Polyimides conventional

For the preparation of polyimides, conventional dianhydrides have been combined with aliphatic and aromatic diisocyanates which are well known in the chemistry of polyurethanes. Other more modern diisocyanates have been also studied [109,110]. 

Silicon—Ca.rbon Thermoset. The Sycar resins of Hercules are sihcon—carbon thermosets cured through the hydrosilation of sihcon hydride and sihcon vinyl groups with a trace amount of platinum catalyst. The material is a fast-cure system (<15 min at 180°C) and shows low moisture absorption that outperforms conventional thermosets such as polyimides and epoxies. Furthermore, the Sycar material provides excellent mechanical and physical properties used in printed wiring board (PWB) laminates and encapsulants such as flow coatable or glob-top coating of chip-on-board type apphcations. 

Polyimide It is a high-cost heat and fire resistant plastic, capable of withstanding 500°F (260° C) for long periods and up to 900°F (482° C) for limited periods without oxidation. It is highly creep resistant with good low friction properties. It has a low coefficient of expansion and is difficult to process by conventional means. It is used for critical engineering parts in aerospace, automotive and electronics components subject to high heat, and in corrosive environments. 

Acetylene terminated polyimide prepolymers have many advantages over conventional polyimides in the areas of processing and solvent resistance. In addition, the presence of the isoimide structure further extends the the utility of these systems by modification of the solubility properties and glass transition temperature. 

Imides - Polyimides (PI) have been conventionally prepared by the chemical or thermal cyclodehydration of polyamic acids formed from the solution reaction of aromatic tetracarboxylic dianhydrides and aromatic diamines. The early PI were insoluble and relatively intractable. The polyamic acid was the processable intermediate. However, the polyamic acid precursor has two major shortcomings, hydrolytic instability and the evolution of volatiles during the thermal conversion to PI. In addition, residual solvent was left in adhesive tapes and prepregs to obtain tack, drape and flow. During the fabrication of components, the evolution of volatiles caused processing problems and led to porosity in the part. As work progressed on PI, other synthetic routes were investigated (e.g. reaction of esters of aromatic tetracarboxylic acids with diamines... 

Polyetherimides (PEI) are polyimides containing sufficient ether as well as other flexibi-lizing structural units to impart melt processability by conventional techniques, such as injection molding and extrusion. The commercially available PEI (trade name Ultem) is the polymer synthesized by nucleophilic aromatic substitution between 1,3-bis(4-nitrophthalimido) benzene and the disodium salt of bisphenol A (Eq. 2-209) [Clagett, 1986]. This is the same reaction as that used to synthesize polyethersulfones and polyetherketones (Eq. 2-206) except that nitrite ion is displaced instead of halide. Polymerization is carried out at 80-130°C in a polar solvent (NMP, DMAC). It is also possible to synthesize the same polymer by using the diamine-dianhydride reaction. Everything being equal (cost and availability of pure reactants), the nucleophilic substitution reaction is probably the preferred route due to the more moderate reaction conditions. 

X-ray powder diffraction was recorded using a conventional x-ray powder diffractometer with Cu-Ka radiation. Polyimide film on which sample particles are deposited is glued on a glass sample holder with vacuum grease. Figure 1.6.9 shows the recorded diffraction pattern. An analysis of the pattern is made by comparing the lattice parameters and diffraction intensities of the particles and those of known iron compounds, and shows that the particles are Fe304. 

Next we consider the dispersion polymerization by polyaddition. In a typical method to prepare polyimide particles, polyamic acid solution is first obtained by coupling of pyromellitic dianhydride and oxy-dianiline, and then by heating the solution. The condensation reaction on heating causes crystallization of polyimide in a spherical form (Fig. 11.2.5, left) (33). However, on the contrary to this conventional method, polyamic acid microspheres could be obtained by dispersion polymerization if an appropriate medium is chosen (34). When a solvent that has a solubility parameter around 17 Mpa is used, submicrometer-sized monodisperse polyamic acid parti-... 

To generate high-molecular-weight perfluorinated polyimides, it is first necessary to determine how fluorine affects the reactivity of the monomers. In particular, the effect of substituting hydrogen with fluorine on diamine reactivity is important because kinetic studies of the acylation of conventional monomers have revealed that acylation rate constants can differ by a factor of 100 among different dianhydrides, and by a factor of 10 among different diamines. ... 

Table 14.5 lists the thermal, electrical, and optical properties of perfluorinated polyimides, along with those of partially fluorinated and unfluorinated polyimides. Because of die flexible structure of the lOFEDA component, the polymer decomposition temperatures and values of perfluorinated polyimides are slightly lower than those of conventional polyimides. This coincides with the results of Hougham et al. who reported that an increase in fluorine content in... 

High water absorption is die other problem with insulation materials, because it causes corrosion of metal wiring and instability of electrical properties such as the dielectric constant. Conventional polyimides have relatively high water absorption because of tiie presence of polar imide rings. However, the water absorption decreases when fluorine is introduced into polyimide molecules because of the former s hydrophobic nature. ... 

A high optical transparency is a basic requirement for optical applications. However, conventional polyimides such as PMDA/ODA have a low optical transparency owing to their dark yellow coloration (they are semitransparent, not opaque). Colorless polyimides have been developed for use in space components, such as solar cells and thermal control systems for the first time. ... 

Stability for use in optical interconnects. In the near future, optoelectronic integrated circuits and optoelectronic multichip modules will be produced. Materials with high thermal stability will thus become very important in providing compatibility with conventional 1C fabrication processes and in ensuring device reliability. Polyimides have excellent thermal stability so they are often used as electronic materials. Furuya et al. introduced polyimide as an optical interconnect material for the first time. Reuter et al. have applied polyimides to optical interconnects and have evaluated the fluorinated polyimides prepared from 6FDA and three diamines, ODA (3), 2,2-bis(3-aminophenyl) hexafluoropropane (3,3 -6F) (4), and 4,4 -6F (2), as optical waveguide materials. 

With the progress in optical communications, there has been a corresponding demand for the use of polyimides in optical components. Table 15.1 summarizes the primary requirements for optical communication materials and the approach used in this work. Thermal stability above 300°C is required for compatibility with conventional 1C fabrication. Polyimides have sufficient thermal stability in addition to easy processability for this use.z... 

To achieve a high fluorine content in polyimides, 6FDA and TFDB are selected for polyimide synthesis (Figure 15.1). 6FDA is a typical monomer for fluorine-containing polyimides. Polyimides synthesized from 6FDA have a high fluorine content and a flexible structure compared with other conventional... 

Aromatic polyimides have many anisotropic imide rings and benzene rings, and they are easy to orient by a film-forming process. Molecular orientation in polyimide films causes in-plane/out-of-plane birefringence (AnJ. Russell et al. have reported the A/ / of conventional PMDA/ODA. On the other hand, spin-coated polyimide films just after preparation do not cause Ann, as noted in the... 

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