Patent GB-873226-A (GB)
Title: Improvements in or relating to the catalytic polymerisation of olefins and to catalysts therefor
Inventor: DUCK EDWARD WILLIAM
IPC: C08F10/00
Filed: 1957-06-28
Abstract: Polyolefins having a softening-point (30 degrees angle) of at least 115 DEG C. as determined in accordance with BSS 1493/1948 are prepared by polymerizing an a -olefin with the aid of a catalyst containing a Group IV(a), V(a), VI(a), VII(a) or VIII metal in two different valency states formed by mixing (1) a compound of a metal of the said Groups in its normal maximum valency state with (2) a compound of a metal of Group II or III(b) which contains in its molecular structure (a) a carbon-oxygen-metal bond and (b) a hydrogen-metal and/or a carbon-metal bond.  In a modification of the process, component (1) comprises at least two compounds, in the normal maximum valency state and in the next lower valency state respectively, of a metal of the said Groups; the catalyst produced in this modification is claimed per se.  TiCl3 and TiCl4 are preferred for component (1) but also mentioned are Ti and Zr tetrahalides generally, MnCl2, FeCl3, TiEt4, Cr acetylacetonate, MoCl5, VCl4 and WCl6.  Component (2) includes compounds (i) in which the metal atom is part of a ring e.g. R-Al(-O-CH2)2 and R-Al (O-CH2)2CH2, (ii) containing a plurality of metal atoms e.g. (R2Al-O-CH2-)2, (RZn-O-CH2-)2 and [RAl(O-CH2R)-O-]2 (CH2)n and (iii) derived from CnF2n+1CH2OH alcohols e.g. CF3CH2OH specified components (2) in examples are PrZnOPr, EtAl(OR1)2 wherein R1 is ethyl, phenyl and p-chlorophenyl, mono (or di)-isobutyl aluminium di- (or mono-)-n-nonalate and Et-Al(OCH2)2. o-Dichlorobenzene and white oil are mentioned as diluents in addition to the usual hydrocarbons. C1-10 aliphatic alcohols e.g. methanol or 3 : 5 : 5-trimethylhexanol may be added to the reaction mixture.  The catalyst may be aged before use. The invention is preferably applied to the polymerization or copolymerization of ethylene, but is also stated to be applicable to propylene.  Specifications 799,392, 799,823, 801,031, 810,023, 816,614, 819,867, 837,053, 837,064, 840,859, 851,112 and 851,113 are referred to.ALSO:Polyolefins having a softening-point (30 degrees angle) of at least 115 DEG C. as determined in accordance with BSS 1493/1948 are prepared by polymerisng an a -olefin with the aid of a catalyst containing a Group IVA, VA, VIA, VIIA or VIII metal in two different valency states formed by mixing (1) a compound of a metal of the said Groups in its normal maximum valency state with (2) a compound of a metal of Group II or IIIb which contains in its molecular structure (a) a carbon-oxygen-metal bond and (b) a hydrogen-metal and/or a carbon-metal bond.  In a modification of the process, component (1) comprises at least two compounds, in the normal maximum valency state and in the next lower valency state respectively, of a metal of the said Groups; the catalyst produced in this modification is claimed per se.  TiCl3 and TiCl4 are preferred for component (1) but also mentioned are Ti and Zr tetrahalides generally, MnCl2, FeCl3, TiEt4, Cr acetylacetonate, MoCl5, VCl4 and WCl6.  Component (2) includes compounds (i) in which the metal atom is part of a ring, e.g. R\\Al(-O-CH2)2 and R-Al(O-CH2)2CH2, (ii) containing a plurality of metal atoms, e.g. (R2Al-O-CH2-)2, (RZn-O-CH2-)2 and [RAl(O-CH2R)-O-]2(CH2)n and (iii) derived from CnF2n+1CH2OH alcohols, e.g. CF3CH2OH; specified components (2) in examples are PrZnOPr, EtAl(OR)2 wherein R1 is ethyl, phenyl and p-chlorophenyl, mono (or di)-isobutyl aluminium di (or mono)-n-nonalate and Et-Al(OCH2)2.  o-Dichlorobenzene and white oil are mentioned as diluents in addition to the usual hydrocarbons. C1-10 aliphatic alcohols, e.g. methanol or 3 : 5 : 5-trimethylhexanol, may be added to the reaction mixture.  The catalyst may be aged before use.  The invention is preferably applied to the polymerisation or copolymerisation of ethylene, but it is also stated to be applicable to propylene.  Specifications 799,392, 799,823, 801,031, 810,023, 816,614, 819,867, 837,053, 837,064, 840,859, 851,112 and 851,113 are referred to.