and Water Uptake", J. Appl. Polym. Sci, 100, pp. 810-818, 2006. A. S. Mathews, I. Kim, C. S. Ha, "Synthesis, characterization and properties of fully aliphatic polyimides and their derivatives for microelectronics and optoelectronics applications", Macromol. Res., 15(2), pp. 114128, 2007 Y. Zhang, S. Ke, H. Huang, L. Zhao, L. Yu, H. L. W. Chen, "Dielectric relaxation in polyimide nanofoamed films with low dielectric constant", Appl. Phys. Lett. 92(5), pp. 052910(1-3), (2008).