Patent GB-871643-A (GB)
Title: Preparation of metal-containing catalysts and their use in the polymerisation of epoxides
IPC: C08F4/00
Filed: 1959-12-23
Abstract: Olefine oxides are polymerized by contacting an olefine oxide with from 0,02-10% of its weight of a catalyst prepared by reacting an alkaline earth metal hexammoniate with 0,3-1,0 mole of an olefine oxide and 0,2-0,8 mole of an organic nitrile per mole of hexammoniate in liquid ammonia.  The catalyst appears to have the formula ROMNH2 in which R is the radical corresponding to the olefine used in the preparation of the catalyst (i.e. ethyl in the case of ethylene oxide) and M is the alkaline earth metal, the organic nitrile apparently serving to activate the product.  The olefine used in the preparation of the catalyst contains only carbon, hydrogen and oxirane oxygen.  The catalysts so obtained may be slurried or suspended in an inert organic liquid, such as a dialkyl ether of an alkylene glycol or an aliphatic or cycloaliphatic hydrocarbon, before being used to catalyse the polymerization of olefine oxides.  The olefine oxides which may be polymerized or copolymerized are those of formula:  <FORM:0871643/IV (a)/1> in which R1 may be hydrogen, haloaryl, or an alkyl, aryl, cycloalkyl, aralkyl or alkaryl hydrocarbon group; or the R1 groups can form with the epoxy carbon atoms a saturated aliphatic hydrocarbon nucleus containing 4-10 carbon atoms.  Preferably the epoxide monomer is a lower olefine oxide, e.g. ethylene oxide, propylene oxide, 1, 2-epoxybutane or 2, 3-epoxybutane.  Also specified are 1, 2-epoxydodecane and 7-oxabicyclo [4,1,0]-heptane, the latter as a copolymerizable monomer with ethylene oxide.  The polymerization may be carried out at temperatures from -30 DEG -150 DEG C. and is preferably carried out in the liquid phase in an inert atmosphere, e.g. nitrogen.  The polymers may be prepared by bulk polymerization in the absence of a solvent or diluent, suspension polymerization in the presence of a diluent which is a solvent for the monomer but not for the polymer, or solution polymerization in the presence of a solvent for both the monomer and polymer.  The products of suspension polymerization are granular, and have reduced viscosities (in acetonitrile) of from 1 to over 50.  Uses: Shaped articles, e.g. buttons, brush handles, lamp bases; sizes for yarns; films.  Specifications 839,171 and 869,114 are referred to.ALSO:An alkaline earth metal hexammoniate is reacted with 0.3-1.0 moles of an olefine oxide and 0.2-0.8 mole of an organic nitrile, per mole of hexammoniate in an excess of liquid ammonia, the excess liquid ammonia being subsequently evaporated, to give a compound in which the ring of the olefine oxide opens and the oxygen atom is attached directly to the alkaline earth metal.  The other valency bond of the alkaline earth metal is probably attached to a -NH2 group, the organic nitrile serving to activate the product. Suitable olefine oxides are, for example, epoxyalkanes, epoxycycloalkanes and phenyl substituted epoxyalkanes.  The preferred organic nitriles are saturated aliphatic nitriles.  The preferred temperatures for carrying out the process are from above the freezing-point of liquid ammonia to 25 DEG C.  The products are used as catalysts in the polymerization of olefine oxides (see Group IV(a)).  Specifications 839,171 and 869,114 are referred to.