Spiro Polymer Synthesis and Characterization.
Technical rept. 1 Jun 66-30 Apr 68,
STANFORD RESEARCH INST MENLO PARK CA
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Three routes to the synthesis of spiro polymers have been investigated. These are polycyclodimerization of diolefins, preparation of polydiketopiperazines, and condensation of aromatic dianhydrides and aliphatic spiro tetraamines. The polydiketopiperazine route failed because of steric hindrance. The polycyclodimerization route failed with compounds such as 1,3-dimethylenecyclobutane, and synthetic difficulties precluded an investigation of this route with fluorodiolefins. The method was successful with substituted bis-maleimides which could be photochemically dimerized to yield polymer structures linked through cyclobutane rings. The condensation of the spiro tetraamines 2,2-bisaminomethyl-1,3-diaminopropane or 1,4-bisaminomethyl-1,4-diaminocyclohexane with pyromellitic dianhydride or 1,4,5,8-naphthalenetetracarboxylic dianhydride was studied in detail and high molecular weight, soluble polymers were obtained using either spiro tetraamine with 1,4,5,8-naphthalenetetracarboxylic dianhydride, but not with pyromellitic dianhydride. The polymer from 1,4-bisaminomethyl-1,4-diaminocyclohexane and 1,4,5,8-naphthalenetetracarboxylic dianhydride was shown by light scattering to have a molecular weight of 60,000, and model compound studies have shown that the polymer was completely cyclized. Author
- Physical Chemistry
- Polymer Chemistry