Chain growth reaction process
AssigneeBP Chemicals Limited
InventorsGeorge Johan Peter Britovsek, Steven Alan Cohen, Vernon Charles Gibson
Life of this patent
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Abstract
A process is disclosed for the preparation of zinc alkyl chain growth products via a catalysed chain growth reaction of an alpha-olefin on a zinc alkyl, wherein the chain growth catalyst system employs a group 3-10 transition metal, or a group 3 main group metal, or a lanthanide or actinide complex, and optionally a suitable activator. The products can be further converted into alpha-olefins by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, or into primary alcohols, by oxidation of the resulting zinc alkyl chain growth product to form alkoxide compounds, followed by hydrolysis of the alkoxides.
Claims55
A composition comprising a plurality of alkyl zinc compounds and a group 3-10 transition metal complex or a lanthanide or actinide complex, and optionally an activator, wherein the mole ratio of the complex to the plurality of zinc alkyl compounds in the composition is in the range of from about 1:10,000,000 to 1:100 and wherein the alkyl groups of the plurality of zinc alkyl compounds follow a Poisson statistical distribution of chain lengths up to about 200 carbon atoms or a Schulz-Flory statistical distribution of chain lengths up to about 50,000 carbon atoms.
A process for the preparation of alpha-olefins, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product is carried out using a Ni catalyst.
A process for the preparation of zinc alkyl chain growth products via a catalysed chain growth reaction of an alpha-olefin on a zinc alkyl compound, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the zinc alkyl compound is a species or mixture of species containing a R′R″ CH—Zn or R′R″ C—Zn moiety, wherein R′ and R″ are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, and substituted hydrocarbyl, and may be linked to form a cyclic species, subject to the proviso that in the case of R′R″ C—Zn, the C bonded to the Zn is unsaturated.
A process for the preparation of alpha-olefins, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the zinc alkyl compound is a species or mixture of species containing a R′R″ CH—Zn or R′R″ C—Zn moiety, wherein R′ and R″ are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, and substituted hydrocarbyl, and may be linked to form a cyclic species, subject to the proviso that in the case of R′R″ C—Zn, the C bonded to the Zn is unsaturated.
A process for the preparation of zinc alkyl chain growth products via a catalysed chain growth reaction of an alpha-olefin on a zinc alkyl compound, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a metallocene catalyst, which contains at least one cyclopentadienyl-based ring ligand.
A process for the preparation of alpha-olefins, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a metallocene catalyst, which contains at least one cyclopentadienyl-based ring ligand.
A process for the preparation of zinc alkyl chain growth products via a catalysed chain growth reaction of an alpha-olefin on a zinc alkyl compound, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a complex of the Formula (I):
- wherein M is Y[II], Y[III], Sc[II], Sc[III], Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II], X represents an atom or group covalently or ionically bonded to the transition metal M;
- Y1 is C or P(Rc);
- Y2 is —O(R7), —O (in which case the bond from O to M is covalent), —C(Rb)═O, —C(Rb)═N(R7), —P(Rb)(Rd)═N(R7) or —P(Rb)(Rd)═O;
- Ra, Rb, Rc, Rd, R5 and R7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and SiR′3 where each R′ is independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group and a substituted heterohydrocarbyl group, and adjacent ones of Ra, Rb, Rc, Rd, R5 and R7 may be joined together to form a ring;
- G is a direct bond between Y1 and Y2, L is a group datively bound to M;
- n is from 0 to 5;
- m is 1 to 3 and q is 1 or 2.
A process for the preparation of alpha-olefins, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a complex of the Formula (I):
- wherein M is Y[II], Y[III], Sc[II], Sc[III], Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II], X represents an atom or group covalently or ionically bonded to the transition metal M;
- Y1 is C or P(Rc);
- Y2 is —O(R7), —O (in which case the bond from O to M is covalent), —C(Rb)═O, —C(Rb)═N(R7), —P(Rb)(Rd)═N(R7) or —P(Rb)(Rd)═O;
- Ra, Rb, Rc, Rd, R5 and R7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and SiR′3 where each R′ is independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group and a substituted heterohydrocarbyl group, and adjacent ones of Ra, Rb, Rc, Rd, R5 and R7 may be joined together to form a ring;
- G is a direct bond between Y1 and Y2, L is a group datively bound to M;
- n is from 0 to 5;
- m is 1 to 3 and q is 1 or 2.
