A New Reaction of Bisphenol A and Preparation of Polysubstituted 9,9-Dimethylxanthenes
摘要:
A new transformation of bisphenol A (1) to polymethylated 9,9-dimethylxanthenes 2-5 in the presence of an exogenous phenol is described. The reaction proceeds with concurrent liberation of phenol, is catalyzed by strong acid, and takes place at synthetically useful rates at temperatures above 100 degrees C. Materials chemically related to bisphenol A polycarbonate 10, chroman fl, and tars generated during the manufacture of 1, behave similarly. The product xanthenes are useful as precursors to novel xanthene polyesters such as 33 having high glass transition temperatures relative to analogous materials based on 12 or 13. Catalytic oxidation of xanthenes 2-4 affords highly insoluble diacids that are esterified to the esters 6-8. A mechanistic framework accounting for the appearance of chroman 23 and spiroketal 24 as intermediates is given. Overall, the reaction has the characteristics of a complex series of equilibria in which xanthenes such as 2 are strongly favored.
A New Reaction of Bisphenol A and Preparation of Polysubstituted 9,9-Dimethylxanthenes
摘要:
A new transformation of bisphenol A (1) to polymethylated 9,9-dimethylxanthenes 2-5 in the presence of an exogenous phenol is described. The reaction proceeds with concurrent liberation of phenol, is catalyzed by strong acid, and takes place at synthetically useful rates at temperatures above 100 degrees C. Materials chemically related to bisphenol A polycarbonate 10, chroman fl, and tars generated during the manufacture of 1, behave similarly. The product xanthenes are useful as precursors to novel xanthene polyesters such as 33 having high glass transition temperatures relative to analogous materials based on 12 or 13. Catalytic oxidation of xanthenes 2-4 affords highly insoluble diacids that are esterified to the esters 6-8. A mechanistic framework accounting for the appearance of chroman 23 and spiroketal 24 as intermediates is given. Overall, the reaction has the characteristics of a complex series of equilibria in which xanthenes such as 2 are strongly favored.
Xanthene polyesters and polyamides are provided resulting from the reaction of alkylene, cycloaliphatic or aromatic diols or organo diamines with xanthene dicarboxylic esters or xanthene dicarboxylic acid halides. These amorphous, or crystalline film forming, high performance thermoplastics are useful in automative applications, and include copolymers and blends of such xanthene polymers.
Disclosed herein are polyester compositions comprising the reaction product of: a) a precursor component comprising xanthene dicarboxylic acid (XDA), or a reactive derivative thereof; b) a terephthalate component comprising at least one di(C1-C3 alkyl) terephthalate, or terephthalic acid, or a combination thereof; c) a diol component comprising 1,4-cyclohexane dimethanol (CHDM); and d) at least one metal catalyst; methods of making same, and articles comprising the disclosed compositions. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.