Aliphatic polyimides

Last but not least, some of us have recently synthesized polyimide-aliphatic polyester triblock and graft copolymers in collaboration with Hedrick and his coworkers [ 97,98]. Well-defined aminophenyl or diaminophenyl end-functional polyester oligomers have been synthesized on purpose and used as end-cappers or macromonomers leading to the aforementioned triblock or graft copolymers, respectively. The polyimide-polyester copolymers so obtained proved to be highly efficient promoters of polyimide nanofoams (for more details see Sect. 4.2). 

Dicyclic polyimide - - Aliphatic and aromatic products TGA also applied [81]... 

Polyamide or polyimide polymers are resistant to aliphatic, aromatic, and chlorinated or fluorinated hydrocarbons as well as to many acidic and basic systems but are degraded by high-temperature caustic exposures. 

The synthesis of polyimides with the pending group (aliphatic or fluorinated substituent) and some relationships between the polymeric structure and the value of the tilt angle have been reported.35... 

In addition to the research on fluorinated and cardo polyimides, an important work was devoted to the semiaromatic cycloaliphatic polyimides. Volk-sen points out the potential interest of these materials in electronic industry.64 He reports that the simplest procedure to prepare these materials is to use a cycloaliphatic dianhydride and an aromatic diamine (Fig. 5.9) instead of an aliphatic diamine and an aromatic dianhydride, which leads to formation of gels. 

Some examples concerning the polyimide synthesis by condensation of the crystalline salts obtained with the aliphatic or aromatic diamines and aromatic tetraacids will be discussed in Section 5.4.1. 

Alicyclic dianhydrides are interesting for electronic applications. The polyimides obtained from them are colorless with high transparency in the visible range, exhibit low birefringence,125 and have a low dielectric constant.126 The reactivity of the polycyclic aliphatic dianhydride has been investigated. For example, bicyclo-[2,2,2]-oct-7-ene tetracarboxylic dianhydride reacts quickly with an aromatic amine because the bicyclo-imide is less strained than the corresponding dianhydride.127... 

The competition at 200°C between an aliphatic and an aromatic amine toward the formation of an imide is a very selective reaction (Fig. 5.1) for the formation of an aliphatic imide.141 This reaction suggests that the reactive processing in extruder, for example, could be used to transform a melt-processable polyimide with an oligomer end capped with an aliphatic amine. In order to get a perfecdy alternate block polyimide-block siloxane, Rogers et al. used low-temperature transimidization.142 An oligomeric aromatic imide was end capped... 

The first patent of Edwards and Robinson147 claims the condensations of pyromel-litic acid and aliphatic diamine salt to prepare polyimide. Recently, that approach has been revisited, and biphenyl tetracarboxylic and pyromellitic acids give a salt monomer by reaction with 1 mol of an aliphatic diamine (octamethylene diamine and dodecamethylene diamine). The salts were polymerized under 250 MPa at 250°C for 5 h in closed reaction vessels (Fig. 5.32) giving crystalline polymers.148 By reaction of pyromellitic tetraacid with oxydianiline, it has been possible to isolate a monomeric salt. It was polymerized under 30 MPa giving a PMDA-ODA polyimide with water elimination. 

Phthalazinone, 355 synthesis of, 356 Phthalic anhydride, 101 Phthalic anhydride-glycerol reaction, 19 Physical properties. See also Barrier properties Dielectric properties Mechanical properties Molecular weight Optical properties Structure-property relationships Thermal properties of aliphatic polyesters, 40-44 of aromatic-aliphatic polyesters, 44-47 of aromatic polyesters, 47-53 of aromatic polymers, 273-274 of epoxy-phenol networks, 413-416 molecular weight and, 3 of PBT, PEN, and PTT, 44-46 of polyester-ether thermoplastic elastomers, 54 of polyesters, 32-60 of polyimides, 273-287 of polymers, 3... 

Aromatic nitrations, 17 160-161 by-products of, 17 161 kinetics of, 17 162 Aromatic nitriles, 17 243 Aromatic nucleophilic displacement, polyimide synthesis via, 20 273 Aromatic phosphines, 19 60, 62 Aromatic poly(monosulfide ketone)s, 23 709 Aromatic poly(monosulfide)s, 23 706 Aromatic polyamide copolymers, laboratory synthesis of, 19 720 Aromatic polyamide fibers, 24 614 Aromatic polyamides, 10 210-212 19 713-738. See also Aliphatic polyamides (PA)... 

Asano, N., Aoki, M., Suzuki, S., Miyatake, K., Uchida, H. and Watanabe, M. 2006. Aliphatic/aromatic polyimide ionomers as a proton conductive membrane for fuel cell applications. Journal of the American Chemical Society 128 1762-1769. 

