Patent GB-1022673-A (GB)
Title: Catalyst and process for olefin polymerization
IPC: C07C2/30
Filed: 1963-02-06
Abstract: Oligmers such as dimers, and trimers &c., are made by polymerizing normally gaseous olefins at a temperature of 150 DEG  to 1000 DEG F., and a pressur of 15 to 3000 p.s.i., in the presence of a catalyst consisting of the reaction product on a boron compound and an aluminium compound. The boron compound is selected from boron alkyls or hydrides, boric acid, monoalkyl boric acids, boric oxide, or sodium borate, and the aluminium compound from aluminium alkoxides, phosphates, hydroxides, acetylacetonates, silicofluorides, citrates, and mixtures. The mole ratio of the boron compound to the aluminium compound is 0.01:1 to 100:1.  The reaction product is made by heating a mixture of the compounds at a temperature of 250 DEG  to 800 DEG F. for a period of 0.01 to 10 hours. Olefins exemplified are propylene, butene-1, and ethylene. The oligmers are isolated from the liquid polymers by fractional distillation.ALSO:A polymerization catalyst comprises a reaction product, prepared in the absence of water, of a boron compound and an aluminium compound, in which the boron compound is selected from boron alkyls, monoalkyl boric acids, boron hydrides and boron oxides, and the aluminium compound is selected from aluminium alkoxides, phosphate, hydroxides, acetyl-acetonates, silicofluorides, citrates, and mixtures thereof. The mole ratio of the boron compound to the Al compound is from 0.01 : 1 to 100 : 1.  The reaction product is obtained by heating a mixture of the above compounds at a temperature of 250 DEG  to 800 DEG  F. for a period of 0.01 to 10 hours.  The catalyst may be supported on an inert carrier material.  The catalyst is used for polymerizing normally gaseous olefins to liquid polymers, at a temperature of about 150 DEG  to 1000 DEG  F. and a pressure of 15 to 3000 pounds per square inch.  Specified olefins are ethylene, propylene, butene-1, butene-2, and isobutylene.  Specified boron and aluminium compounds are tri-n-ethyl, n-propyl, butyl, or amyl borane, diborane, pentaborane, decaborane, aluminium ethoxide, aluminium propoxide, and aluminium tertiary butoxide.  Carriers mentioned are alumina, charcoal, diatomaceous earths, quartz, kaolin, silica, and fuller's earth.  The polymerization may be carried out in bulk, or in a hydrocarbon diluent or solvent.  The liquid polymer may be separation into fractions such as dimers and trimers.ALSO:A catalyst for forming liquid polymers comprises a reaction product prepared in the absence of water, of a boron compound and an aluminium compound, in which the boron compound is selected from boron alkyls, or hydrides, boric acid or esters, mono-, or dialkyl, or aryl boric acids, boric oxide, or sodium borate, and the aluminium compound from aluminium alkoxides, phosphates, hydroxides, acetylacetonates, silicofluorides, citrates, or mixtures thereof.  The mole ratio of the boron compound to the aluminium compound is 0,01 : 1 to 100 : 1. The reaction product is obtained by heating a mixture of the compounds at a temperature of 250-800  DEG F. for a period of 0,01-10 hours.  The catalyst may be supported on an inert carrier. Exemplified catalysts are aluminium isopropoxide and tri-n-butyl borane supported on alumina, and also supported on silica, and charcoal, aluminium isopropoxide, tri-n-butyl borane, and boric anhydride, supported on silica, aluminium phosphate and tri-n-butylborane, aluminium citrate and tri-n-butylborane, sodium borate and aluminium isopropoxide, tri-n-butyl borane and aluminium acetylacetone, boric anhydride or acid and aluminium isopropoxide, trimethyl borate and aluminium ethoxide, and tri-n-butylborane and aluminium silicofluoride.  Carriers mentioned are alumina, charcoal, diatomaceous earths, quartz, kaolin, silica, and fuller's earth.  The liquid polymers produced include fractions containing dimers, trimers &c.