Synthesis of Polyspirocyclobutanes and Related Spiropolymers. Part 1. Poly(trispiro(3.1.3.1.3.1)-tridecane-1,3-dione)
Abstract
Dispiro(3.1.3.1)decane-2,8-dicarboxylic acid was synthesized as a polymer intermediate from pentaerythritol via a seven-step process. The diacid was converted to dispiro(3.1.3.1)decane-2,8-dicarbonyl dichloride and the bis- acid chloride dehydrohalogenated in benzene solution with triethylamine to give the corresponding diketene derivative. This unisolable monomer polymerized to poly(trispiro(3.1.3.1.3.1)tridecane-1,3-dione). An alternate procedure in place of the tedious synthesis of dispiro(3.1.3.1)-decane-2,8-dicarboxylic acid was investigated. In seeking a short route to the key intermediate, 1,1,3,3- tetrakis(hydroxymethyl)cyclobutane, 3,3-bis(chloromethyl) oxetane was condensed with diethyl malonate to give diisoamyl and diethyl 6-oxaspiro-(3.3)heptane-2,2- dicarboxylate. From these esters were formed diisoamyl and diethyl 3,3- bis(hydroxymethyl)cyclobutane-1,1-dicarboxylate. The hydroxyesters were polymerized to form a spiropolymer whose structure was probably that of poly(3, 3-bis-(Hydroxymethyl)cyclobutane-1,1-dicarboxylate). Boron trifluoride-catalyzed polymerization of diethyl 6-oxaspiro(3.3)heptane-2,2-dicarboxylate gave a polyoxetane.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jun 01, 1968
- Accession Number
- AD0865324
Entities
People
- Clay M. Sharts
- Derril L. Steele
Organizations
- San Diego State University