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US 7,834,112 B2Granted
Method of polymerization of olefins
AssigneeBasell Polyolefine GmbH
InventorsShahram Mihan, Birgit Dorer, Markus Enders, Pablo Fernandez
Life of this patent
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Abstract
A process for the polymerization of olefins using a metal complex of group 3, 4, 5, 6, 7, 8, 9 or 10 of the Periodic Table comprising at least one group C═NR1, C═PR1, C═O, C═S or a heteroaromatic ring system containing at least one atom from the group consisting of N, P, O and S, can be used for controlling the width of the molar mass distribution of the resulting polymers.
Claims7
A process for the polymerization of olefins, which comprises polymerizing the olefins in the presence of a catalyst system comprising the reaction product of:
- A) a metal complex of formula (Cp)(—Zm-A)MXk, where the variables have the following meanings:
- Cp is a cyclopentadienyl system,
- Z is a divalent bridge between A and Cp,
- A is an unsubstituted, substituted or fused, heteroaromatic ring system containing at least one atom selected from the group consisting of N, P, O and S,
- M is a metal of group 3, 4, 5 or 6 of the Periodic Table,
- X are each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C6-C20-aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR6R7, OR6, SR6, SO3R6, OC(O)R6, BF4−, PF6− or a bulky noncoordinating anion,
- R6-R7 are each, independently of one another, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR83, where the organic radicals R6-R7 may also be substituted by halogens or two radicals R6-R7 may also be joined to form a five- or six-membered ring,
- R8 are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or two radicals R8 may also be joined to form a five- or six-membered ring,
- k is 1, 2 or 3 and
- m is 0,
- B) optionally an organic or inorganic support,
- C) one or more cation-forming compounds selected from strong, uncharged Lewis acids of the compounds of formula (F XII):
- M2DX1DX2DX3D (F XII)
- where
- M2D is an element of group 13 of the Periodic Table of the Elements,
- X1D, X2D, X3D are each hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, or fluorine, chlorine, bromine or iodine,
- salt-like compounds of the cation of the formula (F XIII):
- [((M3D)a+Q1Q2 . . . Qz]d+ (F XIII)
- where
- M3D is an element groups 1 to 16 of the Periodic Table of the Elements,
- Q1 to Qz are singly negatively charged groups of C1-C28 alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 atoms in the aryl radical and from 1 to 28 carbon atoms in the alkyl radical, C3-C10-cycloalkyl which may bear C1-C10-alkyl groups as substituents, halogen, C1-C28-alkoxy, C6-C15-aryloxy, silyl or mercaptyl groups,
- a is an integer from 1 to 6,
- z is an integer from 0 to 5,
- d is the difference a-z, but d is greater than or equal to 1,
- protonated amine or aniline derivatives as Brønsted acid cations with noncoordinating counterions, or alumoxane;
- and
- D) optionally one or more metal compounds of group 13 of the Periodic Table, with a compound of the formula F-I
- M1(R3)rA(R4)sA (F-I)
- where
- M1 is Li, Na, or Be,
- R3 is C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part,
- R4 is hydrogen, halogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or alkoxy having from 1 to 10 carbon atoms in the alkyl radical,
- rA is 1 or 2
- and
- sA is 0 or 1, where the sum rA+sA corresponds to the valence of M1, resulting in modification of the heteroaromatic ring system,
- wherein the reaction is carried out prior to the polymerization, and
- the olefins are selected from the group consisting of linear or branched C2-C12-1-alkenes and aryl substituted α-olefins.
34 more elements
A process for the polymerization of olefins, which comprises polymerizing the olefins in the presence of a catalyst system comprising the reaction product of:
- A) a metal complex of formula (Cp)(—Zm-A)MXk, where the variables have the following meanings:
- Cp is a cyclopentadienyl system,
- Z is a divalent bridge between A and Cp,
- A is an unsubstituted, substituted or fused, heteroaromatic ring system containing at least one atom selected from the group consisting of N, P, O and S,
- M is a metal of group 3, 4, 5 or 6 of the Periodic Table,
- X are each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C1-C10-alkenyl, C6-C20-aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR6R7, OR6, SR6, SO3R6, OC(O)R6, BF4−, PFb− or a bulky noncoordinating anion,
- R6-R7 are each, independently of one another, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR83, where the organic radicals R6-R7 may also be substituted by halogens or two radicals R6-R7 may also be joined to form a five- or six-membered ring,
- R8 are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or two radicals R8 may also be joined to form a five- or six-membered ring,
- k is 1, 2 or 3 and
- m is 0,
- B) optionally an organic or inorganic support,
- C) one or more cation-forming compounds, and
- D) one or more metal compounds of group 13 of the Periodic Table, with a compound of the formula F-I
- M1(R3)rA(RA)sA (F-I)
- where
- M1 is Li, Na, K, or Be,
- R3 is C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part,
- R4 is hydrogen, halogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or alkoxy having from 1 to 10 carbon atoms in the alkyl radical,
- rA is 1 or 2
- and
- sA is 0 or 1, where the sum rA+sA corresponds to the valence of M1, resulting in modification of the heteroaromatic ring system,
- wherein the reaction is carried out prior to the polymerization, and
- the olefins are selected from the group consisting of linear or branched C2-C12-1-alkenes and aryl substituted α-olefins.
