SOLID STATE POLYMERIZATION OF OXETANES BY IONIZING IRRADIATION

Journal Article · Sun Dec 31 23:00:00 EST 1961 · Makromolekueare Chemie (Switzerland)

DOI:https://doi.org/10.1002/macp.1962.020520107· OSTI ID:4828994

Nakashio, S; Kondo, M; Ysuchita, H; Yamada, M

In the radioinduced polymerization of 3,3-bis(halogenomethyl) oxacyclobutanes, the rate in solid state is much more rapid than in the liquid state including solution system. This rate depends on the crystal state and is more rapid in proportion as the orientation of crystals being preferable. It was observed that the reaction rate also depended on the crystal size and was more rapid with larger crystals. Saturation points of polymerization yield were observed, and these points also depended on the crystal state. X-ray diffraction analysis was used to explore the solid state polymerization of a single crystal of 3,3-bis (chloromethyl) oxacyclobutane; it was observed that the degree of orientation of the crystal is an important factor in the solid state polymerization. The preferred orientation of the crystal affected that of its polymer. The rate of polymerization was proportional with the dose rate whereas the degree of polymerization was less dependent. The activation energy of the polymerization of 3,3-bis(chloromethyl) oxacyclobutane is equal to 4.1 kcal/mole in the range of --30 to 19 deg C (m.p. of the monomer), 0.3 kcal/mole below -- 100 deg C. These solid state polymerizations may be assumed to proceed by an ionic mechanism. In the polymerization of derivatives of 3,3-bis(halogenomethyl) oxacyclobutanes the reaction proceeds with rates in the following order; Cl- > Br- >>7 I-. (auth)

• Research Organization: Takarazuka Radiation Lab., Japan
• NSA Number: NSA-16-020503
• OSTI ID: 4828994
• Journal Information: Makromolekueare Chemie (Switzerland), Journal Name: Makromolekueare Chemie (Switzerland) Vol. Vol: 52; ISSN MACEA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

ALKENES
BROMINATED HYDROCARBONS
BUTANE
CHEMICAL REACTIONS
CHEMISTRY
CONFIGURATION
CRYSTALS
EXCITATION
GAMMA RADIATION
GRAIN SIZE
LATTICES
METHYL RADICALS
METHYLENE RADICALS
MONOCRYSTALS
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC IODINE COMPOUNDS
OXIDES
POLYMERIZATION
PROPANE
RADIATION CHEMISTRY
REACTION KINETICS
TEMPERATURE
X RADIATION