Patent GB-727944-A (GB)
Title: Polymerization of olefins
IPC: C07C2/20
Filed: 1953-05-04
Abstract: Olefines are polymerized in the presence of a catalyst comprising a co-ordination compound obtained by combining boron trifluoride and an acid of phosphorus at a temperature below 50 DEG  F. (see Group III). The activity of the catalyst is modified by the addition of free acid of phosphorus, e.g. in the molar ratio of coordination compound to free acid of 1 : 9 to 9 : 1; on the other hand the catalyst may contain excess boron trifluoride to maintain maximum activity during long periods.  The catalyst can be used in liquid form or as a thin film on nonporous inert materials, but is preferably supported on a finely divided porous adsorbent.  Polymerization is carried out by a continuous fixed bed, suspension, or fluidized process.  Olefines mentioned are propylene, butylenes, pentenes, heptenes, octenes, butadiene and isoprene; the feed may also contain diluents such as paraffins or nitrogen.  Reaction temperatures up from below room temperature to 500 DEG  F. (preferably 70-300 DEG  F.), and pressures up to 1500 lbs. per sq. inch, may be employed.  Examples are given showing the effect of addition of extraneous boron trifluoride during polymerization, of the addition of co-ordination compound during polymerization, and of pretreating the catalyst with boron trifluoride.  The polymerization products may be used as motor fuel blending agents or chemical intermediates.ALSO:Olefines are polymerized in the presence of a catalyst comprising a co-ordination compound obtained by combining boron trifluoride and an acid of phosphorus at a temperature below 50 DEG  F. (see Group III).  The activity of the catalyst is modified by the addition of free acid of phosphorus, e.g. in the molar ratio of coordination compound to free acid of 1 : 9 to 9 : 1; on the other hand the catalyst may contain excess boron trifluoride to maintain maximum activity during long periods.  The catalyst can be used in liquid form or as a thin film on nonporous inert materials, but is preferably supported on a finely divided porous adsorbent.  Polymerization is carried out by a continuous fixed bed, suspension, or fluidized process.  Olefines mentioned are propylene, butylenes, pentenes, heptenes, octenes, butadiene and isoprene; the feed may also contain diluents such as paraffins or nitrogen.  Reaction temperatures of from below room temperature to 500 DEG  F. (preferably 70-300 DEG  F.), and pressures up to 1500 lbs. per square inch may be employed.  Examples are given showing the effect of addition of extraneous boron trifluoride during polymerization, of the addition of co-ordination compound during polymerization, and of pretreating the catalyst with boron trifluoride.  The polymerization products may be used as motor fuel blending agents or chemical intermediates.ALSO:A co-ordination compound formed by combining boron trifluoride with an acid of phosphorus at a temperature below 50 DEG  F. is used as a catalyst for the polymerization of olefines (see Groups IV (a) and IV (b)). Orthophosphoric, pyrophosphoric, metaphosphoric, hypophosphoric, phosphorous, and metaphosphorus acids may be used; some water may be present in the acid.  The compounds are formed either by treating the liquid acid with gaseous boron trifluoride or by adding an organic aliphatic ether complex of boron trifluoride to the acid and then removing excess ether by distillation; the mixture is cooled during reaction, the temperature preferably being kept at 20 DEG -40 DEG  F. Typical compounds have the formulae H3PO4.BF3, HPO3.BF3, H4P2O7,BF3, and H4P2O7.2BF3.  The activity of the catalyst is modified by the addition of free acid of phosphorus, e.g. in the molar ratio of co-ordination compound to free acid of 1 : 9 to 9 : 1; on the other hand the catalyst may contain excess boron trifluoride to maintain maximum activity during long periods.  The catalyst may also contain metal salts of acids of phosphorus, e.g. salts of Cu, Fe, Ni, U, Zn, Co, Mn, Ag, Cd, and Cr, and also oxides or sulphates of Ti, Zr, Th, or V.  The addition of boric anhydride extends the life of the catalyst by reacting with hydrogen fluoride released to regenerate boron trifluoride.  The catalyst can be used in liquid form or as a thin film on non-porous inert materials such as quartz chips, pumice, copper turnings, or sand; preferably it is supported on a finely divided porous adsorbent, such as activated carbon, silica gel, kieselguhr, Fullers earth, or bentonite; the catalyst and carrier may be mixed at reduced pressure.