| 主权项 |
1. A method to prepare a dual catalyst comprising
(i) from 20 to 80 mole % of a phenoxide catalyst of the formula:wherein R2, R3, and R5 are hydrogen atoms , R1 is a cyclohexyl radical, R4is methoxy radical, and R6 is a t-butyl radical M is selected from the group consisting of Ti, Zr and Hf, X is a chlorine atom, n is 1 or 2 and t is 2 or 3 and the sum of n+m is the valence of M.
and (ii) from 80 to 20 mole % of a phosphinimine catalyst of the formula:wherein M is a group 4 metal having an atomic weight less than 179; PI is a phosphinimine ligand of the formula:wherein each R15 is independently selected from the group consisting of C1-6 hydrocarbyl radicals; L is a monoanionic ligand selected from the group consisting of a cyclopentadienyl radical which is unsubstituted or substituted by a substituent selected from the group consisting of a C1-6 alkyl radical which is substituted by 2n+1 fluorine atoms where n is the number of carbon atoms in the alkyl radical, and a C6F5 radical which cyclopentadienyl ligand is optionally further substituted with up to two C3-6 alkyl radicals in the 2 or 3 position relative to the fluorine containing substituent; Y is an activatable ligand selected from the group consisting of a hydrogen atom, a chlorine atom and a C1-4 alkyl radical ; t is 1 or 2; q is 1; and p is an integer and the sum of t+q+p equals the valence state of M.; both on an inorganic support comprising:
impregnating a porous particulate inorganic oxide support having an average particle size from 10 to 150 microns, a surface area greater than 100 m2/g and a pore volume greater than 0.3 ml/g with not less than 1 wt % of a 5 to 15 wt % aqueous solution of Zr(SO4)2.4H2O thereof to provide from 0.010 to 0.050 mmol of Zr per gram of treated support, not less than 1 weight % based on the weight of the support of Zr(SO4)2.4H2O; (ii) recovering the impregnated support; (iii) calcining said impregnated support at a temperature from 300° C. to 600° C. for a time from 2 to 20 hours in an inert atmosphere; (iv) contacting said impregnated calcined support with a hydrocarbyl solution containing at least 5 weight % of an aluminum activator compound of the formula R122AlO(R12AlO)rAlR122 wherein each R12 is independently selected from the group consisting of C1-20 hydrocarbyl radicals and r is from 3 to 50 to provide from 0.1 to 30 weight % of said aluminum compound based on the weight of said calcined support; optionally separating said activated support from said hydrocarbyl solution; and contacting said activated support with one or more hydrocarbyl solutions containing at least 5 weight % of a phosphinimine catalyst, a phenoxide ligand containing catalyst or both; and (v) optionally contacting said catalyst with a hydrocarbyl solution of an anti static comprising (I) from 3 to 48 parts by weight of one or more polysulfones comprising:
(a) 50 mole % of sulphur dioxide;(b) 40 to 50 mole % of a C6-20 an alpha olefin; and(c) from 0 to 10 mole % of a compound of the formula ACH═CHB where A is selected from the group consisting of a carboxyl radical and a C1-15 carboxy alkyl radical and B is a hydrogen atom or a carboxyl radical provided if A and B are carboxyl radicals A and B may form an anhydride; (II) from 3 to 48 parts by weight of one or more polymeric polyamides of the formula:
R20N[(CH2CHOHCH2NR21)a—(CH2CHOHCH2NR21—R22—NH)b—(CH2CHOHCH2NR23)cH]xH2-x—wherein R21 is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms; R22 is an alkylene group of 2 to 6 carbon atoms; R23 is the group R22—HNR21; R20 is R21 or an N-aliphatic hydrocarbyl alkylene group having the formula R21NHR22; a, b and c are integers from 0 to 20 and x is 1 or 2; with the proviso that when R20 is R21 then a is greater than 2 and b=c=0, and when R20 is R21NHR22 then a is 0 and the sum of b+c is an integer from 2 to 20; and
(III) from 3 to 48 parts by weight of C10-20 alkyl or arylalkyl sulphonic acid, to provide from 50 to 250 ppm of antistatic based on the weight of the catalyst; and (vi) recovering and drying the catalyst. |
