Modified Polyimides

Polyimides. In situ co-deposition of metal salts such as Co(II), or LiCl into a polyimide precursor from 3,3, 4,4 -tetracarboxybenzophenone dianhydride and 4,4 -diaminobenzophenone with subsequent thermal curing offers surface-conductive polyimide film [43]. By similar procedures, Taylor et al. prepared a series of polyimides modified with Pd, Pt, Ag, Au, Cu, Sn, Ti and magnetic-Fe [44, 45, 46]. 

Figure 6. External reflectance 1R spectra of the PMDA-ODA polyimides modified with 1 M KOH aqueous solution at 22 °C for (a) 0 min, (b) 1 min and (c) 10 min. The angle of 1R incidence was 37 0 from the sample surface.

Synthesis of Polymers. Polyamic acid solutions were prepared by condensation of the aromatic anhydride and amine in N,N-dimethylacetamide (DMAc). Polyimide modified electrodes were made by casting or spin coating the precursor polyamic acid solution onto stainless steel or platinum substrates. Imidization was achieved by either heating the films to 400°C for 60 min or through a chemical dehydration process involving immersion in a 1 1 mixture of acetic anhydride and pyridine (6). BTDA-DAPI films were made by casting from a DMAc solution and heating to 100 C. 

Includes acetal, granular fluoropolymers, polyamide-imide, polycarbonate, thermoplastic polyester, polyimide, modified polyphenylene oxide, polyphenylene sulfide, polysulfone, polyetherimide and liquid crystal polymers. 

Jin Jin, F.-L., Park, S.-J. Thermal properties and toughness performance of hyperbranched-polyimide-modified epoxy resins. J. Polym. Sci. Part B Polym. Phys. 44 (2006) 3348-3356. 

In addition, the orientational distribution of the liquid crystal is affected by surface effects. Deuterium NMR can be applied to study the director field in microcavities [103, 107-110, 112]. Figure 9 shows deu-teron NMR spectra of selectively deuterat-ed 4- -pentyl-4 -cyanobiphenyl confined in parallel polyimide-modified cylindrical pores of a Nuclepore membrane. The suggested models for the director field in such cylindrical pores with parallel anchoring. 

J. L. Hedrick, H.-J. Cha, R. D. Miller, D. Y. Yoon, H. R. Brown, S, Srinivasan, R. D. Pietro, R. F. Cook, J. P. Hummel, D. P. Klaus, E. G. Liniger, E. E, Slmonyi (1997) Polymeric organic-inorganic hybrid nanocomposites preparation of polyimide-modified poly(silsesqui-oxane) using functionalized poly(amic acid alkyl ester) precursor. Macromolecules 30, 8512. 

Thermosetting-encapsulation compounds, based on epoxy resins (qv) or, in some niche appHcations, organosiHcon polymers, are widely used to encase electronic devices. Polyurethanes, polyimides, and polyesters are used to encase modules and hybrids intended for use under low temperature, low humidity conditions. Modified polyimides have the advantages of thermal and moisture stabiHty, low coefficients of thermal expansion, and high material purity. Thermoplastics are rarely used for PEMs, because they are low in purity, requHe unacceptably high temperature and pressure processing conditions. 

Other organic—inorganic hybrids include poly(ethyloxazoline)—siUca, poly(vinyl alcohol)—siUca, poly(arylene ether) ketone—siUca, polyimide—siUca, polyozoline—sihca, poly(ethylene oxide)—siUca, and polymers—modified alkoxysilane. 

In 1990 the majority of U.S. PCB production resulted from subtractive or print-and-etch processing additive processes were less than 6% of the total multilayer boards accounted for 55.8%. The ratio of rigid to flexible surface areas plated is about 15 1. High performance plastics including polyimide. Teflon, and modified epoxy comprised 6% of the market ( 324 million) flexible circuits were 6.6% ( 360 million) (42). 

In this section discussion will be confined to the true polyimides whilst the modified materials will be considered in Section 18.14. 

Methods of preparation of the laminates depend on the partieular grade of polyimide resin used but in one process the polyimide precursor is dissolved in acetone and this solution is used to impregnate the glass or carbon fibre and thus produce a pre-preg . The pre-preg is dried and then pre-cured at about 200°C for about 3 hours. This operation reduces the volatile content and also modifies the flow properties to make them more suitable for the subsequent... 

The polyester-imides form yet another class of modified polyimide. These are typified by the structure shown in Figure 18.43. 

After deposition of 0.5 nm of copper onto plasma modified polyimide, the peaks due to carbon atoms C8 and C9 and the oxygen atoms 03 and 04 were reduced in intensity, indicating that new states formed by the plasma treatment were involved in formation of copper-polyimide bonds instead of the remaining intact carbonyl groups. Fig. 28 shows the proposed reaction mechanism between copper and polyimide after mild plasma treatment. 

After metallization of the plasma-modified polyimide, there were a number of peaks in the TOF-SIMS spectra that confirmed the existence of Cu-N bonds as required by the proposed reaction mechanism (see Fig. 28). The most significant... 

Potyimides obtained by reacting pyromellitic dianhydride with aromatic amines can have ladder-like structures, and commercial materials are available which may be used to temperatures in excess of 300°C. They are, however, somewhat difficult to process and modified polymers such as the polyamide-imides are slightly more processable, but with some loss of heat resistance. One disadvantage of polyimides is their limited resistance to hydrolysis, and they may crack in aqueous environments above 100°C. 

PI nanocomposites have been prepared by various methods with different fillers. The nanocomposites might have many applications starting from barrier and thermal resistance to a compound with low coefficient of thermal expansion (CTE) [154-167]. These hybrid materials show very high thermal and flame retardation as well as barrier resistance and adhesion. Tyan et al. [158] have shown that depending on the structure of the polyimide the properties vary. Chang et al. [159] have also investigated the dependency of the properties on the clay modifiers. 

Recent work has focused on a variety of thermoplastic elastomers and modified thermoplastic polyimides based on the aminopropyl end functionality present in suitably equilibrated polydimethylsiloxanes. Characteristic of these are the urea linked materials described in references 22-25. The chemistry is summarized in Scheme 7. A characteristic stress-strain curve and dynamic mechanical behavior for the urea linked systems in provided in Figures 3 and 4. It was of interest to note that the ultimate properties of the soluble, processible, urea linked copolymers were equivalent to some of the best silica reinforced, chemically crosslinked, silicone rubber... 

As mentioned earlier, siloxanes impart a number of beneficial properties to polymeric systems into which they are incorporated, including enhanced solubility, resistance to degradation in aggressive oxygen environments, impact resistance and modified surface properties. These particular advantages render polysiloxane-modified polyimides attractive for aerospace, microelectronic and other high performance applications (40-43). 

One of the major goals of this endeavor was to solubilize the normally intractable polyimides by the incorporation of siloxane segments, and, optionally, by solution imidization. Solubilities of a series of siloxane-modified polyimide copolymers were evaluated in a variety of solvents as indicated in Table I. Copolymer solubility was found to be a function of the siloxane oligomer concentration... 

Values of the upper glass transition temperatures of the siloxane modified polyimides were found to be a function of both the level of incorporated siloxane as well as the siloxane molecular weight (Table II). The upper transition temperature of the solution... 

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