Radical high polymerization of dialkyl fumarates with bulky substituents leading to less-flexible rod-like polymers
✍ Scribed by Otsu, T. ;Minai, H. ;Toyoda, N. ;Yasuhara, T.
- Book ID
- 102938521
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1985
- Weight
- 504 KB
- Volume
- 12
- Category
- Article
- ISSN
- 0025-116X
No coin nor oath required. For personal study only.
✦ Synopsis
Dialkyl fumarates with bulky ester substituents were found to homopolymerize easily in the presence of 2,2'-azobisisobutyronitrile. Among these fumarates, diisopropyl fumarate(DiPF1 homopolymerized with the above initiator(20mol/ 1) in bulk at 40~60'C to give homopolymers with number-average molecular weight of 70 000-221 000. Similar results were also observed for di-t-butyl fumarate (DtBF) and Methyl-t-butyl fumarate (MtBF) .
These polymers were found to consist of a lessflexible rod-like poly@koxycarbonylmethylene) from the molecular model and the solution property measurements. These polymers which were colorless powdersdid not melt before thermal degradation, but they were soluble in most organic solvents. From TG thermogram observed in a nitrogen atmosphere, the DiPF polymer showed T(init.)=257"C and T(max.)r316°C, and the main degradation products at 400°C,except gaseous materials,were isopropanol and DiPF monomer(32:l in mole ratio).
These thermal degradation behavior was different from that for the polymers of DtBF and MtBF which underwent degradation from lower temperatures like 190OC. Acid and alkaline hydrolyses of the DiPF polymer were observed to occur very hardly.