Patent GB-831806-A (GB)
Title: Novel process and catalyst for production of olefin polymers
IPC: C08F10/00
Filed: 1956-11-07
Abstract: A catalyst for polymerizing olefines consists of 3 components mixed together: (1) an organic compound containing Ti, Zr, Hf or Th; (2) a metal hydride in which one or more H atoms may be replaced by hydrocarbon radicals and the metal has a valency at least 2, selected from Group II to VIII and preferably from Group II and III; and (3) a halogen or halogen hydride.  The organic metal compound (1) consists of salts of monobasic organic acids; complex salts of dibasic organic acids containing also an alkali metal or ammonia; compounds of the type XM(OR) or M(OCH2CH2)NH, where X= halogen, R is a hydrocarbon radical not exceeding 20 C atoms, e.g. alkyl, alkenyl, cycloalkyl, cycloalkenyl or acyl which may also contain O and/or halogen substituents; or acetyl acetonates.  Examples are: titanium butyrate, sodium titanium oxalate; titanium butoxide, dichlor-diethyl zirconate, tetra-isopropyl titanate; alkoxides or mono- or poly-ethanolamine salts of the specified metals. Numerous examples given.  Examples of (2) are tri-ethyl and tri-methyl aluminium, diethyl aluminium hydride, dimethyl beryllium, tri-isopropyl gallium, and similar compounds of Hg, In, Zn, and complexes of these with ethers, amines, alkali metal hydrides or alkyls, e.g. LiAlH4, NaBe(C2H5)3.  The halogen or halogen hydride component includes HF and ICl.  Preferred catalyst mixtures are: (1) tri-ethyl aluminium, titanium butoxide and HCl; (2) tri-ethyl aluminium, titanium acetyl acetonate and chlorine; (3) tri-ethyl gallium, zirconium butoxide and chlorine; (4) diethyl beryllium, titanium potassium oxalate, and HBr. 1-Olefines containing up to 8 C atoms may be polymerized at temperatures up to 500 DEG  F. and preferably at 100 to 1000 lbs. p.s.i.g.  Branched chain, or aryl, olefines, di- and poly-olefines may also be treated alone or to form co-polymers.  Other compounds, e.g. acrylonitrile, vinyl chloride, 2-vinyl pyridine or methyl acrylate may be present.  The polymerization may be effected with inert diluents including paraffinic and aromatic hydrocarbons.ALSO:A catalyst for polymerizing olefines consists of 3 components mixed together (1) an organic compound containing Ti, Zr, Hf or Th, (2) a metal hydride which may also contain substituted hydrocarbon radicals and where the metal has a valency of at least 2 and is selected from Group II to VIII and preferably from Group II and II, and (3) a halogen or halogen hydride.  The organic compounds (1) include salts of mono-basic organic acids, e.g. titanium butyrate sodium titanium oxalate; complex salts of di-basic organic acids containing also an alkali metal or ammonia; compounds of the type XM(OR) or M(OCH2CH2)NH, where X=halogen, M is Ti, Hf, Zr, or Th, R=an hydrocarbon radical not exceeding 20 C atoms, or substituted radicals containing oxygen and/or chlorine, e.g. titanium butoxide, tetra isopropyl titanate, dichloro-diethyl zirconate; alkoxides or mono- or poly-ethanolamine salts of the specified metals or their acetyl acetonates.  Numerous examples are given.  Examples of metal hydrides &c. (2) include tri-methyl or triethyl aluminium, di-ethyl aluminium hydride, dimethyl besyllium, tri-isopropyl gallium and similar compounds, of mercury, indium, and zinc, and complexes of these formed with ethers, thio-ethers, amines, alkali metal hydrides or alkyls, e.g. LiAlH4, NaBe(C2H5)3.  Examples of halogen or halogen hydrides include addition to the elements themselves, iodine chloride bromide or fluoride, hydrogen fluoride and similar compounds. Preferred catalyst mixtures are (1) tri-ethyl aluminium, titanium butoxide and HCl, (2) tri-ethyl aluminium, titanium acetyl acetonate and chlorine, (3) tri-ethyl gallium, zirconium butoxide, and chlorine, (4) di-ethyl beryllium, titanium potassium oxalate, and HBr.; 1-olefines containing up to 8 C atoms may be polymerized at temperatures up to 500 DEG  F. and preferably at 100 to 1000 lb. p.s.i.g.  Branched chain, aryl, di- and polyolefines may also be treated alone or to form copolymers. Other compounds, e.g. acrylonitrile, vinyl chloride, 2-vinyl pyridine, methyl acrylate may be present.  The polymerization may be effected with inert diluents including paraffinic and aromatic hydrocarbons.