A process for the preparation of zinc alkyl chain growth products via a catalysed chain growth reaction of an alpha-olefin on a zinc alkyl compound, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a complex of the Formula (II):
- wherein M is Y[II], Y[III], Sc[II], Sc[III], Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II], X represents an atom or group covalently or ionically bonded to the transition metal M;
- Ra, Rb, Rx, and R5 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and SiR′3 where each R′ is independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group and a substituted heterohydrocarbyl group, and adjacent ones of Ra, Rb, Rx, and R5 may be joined together to form a ring;
- L is a group datively bound to M;
- n is from 0 to 5;
- m is 1 to 3 and q is 1 or 2.
A process for the preparation of alpha-olefins, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a complex of the Formula (II):
- wherein M is Y[II], Y[III], Sc[II], Sc[III], Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II], X represents an atom or group covalently or ionically bonded to the transition metal M;
- Ra, Rb, Rx, and R5 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and SiR′3 where each R′ is independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group and a substituted heterohydrocarbyl group, and adjacent ones of Ra, Rb, Rx, and R5 may be joined together to form a ring;
- L is a group datively bound to M;
- n is from 0 to 5;
- m is 1 to 3 and q is 1 or 2.
A process for the preparation of zinc alkyl chain growth products via a catalysed chain growth reaction of an alpha-olefin on a zinc alkyl compound, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a complex of the Formula (III):
- wherein M is Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II], Cu[I], Cu[II];
- X represents an atom or group covalently or ionically bonded to the transition metal M;
- Ra, Rb, R5 and R7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and SiR′3 where each R′ is independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl, and Ra and Rb may be joined together to form a ring;
- and L is a group datively bound to M;
- n is from 0 to 5;
- m is 1 to 3 and q is 1 or 2.
A process for the preparation of alpha-olefins, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a complex of the Formula (III):
- wherein M is Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II], Cu[I], Cu[II];
- X represents an atom or group covalently or ionically bonded to the transition metal M;
- Ra, Rb, R5 and R7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and SiR′3 where each R′ is independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl, and Ra and Rb may be joined together to form a ring;
- and L is a group datively bound to M;
- n is from 0 to 5;
- m is 1 to 3 and q is 1 or 2.
A process for the preparation of zinc alkyl chain growth products via a catalysed chain growth reaction of an alpha-olefin on a zinc alkyl compound, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a complex of the Formula (IV):
- wherein M[T] is Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II];
- X represents an atom or group covalently or ionically bonded to the transition metal M;
- T is the oxidation state of the transition metal M and b is the valency of the atom or group X;
- Y1 is C or P(Rc), A1 to A3 are each independently N or P or CR, with the proviso that at least one is CR;
- and R, Rc, R4, R5, R6 and R7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and SiR′3 where each R′ is independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl.
A process for the preparation of alpha-olefins, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system comprises a complex of the Formula (IV):
- wherein M[T] is Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II];
- X represents an atom or group covalently or ionically bonded to the transition metal M;
- T is the oxidation state of the transition metal M and b is the valency of the atom or group X;
- Y1 is C or P(Rc), A1 to A3 are each independently N or P or CR, with the proviso that at least one is CR;
- and R, Rc, R4, R5, R6 and R7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and SiR′3 where each R′ is independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl.
A process for the preparation of zinc alkyl chain growth products via a catalysed chain growth reaction of an alpha-olefin on a zinc alkyl compound, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system is 2,6-diacetylpyridinebis(2,4,6 trimethyl anil)FeCl2 or 2,6-diacetylpyridinebis(2,6 diisopropyl anil)FeCl2.
A process for the preparation of alpha-olefins, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, wherein the mole ratio of the complex in the catalyst system to the zinc alkyl compound is in the range of from about 1:10,000,000 to 1:100, and wherein the chain growth catalyst system is 2,6-diacetylpyridinebis(2,4,6 trimethyl anil)FeCl2 or 2,6-diacetylpyridinebis(2,6 diisopropyl anil)FeCl2.
A process for the preparation of primary alcohols, comprising contacting an alpha-olefin and a zinc alkyl compound with a chain growth catalyst system which employs a group 3-10 transition metal complex or a group 3 main group metal complex, or a lanthanide or actinide complex, and optionally an activator to form a zinc alkyl chain growth product, followed by oxidation of the zinc alkyl chain growth product to form alkoxide compounds, followed by hydrolysis of the alkoxides compounds to produce primary alcohols.
Dependencies are inferred from the claim text.