Polyethylene and catalyst composition for its preparation
View Patent ↗Polyethylene which comprises ethylene homopolymers and copolymers of ethylene with α-olefins and has a molar mass distribution width M w /M n of from 6 to 100, a density of from 0.89 to 0.97 g/cm 3 , a weight average molar mass M w of from 5000 g/mol to 700,000 g/mol and has from 0.01 to 20 branches/1000 carbon atoms and at least 0.5 vinyl groups/1000 carbon atoms, wherein the 5-50% by weight of the polyethylene having the lowest molar masses have a degree of branching of less than 10 branches/1000 carbon atoms and the 5-50% by weight of the polyethylene having the highest molar masses have a degree of branching of more than 2 branches/1000 carbon atoms, a process for its preparation, catalysts suitable for its preparation and also fibers, moldings, films or polymer blends in which this polyethylene is present.
1. A catalyst composition comprising at least two different polymerization catalysts, wherein A is at least one polymerization catalyst based on a monocyclopentadienyl complex of metal of groups 4-6 of the Periodic Table of the Elements wherein the cyclopentadienyl system is substituted by an uncharged donor (A1) or a hafnocene (A2); and B) is at least one polymerization catalyst based on an iron component having a tridentate ligand bearing a least two ortho, ortho-disubstituted aryl radicals (B);
wherein A1 has the general formula III
E 1A -E 5A are each carbon or not more than one E 1A to E 5A phosphorus;
R 1A -R 4A are each, independently of one another, hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR 5A 2 , N(SiR 5A 3 ) 2 , OR 5A , OSiR 5A 3 , SiR 5A 3 , BR 5A 2 , where the organic radicals R 1A -R 4A may also be substituted by halogens and two vicinal radicals R 1A -R 4A may also be joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S;
R 5A are each, independently of one another, hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, alkylaryl having from 1 to 10 carbon atoms in the aklyl part and 6-20 carbon atoms in the aryl part and two geminal radicals R 5A may also be joined to form a five- or six-membered ring;
Z is a divalent bridge between A and Cp which is selected from
L 1A -L 3A are each, independently of one another, silicon or germanium;
R 6A -R 11A are each, independently of one another, hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 8 -C 20 aryl, alkylaryl having from 1 to 10 carbon atoms in the aklyl part and 6-20 carbon atoms in the aryl part or SiR 12A 3 , optionally R 6A -R 11A are substituted by halogens and two geminal or vicinal radicals R 6A -R 11A are joined to form a five- or six-membered ring;
R 12A are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, C 1 -C 10 alkoxy or C 6 -C 10 aryloxy; optionally two radicals R 12A are joined to form a five- or six-membered ring;
A is an uncharged donor group containing one or more atoms of groups 15 and 16 of the Periodic Table of the elements;
M A is a metal selected from the group consisting of titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten;
K is 0 is 1.
and wherein A2 has the general formula VI;
wherein X B is fluorine, chlorine, bromine, iodine, hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 6 -C 15 aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, —OR 60 or —NR 6B R 7B , or two radicals X B form a substituted or unsubstituted diene ligand; radicals X B are identical or different and optionally are joined to one another;
E 1B -E 5B are each carbon or not more than one E 1B to E 5B is phosphorus or nitrogen;
l is 1, 2 or 3 and is, depending on the valence of Hf, provided that the metallocene complex of the general formula (VI) is uncharged;
R 6B and R 7B are each C 1 -C 10 alkyl, C 6 -C 15 aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part;
R 1B to R 5B are each, independently of one another hydrogen, C 1 -C 22 alkyl, 5-to 7-membered cycloalkyl or cycloalkenyl which optionally bears C 1 -C 10 alkyl groups as substituents, C 2 -C 22 alkenyl, C 6 -C 22 aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR 6B 2 , N(SiR 5B 3 ) 2 , OR 8B , OSiR 8B 3 , SiR 8B 3 , where the organic radicals R 1B -R 5B are optionally substituted by halogens or two radicals R 1B -R 5B are joined to form a five-, six- or seven-membered ring, or two vicinal radicals R 1D -R 5D are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S;
radicals R 8B are identical or different and each selected from C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 15 alkyl, C 1 -C 4 alkoxy or C 8 -C 10 aryloxy;
Z 1B is X B or
wherein R 9B -R 13B are each, independently of one another, hydrogen, C 1 -C 22 alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl which optionally bears C 1 -C 10 alkyl groups as substituents, C 2 -C 22 alkenyl, C 6 -C 22 aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and 6-21 carbon atoms in the aryl part, NR 14B 2 , N(SiR 14B 3 ) 2 , OR 14B , OSiR 14B 3 , SiR 14B 3 ; radicals R 8B -R 13B are optionally substituted by halogens and two radicals R 9B -R 13B are optionally joined to form a five-, six- or seven-membered ring; optionally two vicinal radicals R 9B -R 13B are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S;
radicals R 14B are identical or different and are each C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 15 aryl, C 1 -C 4 alkoxy or C 6 -C 10 aryloxy;
E 6B -E 10B are each carbon or not more than one E 6B to E 10B is phosphorus or nitrogen, or wherein the radicals R 4B and Z 1B together form an —R 15B v —A 1B — group;
R 16 B is
R 16B -R 21B are identical or different and are each a hydrogen atom, a halogen atom, a trimethylsilyl group, a C 1 -C 10 alkyl group, a C 1 -C 10 fluoroalkyl group, a C 6 -C 10 fluoroaryl group, a C 6 -C 10 aryl group, a C 1 -C 10 alkoxy group, a C 7 -C 15 alkylaryloxy group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group or a C 6 -C 40 alkylaryl group or two adjacent radicals together with the atoms connecting them form a saturated or unsaturated ring having from 4 to 15 carbon atoms;
M 2B -M 4B are each silicon, germanium or tin;
A 1B is —O—, —S—, <NR 22B , <PR 22B , =O, =S, =NR 22 B, —O—R 22B , —NR 22B 2 , —PR 22B 2 or an unsubstituted, substituted or fused, heterocyclic ring system;
R 22B are each, independently of one another, C 1 -C 10 alkyl, C 6 -C 15 aryl, C 3 -C 10 cycloalkyl, C 7 -C 18 alkylaryl or Si(R 22B ) 3 ,
R 23B is hydrogen, C 2 -C 10 alkyl, C 6 -C 15 aryl which may in turn bear C 1 -C 4 alkyl groups as substituents or C 3 -C 10 cycloalkyl;
v is 1 or when A 1B is an unsubstituted, substituted or fused, heterocyclic ring system v is 0;
optionally R 4B and R 12B joint together to form an —R 15B — group.
2. The catalyst composition of claim 1 , which further comprises at least one activating compound.
3. The catalyst composition of claim 1 , which further comprises at least one organic or inorganic support.
4. The catalyst composition of claim 1 , which further comprises at least one metal compound of a metal of group 1, 2, or 13 of the Periodic Table.
5. The catalyst composition of claim 1 , which is prepolymerized with one or more linear C 2 -C 10 1-alkenes.