Patent GB-920469-A (GB)
Title: Improvements in and relating to polymers
IPC: C08G65/26
Filed: 1961-04-26
Abstract: In a process for the production of an epoxide polymerization catalyst 1 mole of alkaline earth metal hexaminoniate is reacted with from 0,05-1 mole of olefin oxide and from 1,95-1 moles of a hydroxy-containing organic compound in liquid ammonia in excess of that necessary to form the hexaminoniate, and excess ammonia is evaporated from the resulting product.  Preferably the alkaline earth metal is calcium but barium and strontium are also mentioned.  The alkaline earth metal hexaminoniate, olefin oxide and hydroxy-containing organic compound are present in equimolar quantities.  Reaction may be effected between -78 DEG C. and + 133 DEG C. Specified olefin oxides are ethylene oxide, propylene oxide, 1:2- and 2:3-epoxybutanes, the epoxypentanes, epoxyhexanes, epoxyoctanes, epoxydecanes, epoxydodecanes, 2:4:4:-trimethyl-1:2-epoxypentane, 2:4:4-trimethyl-2:3-epoxypentane, styrene oxide, cyclohexylepoxyethane, 1-phenyl-1:2-epoxypropane, 7-oxabicyclo[4:1:0]heptane, 6-oxabicyclo-[3:1:0]hexane, 3-methyl-6-oxabicyclo[3:1:0]hexane and 4-ethyl-6-oxabicyclo[3:1:0]hexane.  Specified hydroxy-containing organic compounds are methanol, ethanol, iso- and n-propanols, n-, sec- and tert-butanols, the pentanols and hexanels, 2-ethyl hexanol, the octanols and dodecanols, octadecanol, cyclopentanol, cyclohexanol, cycloheptanols, 2-methylcyclopentanol, 3-butylcyclohexanol, 3-isopropylcycloheptanol, ethylene glycol, the propylene glycols, the butylene glycols, 1:5-pentanediol, 2-ethylhexane-1:3-diol, 1:6-hexanediol, the octanediols, phenol and cresol.  Examples are given.ALSO:Polymers of epoxides containing an oxirane group are made in the presence of a catalyst which has itself been made by reacting 1 mole of alkaline earth hexammoniate with from 0,05-1 mole of olefin oxide and from 1,95-1,0 moles of a hydroxy-containing organic compound in liquid NH3 and removing excess of the latter from the resulting product.  Specified epoxy monomers are ethylene oxide, propylene oxide, 1:2-butylene oxide, 2:3-butylene oxide, the epoxy-pentanes and -hexanes, 2:3-epoxyheptane, nonene oxide, 5-butyl 3:4-epoxyoctane, 1:2-epoxydodecane, 1:2-epoxyhexadecane, 1:2-epoxyoctadecane, 5-benzyl-2:3-epoxyheptane, 4-cyclohexyl-2:3-epoxypentane, styrene oxide, om- and p-ethyl styrene oxide, glycidyl benzene, 7-oxabicyclo[4:1:0]heptane, 6-oxabicyclo[3:1:0]hexane, 4-propyl-7-oxabicyclo-[4:1:0]heptane and 3-amyl-6-oxabicyclo[3:1:0]-hexane.  In examples ethylene oxide and mixtures of ethylene oxide with propylene oxide, 1:2-epoxybutane or styrene oxide is/are polymerized using as catalyst the product of (1) calcium or strontium hexammoniate with (2) ethylene oxide, 1:2-propylene oxide or epoxybutane and (3) ethylene glycol or n-butanol in excess NH3.ALSO:In a process for the production of an epoxide polymerization catalyst 1 mole of alkaline earth metal hexammoniate is reacted with from 0.5-1 mole of olefin oxide and from 1.95-1.0 moles of a hydroxy-containing organic compound in excess liquid NH3 and evaporating excess NH3 from the resulting product. Preferably the alkaline earth metal is Ca but Ba and Sr are also mentioned.  Specified olefin oxides are ethylene oxide, propylene oxide, 1:2 and 2:3 epoxybutanes, the epoxy-pentanes, -hexanes, -octanes, decanes and dodecanes, 2:4:4-trimethyl-1:2 epoxypentane, 2:4:4-trimethyl 2:3 epoxypentane, styrene oxide, cyclohexylepoxyethane, 1-phenyl 1:2 epoxypropane, 7-oxabicyclo[4:1:0]heptane, 6-oxabicyclo[3: 1:0]hexane, 3 - methyl - 6 - oxabicyclo[3:1:0] hexane and 4-ethyl-6-oxabicyclo[3:1:0]hexane. Specified hydroxy containing organic compounds are methanol, ethanol, iso- and n-propanols, nsec- and tert-butanols, the pentanols and hexanols, 2-ethyl hexanol, the octanols and decanols, octadecanol, cyclopentanol, cyclohexanol, cycloheptanols, 2-methylcyclopentanol, 3-butylcyclohexanol, 3-isopropylcycloheptanol, ethylene glycol, the propylene glycols, the butylene glycols, 1:5 pentanediol, 2-ethylhexane 1:3 diol, 1:6 hexanediol, the octanediols, phenol and cresol.  In examples ethylene oxide and mixtures of ethylene oxide with propylene oxide, 1:2 epoxybutane or styrene is/are polymerized using as catalyst the product of (1) calcium or strontium with (2) ethylene oxide, 1:2 propylene oxide or epoxybutane and (3) ethylene glycol or n-butanol in an excess of liquid ammonia.