As illustrated in Scheme 6, monosilylation of the aliphatic diamine nitrogen atoms and subsequent reaction with the dianhydride yields a polyimide precursor devoid of free carboxylic acid groups, a poly(amic trimethylsilyl ester)... 

The preparation of imides from reaction of isocyanates with anhydrides dates back to the early days of organic chemistry [96]. With the advent of polyimide chemistry in the early 1960s, this chemistry was soon explored for the synthesis of polyimides. However, in contrast to the preparation of polyimides via thejr poly(amic acid) intermediate, the reaction of aromatic dianhydrides with aromatic diisocyanates is much less understood. The reaction of aromatic dianhydrides with aliphatic or aromatic diisocyanates is believed to form a cyclic seven-membered intermediate which then splits out C02 to form the polyimide [97], see Scheme 27. The addition of water, which has been reported to accelerate the anydride/isocyanate reaction, can result in several transformations of either the anhydride or the isocyanate reagent, see Scheme 28... 

Throughout this chapter the chemical concepts employed to synthesize and cure addition poly(imides) have been discussed and their use as matrix resins for fiber composites has frequently been mentioned. The most important property of the imide backbone structure is the inherent thermal stability. The target of achieving the temperature performance of linear poly(imide) has not been reached, because of the aliphatic nature of the reactive endgroups, and because of the low molecular weight of the imide backbone required for processing. Future developments of addition polyimides will, as in the past, focus on the requirement of high thermal and thermal oxidative stability of the crosslinked... 

Polyimides of 6FDA and aliphatic diamines with good low temperature processing and low moisture swelling are known to be useful as hot-melt adhesives (109). Aluminum strips bonded by this polymer (177°C/172 kPa (25 psi) for 15 min) exhibited a lap-shear strength of 53 MPa (7690 psi) at room temperature and 35 MPa (5090 psi) at 100°C. The heat- and moisture-resistant 6F-containing Pis useful in electronic devices are prepared from... 

For highly polar polymers, Hs < —Hw, and the equilibrium concentration is a decreasing function of temperature. This is often found in the most hydrophilic networks, based, for example, on the aromatic amine -aliphatic diepoxide of diglycidyl ether of butane diol (DGEBD) type (Tcharkhtchi et al., 2000), or on particular polyimides (Hilaire and Verdu, 1993). 

The membrane used depends on the nature of the organics. Poly(vinyl alcohol) and cellulose acetate [14] have been used to separate alcohols from ethers. Polyurethane-polyimide block copolymers have been used for aromatic/aliphatic separations [17]... 

Although rigid-rod poly(p-phenyleneterephthalamide) analogues having alkyl side chains did not contain cyclic polymers, the polycondensation of silylated m-phenylenediamine and aliphatic dicarboxyhc acid chloride afforded cyclic polyamides predominantly (Scheme 49) [187]. Furthermore, cyclic polymers were also produced in polycondensations for polyesters, poly(ether ketone)s, polyimides, and polyurethanes [183]. These examples are the products in polycondensation of AB monomers or in A2 + B2 polycondensations, but cyclization of oligomer and polymer was also confirmed in polycondensation of AB2 monomers [ 188-195] and in A2 + B3 [ 196-202] and A2 + B4 polycondensations [203-206], which afford hyperbranched polymers. 

However, the starting point of polyimide synthesis dates away back to the mid 1950s, when Edwards and Robinson had synthesized aliphatic-aromatic polyimides (hereafter referred to as aliphatic polyimides) by the melt polycondensation of nylon-salt-type monomers composed of aliphatic diamines and aromatic tet-racarboxylic acids or their diacid-diesters (Eq. 2) [6,7]. 

Nevertheless, further detailed information was unavailable on the polyimide synthesis from nylon-salt-type monomers that is referred to as salt monomer method , and this method was not really recognized as a simple synthetic method of both aromatic and aliphatic polyimides. In addition, many polyimide investigations have mainly been concentrated on aromatic polyimides, and little information is available about aliphatic polyimides [13-18] that are also potential candidates for engineering plastics. 

Thus, we have recovered the lost salt monomer method for a facile and versatile synthetic method for polyimides. This chapter reviews our recent findings on the rapid synthesis of a series of polyimides by the salt monomer method. This also includes the properties of newly synthesized aliphatic polyimides, and the application of the salt monomer method as well. 

The polycondensation of the salt monomers of both aliphatic-aromatic and wholly aromatic types proceeds according to Eqs. (5) and (3), giving aliphatic and aromatic polyimides, respectively. 

---