Cationic Polymerizations of 1,3,,6-Trioxocane and 2-Butyl-1,3,6-Trioxocane,
Abstract
The polymerization of 1,3,6-trioxocane (TOC) has been reinvestigated. The reaction occurs without an introduction period to give high MW linear polymers. The degree of polymerization is not independent of conversion. Polymers having M sub n as high as 81,000 and M sub w/M sub n approx. 1.4 and with very strong mechanical strength can be obtained. These results contrast with earlier reports of long induction periods and products with M sub n approx. 5,000. Substituents at the 2 position greatly reduces the polymerizability of dioxolane and dioxopanes. It is therefore a significant result that 2-butyl-1,3,6-trioxocane (2-Bu-TOC) is readily polymerized and at a slightly faster rate than polymerization of TOC under identical conditions. The M sub n of poly(2-Bu-TOC) increases monotonically with conversion reaching a value of 7,700. The thermodynamic parameters for the polymerizations of both systems have been obtained. There is strong argument in favor of the open chain oxocarbenium ion as the propagating species for 2-Bu-TOC polymerization over the cyclic oxonium ion.
Document Details
- Document Type
- Technical Report
- Publication Date
- Oct 01, 1986
- Accession Number
- ADA173538
Entities
People
- Baobei Xu
- C. P. Lillya
- James C. Chien
Organizations
- University of Massachusetts Amherst