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US 6,747,106 B2Granted
Polymerization of olefins
AssigneeE. I. Du Pont de Nemours and Company
InventorsYing Wang, Steven Dale Ittel
Life of this patent
Estimating the term…
Abstract
Olefins, such as ethylene, are polymerized using as a polymerization catalyst a complex of a selected transition metal with an anionic ligand that has at least three atoms that may coordinate to the transition metal. Also disclosed are the above selected transition metal complexes, and intermediates thereto.
Claims11
A process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., one or more monomers selected from the group consisting of ethylene and an olefin of the formula H2C═CH(CH2)nH (XXII), and a Cr, Mn, V, Ti, Zr or Hf complex of an anion of the formula (I)
- wherein:
- R1 is hydrocarbyl or substituted hydrocarbyl, R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that R1 and R2 taken together may be orthoarylene or substituted ortho-arylene, or R1, R2 and R3 taken together may form one or more rings;
- Z is a bridging group of the formula (II), (III) or (IV)
- Q is nitrogen, oxygen, phosphorous or sulfur, provided that when Z is (II), Q is oxygen;
- R4 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that when Q is oxygen or sulfur R4 is not present;
- R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3 and R6 together may form a ring;
- R7 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3, R6 and R7 together may form an aromatic ring, or R6 and R7 taken together may form a ring;
- R8 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
- R9 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R4 and R9 taken together may be part of a double bond to an imino nitrogen atom, or R8 and R9 taken together may form a carbonyl with the carbon to which they are attached, or R8 and R9 taken together may form a ring, or R4 and R9 taken together may form a ring, or R4, R8 and R9 taken together may form a ring, or R6, R7, R8 and R9 taken together may form an aromatic ring;
- R10, R11, R12 and R13 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R10, R11, R12 and R13 taken together may be ortho-arylene;
- R14 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R14 and R15 taken together may form a carbonyl with the carbon to which they are attached, or R12, R13, R14, and R15 taken together may form an o-arylene group, or R10, R11, R12, R13, R14, and R15 taken together may form a fused aromatic ring system, or R13 and R14 taken together may form a ring;
- R20 and R21 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or R20 and R21 taken together may form a ring;
- each R22 is individually hydrocarbyl, oxygen or alkoxy, provided that when R22 is oxygen, two of R22 are taken together to form T═O;
- n is an integer of 1 or more;
- T is phosphorous or sulfur whose oxidation state is 3 or greater;
- and
- x is equal to the oxidation state of T minus 2.
14 more elements
A process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., one or more monomers selected from the group consisting of ethylene and H2C═CH(CH2)nH (XXII), with a compound of the formula (V)
- wherein:
- R1 is hydrocarbyl or substituted hydrocarbyl, R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that R1 and R2 taken together may be orthoarylene or substituted ortho-arylene, or R1, R2 and R3 taken together may form one or more rings;
- Z is a bridging group of the formula (II), (III) or (IV)
- Q is nitrogen, oxygen, phosphorous or sulfur, provided that when Z is (II), Q is oxygen;
- R4 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that when Q is oxygen or sulfur R4 is not present;
- R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3 and R6 taken together may form a ring;
- R7 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3, R6 and R7 taken together may form an aromatic ring, or R6 and R7 taken together may form a ring;
- R8 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
- R9 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R4 and R9 taken together may be part of a double bond to an imino nitrogen atom, or R8 and R9 taken together may form a carbonyl with the carbon to which they are attached, or R8 and R9 taken together may form a ring, or R4 and R9 taken together may form a ring, or R4, R8 and R9 taken together may form a ring, or R6, R7, R8 and R9 taken together may form an aromatic ring;
- R10, R11, R12 and R13 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R10, R11, R12 and R13 taken together may be ortho-arylene;
- R14 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R14 and R15 taken together may form a carbonyl with the carbon to which they are attached, or R12, R13, R14, and R15 taken together may form an o-arylene group, or R10, R11, R12, R13, R14, and R15 taken together may form a fused aromatic ring system, or R13 and R14 taken together may form a ring;
- R20 and R21 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or R20 and R21 taken together may form a ring;
- each R22 is individually hydrocarbyl, oxygen or alkoxy, provided that when R22 is oxygen, two of R22 are taken together to form T═O;
- n is an integer of 1 or more;
- T is phosphorous or sulfur whose oxidation state is 3 or greater;
- x is equal to the oxidation state of T minus 2;
- M is Ti, Zr, Hf, V, Mn or Cr;
- m is an integer equal to the valence of M minus 2;
- and
- each L1 is independently a monodentate monoanionic ligand and at least for one of L1 an ethylene molecule may insert between L1 and M, and L2 is a monodentate neutral ligand which may be displaced by ethylene or an empty coordination site, provided that an L1 and L2 taken together may be a monoanionic polydentate ligand and at least for one of these monoanionic polydentate ligands ethylene may insert between said monoanionic polydentate ligand and M.
17 more elements
Dependencies are inferred from the claim text.