20 more elements
A process for the polymerization of olefins, which comprises polymerizing the olefins in the presence of a catalyst system consisting of the reaction product of
- A) a metal complex of formula (Cp)(—Zm-A)MXk, where the variables have the following meanings:
- Cp is a cyclopentadienyl system,
- Z is a divalent bridge between A and Cp,
- A is an unsubstituted, substituted or fused, heteroaromatic ring system containing at least one atom selected from the group consisting of N, P, O and S,
- M is a metal of group 3, 4, 5 or 6 of the Periodic Table,
- X are each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C6-C20-aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR6R7, OR6, SR6, SO3R6, OC(O)R6, BF4−, PF6− or a bulky noncoordinating anion,
- R6-R7 are each, independently of one another, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR83, where the organic radicals R6-R7 may also be substituted by halogens or two radicals R6-R7 may also be joined to form a five- or six-membered ring,
- R8 are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or two radicals R8 may also be joined to form a five- or six-membered ring,
- k is 1, 2 or 3 and
- m is 0,
- B) optionally, an organic or inorganic support,
- C) one or more cation-forming compounds, and
- D) one or more metal compounds of group 13 of the Periodic Table, with a compound of the formula F-I,
- M1(R3)rA(R4)sA (F-I)
- where
- M1 is Li, Na, K, or Be,
- R3 is C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part,
- R4 is hydrogen, halogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or alkoxy having from 1 to 10 carbon atoms in the alkyl radical,
- rA is 1 or 2
- and
- sA is 0 or 1, where the sum rA+sA corresponds to the valence of M1, resulting in modification of the heteroaromatic ring system,
- wherein the reaction is carried out prior to the polymerization, and
- the olefins are selected from the group consisting of linear or branched C2-C12-1-alkenes and aryl substituted α-olefins.
20 more elements
A process for the polymerization of olefins, which comprises polymerizing the olefins in the presence of a catalyst system consisting of the reaction product of
- A) a metal complex of formula (Cp)(—Zm-A)MXk, where the variables have the following meanings:
- Cp is a cyclopentadienyl system,
- Z is a divalent bridge between A and Cp,
- A is an unsubstituted, substituted or fused, heteroaromatic ring system containing at least one atom selected from the group consisting or N, P, O and S,
- M is a metal of group 3, 4, 5 or 6 of the Periodic Table,
- X are each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C6-C20-aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR6R7, OR6, SR6, SO3R6, OC(O)R6, BF4−, PF6− or a bulky noncoordinating anion,
- R6-R7 are each, independently of one another, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR83, where the organic radicals R6-R7 may also be substituted by halogens or two radicals R6-R7 may also be joined to form a five- or six-membered ring,
- R8 are each;
- independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or two radicals R8 may also be joined to form a five- or six-membered ring,
- k is 1, 2 or 3 and
- m is 0,
- B) an organic support or inorganic support selected from silica gel, magnesium chloride or aluminum oxide,
- C) one or more cation-forming compounds and
- D) optionally one or more metal compounds of group 13 of the Periodic Table, with a compound of the formula F-1
- M1(R3)rA(R4)sA (F-I)
- where
- M1 is Li, Na, K, or Be,
- R3 is C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part,
- R4 is hydrogen, halogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or alkoxy having from 1 to 10 carbon atoms in the alkyl radical,
- rA is 1 or 2
- and
- sA is 0 or 1, where the sum rA+sA corresponds to the valence of M1, resulting in modification of the heteroaromatic ring system,
- wherein the reaction is carried out prior to the polymerization, and
- the olefins are selected from the group consisting of linear or branched C2-C12-1-alkenes and aryl substituted α-olefins.
21 more elements
Dependencies are inferred from the claim text.