Bisphenol-A dianhydride

A vessel was charged with bisphenol A dianhydride (490 kg), diaminodiphenyl sulfone (245 kg), phthalic anhydride (11.0 kg), 1,287 liters of o-dichlorobenzene, and sodium phenyl phosphinate (360 g) as the reaction catalyst. The mixture was heated to 150°C to 180°C with removal of water, and the reaction was analyzed for residual amine and anhydride end groups. Additional bisphenol A dianhydride or... 

An easily processable polyimide was prepared by Mercado [2] from the condensation of bisphenol A dianhydride and bis[4-(4-amino-phenoxy)phe-noxyjsulfone that had a Mj, of 76,300 daltons and was used in making thin films. 

Generally, synthesis of dianhydrides is somewhat more complex than that of diamines and until recent time pyromellitic dianhydride (PMDA) and benzophenone-3,3, 4,4 -tetracarboxylic dianhydride (BTDA) had been the only commercially produced aromatic dianhydrides. Some of the significant commercial products developed recently, are Upilex by UBE Ind. and Ultem by General Electric. The former is based on biphenyl-3,3, 4,4 -tetracarboxylic dianhydride (BPDA) and the latter on 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride or bisphenol A dianhydride (BPA-DA). BPDA is produced by oxidative coupling of inexpensive phthalic acid esters in the presence of palladium catalyst [23, 24]. 

A synonym for 4,4 -bis(3,4-dicarboxyl phenox5 henyl)-isopropylid-ene dianhydride is Bisphenol A dianhydride. The synthesis of a wide variety of other dianhydride compounds is detailed in the literature. Modifiers for PI are shown in Figure 15.2. 

PI is widely used as a protective material or an insulation material in the electronic field due to its good properties, e.g., high mechanical strength, high thermal resistance, and solvent resistance. Selected physical properties of a thermoplastic PEI are shown in Table 15.5. Ultem is obtained from bisphenol A dianhydride and MPD. It has a glass transition temperature of 217°C. It should be emphasized that there are a lot of different PI resins with deviating properties. Thus the data given in Table 15.5 are not plainly representative for Pis. 

The acid dianhydride used to make most of the PEIs is 4,4 -bisphenol A dianhydride (BPADA), the structure of which is shown in Figure 5.63. 

A. Ghosh, S. Banerjee, Synthesis, characterization and comparison of properties of novel fluorinated polyimides derived from bisphenol-A-dianhydride, J. Macromol. Sci. Part A Pure Appl. Chem. 45 (7) (2008) 578-584. 

Development Center achieved this in the late 1970s [10], An important feature of this invention was the development of a process to make dianhydrides, specifically dianhydrides based on bisphenol-A. This was achieved by phase-transfer-catalyzed nucleophilic aromatic substitution, as shown in Eq. (8.4). Anitro group was displaced from a phthal-imide by a bisphenol salt to yield a difunctional imide compound, which, in turn, was converted to the bisphenol-A dianhydride (BPADA). Sodium nitrite is made as a by-product. 

Bisphenol-A dianhydride (BPADA) Equation 8.4 BPADA synthesis. 

The polyimide resin formulations were based on combining various amounts of 3,4 oxydianiline and 4,4-(l,3-phenylenedioxy)dianaline with 4,4 bisphenol A dianhydride and 3,3, 4,4 -benzopehnone tetracarboxylic dianhydride and terminated in 4-phenylethynyl phthalate anhydride. 

Eichstadt A E, Ward T C, Bagwell M D, Farr I V, Dunson D L, McGrath J E (2002) S3tnthesis and Characterizahon of Amorphous Partially Aliphatic Polyimide Copolymers Based on Bisphenol-A Dianhydride. Macromolecules 35 7561-7568. 

Eichstadt AE, Ward TC, Bagwell MD, Farr IV, Dunson DL, McGrath JE. S)mthesis and Characterization of Amorphous Partially Aliphatic Pol3hmide Copol)aners Based on Bisphenol- A Dianhydride. Macromolecules 2002 35 7561-7568. 

Miscellaneous Applications. Ben2otrifluoride derivatives have been incorporated into polymers for different appHcations. 2,4-Dichloroben2otrifluoride or 2,3,5,6-tetrafluoroben2otrifluoride [651-80-9] have been condensed with bisphenol A [80-05-7] to give ben2otrifluoride aryl ether semipermeable gas membranes (336,337). 3,5-Diaminoben2otrifluoride [368-53-6] and aromatic dianhydrides form polyimide resins for high temperature composites (qv) and adhesives (qv), as well as in the electronics industry (338,339). 

Polyetherimide synthesis has been achieved by reaction of a dianhydride containing an ether linkage with a diamine, reaction of a diamine containing an ether linkage with a dianhydride, or nucleophilic displacement of halo or nitro groups of a bisimide by bisphenol dianion (19,20). Such Pis exhibit good thermal stabiUty and melt processibiUty. 

Epichlorohydrin with bisphenol A. The curing agents may pose significant health hazards, e.g. amines (triethylamine, p-phenylenediamine, diethylenetriamine) or acid anhydrides (pyromellitic dianhydride)... 

Hedrick et al. reported imide aryl ether ketone segmented block copolymers.228 The block copolymers were prepared via a two-step process. Both a bisphenol-A-based amorphous block and a semicrystalline block were prepared from a soluble and amorphous ketimine precursor. The blocks of poly(arylene ether ether ketone) oligomers with Mn range of 6000-12,000 g/mol were coreacted with 4,4,-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in NMP in the presence of A - me thy 1 morphi 1 i nc. Clear films with high moduli by solution casting and followed by curing were obtained. Multiphase morphologies were observed in both cases. 

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. 

Polyesters extended with dianhydride Via (from bisphenol A diacetate and trimellitic anhydride) instead of PMDA gave results similar to those shown in Table II. Polyesters extended with dianhydrides VIb or Vic gave inferior results. 

For maximum heat resistance, pyromellitic dianhydride is often used. The composition and properties of metal-to-metal adhesives based on a combination of epoxy novolac and a bisphenol A epoxy resin have been described in Sec. 12.5.1. Depending on the cure temperature and the choice of amine curing agent, strength as high as 3000 psi at room temperature and over 1000 psi in the range of-55 to + 150°C is possible. 

Discuss the chemistry of epoxy resins based on diglycidyl ethers of bisphenol A, their preparations, and crosslinking reactions with amines, dianhydrides, and dicyanodiamide. 

Bisphenol A Ester dianhydride derived from trimellitic anhydride 100(1 hr) c ... 

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