Patent FR-1187677-A (FR)
Inventor: BURKE JR OLIVER W
IPC: C07F5/06
Filed: 1957-04-25
Granted: 1959-09-15
Abstract: A polymerization catalyst comprises a monometatalled organic compound "1" and Friedel Crafts compounds "2b" with or without a modifying polar compound "2a" and/or a carrier component "3".  Component "1" is defined as containing a single metal atom bonded to the organic moiety by a carbon-metal bond; said moiety may be polymeric or nonpolymeric, while the metal atoms are selected from Li, Na, K, Rb, Cs, Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, B, Al, Sc, Yb, La, Ga, In, Tl, Ti, Zr, Th, Ge, Sn, Pb and the rare-earth metals.  Component "2b" comprises mixed halides obtained by burning in halogen gases or vapours the ferro-alloys of metals of Periodic Group IV, V, VI, iron group VIII, and Mn, with or without reductive after treatment with metal powders, metal hydrides, metal carbides and/or hydrogen and the said halides may be partially reacted with oxygen water and/or reactive organic compounds such as alcohols.  Component "2a" consists of organic donor compounds containing one or more of O, N, S, Se, Te, halogens; various classes of such compounds being mentioned and a number of peroxides and azo compounds being also specified; such donor compounds include those in which active hydrogen atoms have been replaced by metals.  Component "3" is an organic or inorganic solid not detrimental to the polymerization and including shaped materials and carbon.  Many metals and acid radicals suitable as constituents of this component are listed as are many specified oxides.  The usual hydrocarbons and their halogenated derivatives are mentioned as solvents for catalyst formation and polymerization.  In examples, ethylene and propylene are homopolymerized in presence of catalysts containing components selected from the following: "1": amyl barium, amyl sodium, p-xylene monosodium and a -methylstyrene trimer monosodium; "2a": ethyl ether; "2b" chlorides derived from Fe alloys with V, Mo, W or Cb; "3": NaCl. Also specified as alloys from which "2b" can be derived are Fe-Mn and Fe-Cr.  The monomers which in general may be polymerized with the above catalyst contain at least one polymerizable ethylenic and/or acetylenic linkage; the monomer may itself form the diluent as an alternative to using a separate diluent. Numerous monomers are listed in the Specification; these include the following types: a -olefines; chloro-, fluoro-, chlorofluoro- and bromo-olefines including chloro- and bromo-aryl and alkaryl olefines; aryl and alkaryl olefines; conjugated dienes and trienes.  Specifications 873,616 and 873,658 are referred to.ALSO:A polymerization catalyst comprises a mono-metallated organic compound "1" and Friedel Crafts compounds "2b" with or without a modifying polar compound "2a" and/or a carrier component "3".  Component "1" is defined as containing a single metal atom bonded to the organic moiety by a carbon-metal bond; said moiety may be polymeric or non-polymeric, while the metal atom is selected from Li, Na, K, Rb, Cs, Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, B, Al, Sc, Yb, La, Ga, In, Tl, Ti, Zr, Th, Ge, Sn, Pb and the rare-earth metals.  Component "2b" comprises mixed halides obtained by burning in halogen gases or vapours the ferro-alloys of metals of Periodic Group IV, V, VI, iron Group VIII, and Mn, with or without reductive after treatment with metal powders, metal hydrides, metal carbides and/or hydrogen and the said halides may be partially reacted with oxygen water and/or reactive organic compounds such as alcohols.  Component "2a" consists of organic donor compounds containing one or more of O, N, S, Se, Te, halogens; various classes of such compounds being mentioned and a number of peroxides and azo-compounds being also specified; such donor compounds include those in which active hydrogen atoms have been replaced by metals. Component "3" is an organic or inorganic solid not detrimental to the polymerization and including shaped materials and carbon. Many metals and acid radicals suitable as constituents of this component are listed as are many specified oxides.  The usual hydrocarbons and their halogenated derivatives are mentioned as solvents for catalyst formation and polymerization.  In examples, ethylene and propylene are homopolymerized in presence of catalysts containing components selected from the following:-"1": amyl barium, amyl sodium, p-xylene monosodium and a -methylstyrene trimer monosodium; "2a": ethyl ether; "2b": chlorides derived from Fe alloys with V, Mo, W or Cb; "3": NaCl.  Also specified as alloys from which "2b" can be derived are Fe-Mn and Fe-Cr.  The monomers which in general may be polymerized with the above catalyst contain at least one polymerizable ethylenic and/or acetylonic linkage; the monomer may itself form the diluent as an alternative to using a separate diluent.  Numerous monomers are listed in the Specification; these include the following types:-a -olefines; chloro, fluoro, chlorofluoro and bromo olefines including chloro and bromo aryl and alkaryl olefines; aryl and alkaryl olefins; conjugated dienes and trienes. Specifications 873,616 and 873,658 also are referred to.ALSO:The Specification describes analyses of certain ferro-alloys thus:- (1) Fe-W: W 81.02, Mn 0.13, Mo 0.70, C 0.51, Si 0.17; (2) Fe-V: V 62.0; (3) Fe-Mn: Mn 78.6, C 6.38, Si 1.38; (4) Fe-Mo: Mo 62.6, Si 0.56; (5) Fe-Cr: Cr 71.23, C 0.4, Si 0.57; (6) Fe-Cb: Cb 57.36, C 0.35, Si 6.47%.  In all cases, iron constitutes the approximate balance.  Specifications 873,658 and 873,616 also are referred to.