US 6,388,029 B1 · Process for obtaining polyolefins

Abstract

Catalytic systems particularly suitable for the polymerization of α-olefins containing from two to 20 carbon atoms, as well as for the copolymerization of ethylene with α-olefins containing from three to 20 carbon atoms, dienes, and cycloalkenes in processes wherein the catalyst is suspended in a solvent, in processes in gas phase, as well as in mass polymerization processes at high temperatures and pressures, are disclosed. The catalytic system is a mixture of a catalyst component A and a co-catalyst component B. The catalyst component A is formed by a functionalized inorganic porous oxide, by an organoaluminium compound and by an organometallic compound of a metal of the groups 3, 4, 5, or 6 of the periodic table. Functionalization of the inorganic oxide is by introduction of functional groups to be used to strongly fix the organoaluminium compound and the organometallic compound. The co-catalyst component B, which is used for the activation of the catalyst, is formed of organoaluminium compounds, perfluorinated derivatives of boron, or a mixture thereof.

A process for obtaining polyolefins comprising the step of polymerizing α-olefins under polymerizing conditions with a heterogeneous catalyst component (A) and a co-catalyst (B) to obtain a polymer products, said heterogeneous catalyst component (A) comprising a functionalized support (A.1), an organo aluminum compound (A.2) and at least one metallocene complex of any of groups 3, 4, 5 and 6 of the periodic table (A.3), wherein said metallocene complex (A.3) is linked to the functionalized support (A.1) through said organo aluminum compound (A.2), and wherein:

a) said functionalized support (A.1) results from the reaction of an inorganic porous support comprising one or more oxides of the elements of any of groups 2, 13 and 14 of the periodic table, dehydrated or not, and a functionalizing compound of general formula:
wherein:
R1 is halogen, an alkoxide of formula OR, R being a branched or a non-branched alkyl group having from 1 to 6 carbon atoms, a C5-C7 cycloalkyl group, a C6-C10 aryl group, a C2-C10 alkenyl group, a C7-C10 arylalkyl group or a C7-C40 alkylaryl group;
R2, R3, R4 and R5 are the same or different from each other, are linear or branched C1-C6 alkyl groups, C5-C7 cycloalkyl groups, C6-C10 aryl groups, C2-C10 alkenyl groups, C7-C10 arylalkyl groups, or C7-C40 alkylaryl groups;
R6 is a methylene group or propylene group;
E is selected from the group consisting of —NH2, —NHR, —SH, —OH, and —PHR wherein R has the above defined meaning;
the sum of a+b+c is equal to 3, a being always higher than 0;
and,
d, e independently have values between 0 and 10;
and
b) said metallocene complex of any of groups 3, 4, 5 and 6 of the periodic table (A.3) is represented by the general formula III:
wherein:
M is a transition metal of the groups 3, 4, 5 or 6 of the periodic table;
each X is independently selected from the group consisting of hydrogen, halogen, linear or branched alkyl groups having from 1 to 10 carbon atoms, C1-C10 alkoxyl groups, C5-C7 cycloalkyl groups, C6-C10 aryl groups, C6-C10 aryloxyl groups, C2-C10 alkenyl groups, C7-C10 arylalkyl groups, C7-C40 alkylaryl groups and C8-C40 arylalkenyl groups;
L1 is selected from the group consisting of cyclopentadienyl (Cp) of formula
indenyl (Ind) of formula
and fluorenyl (Flu) of formula
wherein each G is independently selected from the group consisting of hydrogen, linear or branched alkyl groups having from 1 to 10 carbon atoms, C5-C7 cycloalkyl groups optionally substituted by an alkyl group having from 1 to 6 carbon atoms, C6-C10 aryl groups, C2-C10 alkenyl groups, C7-C10 arylalkyl groups and C7-C40 alkylaryl groups;
a group of general formula (IV)
wherein:
R7, R8, R9, R10, R11, R12, R13, and R14 are the same or different from each other, are hydrogen, linear or branched alkyl groups having from 1 to 10 carbon atoms, C5-C7 cycloalkyl groups, optionally substituted by an alkyl group having from 1 to 6 carbon atoms, C6-C10 aryl groups, C2-C10 alkenyl groups, C7-C10 arylalkyl groups or C7-C40 alkylaryl groups, and provided that R7 and R8 optionally are equal to Y;
Y is optionally a halogen or NR11R12 or hydroxyl;
o, p, q, r, s are integers which have values between 0 and 10;
u=5-g;
v=7-g;
z=9-g;
D is equal to L1 or is a heteroatom belonging to group 13, 14, 15, or 16 of the periodic table;
A is a group which binds the ligands L1 and D according to the formula (V):
wherein T is selected from the group consisting of carbon, silicon, germanium and tin;
j is an integer which has a value of 0, 1, 2, 3 or 4;
k is an integer which has a value of 0, 1, 2 or 3;
m, n, and h are integers having a sum equal to 4;
m and n have values of 0, 1 or 2 so that their sum is 1 or 2;
h is no higher than 3;
g is an integer between 0 and 2;
and when h is equal to 3 then the sum of m+n is equal to 1 and g is 0.

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Process for obtaining polyolefins

Life of this patent

Process for obtaining polyolefins

Life of this patent

Abstract

Claims24