Patent GB-1009953-A (GB)
Title: Method for polymerizing olefin oxides
IPC: C08G65/26
Filed: 1962-05-22
Abstract: Olefin oxides having up to 9 carbon atoms are polymerized by contacting with a catalyst composition consisting of (a) a metal phosphate or phosphite, and (b) an organometallic compound. The metal phosphates or phosphites have the general formula HwMxPOy wherein M is at least one of metals and metal oxide groups. Preferably M is a transitional element from Group IV to VIII of the Mendeleef Periodic Table.  Many examples are given which include orthophosphates, pyrophosphates, metaphosphates, phosphites, hypophosphites and polyphosphates.  In addition, compounds of unknown constitution prepared by reaction of phosphoric acid, phosphorus acids; a phosphate or a phosphite with metallic compounds, e.g. halide, oxyhalide, oxides; nitrate or sulphate may be used.  M may contain more than one metal.  The component (a) is preferably used in the dry state and may be calcined at 100-1500 DEG  C. and may be used on a carrier support, e.g. silica, alumina, silica-alumina; or various types of clay. Organo-metallic compounds used have the general formula M1RmR1n wherein M1 is a metal of Group I-III, R is alkyl or aryl, R1 is alkyl, aryl, alkoxy, acyl, hydrogen or halogen, m is at least 1, n is 0 or more, and m+n equals the valancy of M1.  M1 may contain two or more metals, and examples given are Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, B and Al. Component (a) may be used in quantities of 0.01 mol. to 20 mol. per mol. of (b).  Olefin oxides used include ethylene oxide, propylene oxide, epichlorohydrin, and comonomers of the olefin iodide and vinyl monomers, aldehydes and heterocyclic compounds containing O or N may be used.  Polymerization may take place in bulk, solution suspension or dispersion processes which may be batchwise or continuous at 0-200 DEG  C. when the catalyst may be in a fluidized, moving or fixed bed and it is stated that molecular weights of 2,000 to 1,000,000 are obtained.  Examples describe polymerization of ethylene oxide using (1) diethyl zinc and titanium, iron and zirconium phosphates, (2) triethyl aluminium and titanium, vanadium, iron and zirconium phosphates, (3) titanium and zirconium phosphates and various organometallic compounds, (4) zirconium phosphate and triethylaluminium, and (5) propylene oxide using titanium phosphates and triethyl aluminium.ALSO:A catalyst mixture used for polymerizing olefin oxides (see Division C3) consists of (a) a metal phosphate or phosphite, and (b) an organometallic compound. The metal phosphates or phosphites have the general formula HwMxPOy wherein M is at least one of metals and metal oxide groups; w=0 to 3; y=2 to 4; x=0 to 3.  Preferably M is a transitional element from Group IV to VII of the Mendeleef Periodic Table.  Many examples are given which include orthophosphates, pyrophosphates, metaphosphates, phosphites, hypophosphites and polyphosphates.  In addition, compounds of unknown constitution prepared by reaction of phosphoric acids; phosphorus acids, a phosphate or a phosphite with metallic compounds, e.g. halide, oxyhalide, oxides, nitrate or sulphate may be used.  M may contain more than one metal.  The component (a) is preferably used in the dry state and may be calcined at 100-1500  DEG C. and may be used on a carrier support, e.g. silica, alumina, silicon-alumina; or various types of clay. Organometallic compounds used have the general formula M1RmR1n wherein M1 is a metal of Group I to III, R is alkyl or aryl, R1 is alkyl, aryl, alkoxy, acyl, hydrogen or halogen; m is at least 1 and m+n equals the valency of M1.  M1 may contain two or more metals.  Component (a) may be used in quantities of 0,01-20 mol per mole of (b).