Tetrahydroxy spirobisindane

Materials 3-Hydroxy-, 3,5-dihydroxy, 3-amino- and 3,5-diaminobenzoic acid were gifts of BAYER AG (Leverkusen, FRG) and used without further purification. Bisphenol-P and bisaniline-P were purchased from Kennedy and Klim (Little Silver, N.J., USA). Piperazine, l,l,l-tris(4 -hydroxy-phenyl)ethane, phloretic acid tetrahydroxy spirobisindane were purchased from Aldrich Co. (Milwaukee, Wise., USA). All hydroxy acids and phenols were acetylated with an excess of acetic acid and a catalytic amount of pyridine in refluxing toluene. All silylations were conducted with chloro-trimethylsilane and triethylamine in refluxing toluene or dioxane. 

For the description of multicyclic polymers prepared by + />4 polycondensation, in principle, the same type of structural formulas and sum formulas can be used designed for 02 + 3 polycondensates (Formulas 12.5). However, two characteristic differences should be emphasized. First, depending on the stereochemical properties of the monomers even the bridged bicyclic monomers may yield isomers. As illustrated by scheme (a) in Formulas 12.6 (top), 64 monomers based on a tetravalent carbon such as pentaerythritol and its derivatives [e.g. (b) and (c) in Formulas 12.6] cannot form isomers. Yet, for the bicyclic monomers of tetrafunctional benzene derivatives two or three isomers may exist. The condensation of a non-symmetrical monomer, such as tetrahydroxy spirobisindane (TTSBI) with flexible 02 monomers may yield 8 isomeric dimers [18]. In other words, the exponential increase of the number of isomers with higher DPs is steeper than in the case of 02 + 3 polycondensates. The second characteristic difference is the fact, that in 02 + / 4 polycondensations monofuctional multicycles (analogous to those in Formulas 11.2 and 12.3, top) cannot be formed. Hence, only four not five different classes of multicycles exist ... 

S.S -Tetrahydroxy-S -tetramethyl spirobisindane (TTSBI) was depro-tonated with f-BuOK and polycondensed with di(ethylene glycol) tosylate or tri(ethylene glycol) tosylate as shown in Fig. 46. At concentrations of 0.1 or 0.2 mol/L no cross-linking was observed and multicyclic polyethers were isolated in high yields (up to 99%). The formed polymer was an amorphous character with two glass-transition temperatures [151]. 

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