Oligomerization to alpha-olefins

Claim 2

An oligomerization catalyst percursor comprising (i) a transition metal compound wherein the transition metal is selected from the group consisting of nickel, chromium, cobalt, iron, and copper, and mixtures thereof and (ii) at least one organophosphorus sulfonate ligand containing (a) at least one benzene ring having a trivalent phosphorus atom located at one position on the benzene ring and an SO 3 M group located at a position on the benzene ring ortho thereto, or at least one benzene ring having a trivalent phosphorus atom connected through a methylene group to a first position on the benzene ring and an SO 3 M group connected through a methylene group to a second position on the benzene ring ortho to the first position, or at least one bridging or fused aromatic ring system having a trivalent phosphorus atom and an SO 3 M group, each located on the same or different aromatic ring in the system at substituent positions adjacent to one another, or at least one aromatic ring, other than a benzene ring, or heteroaromatic ring, each ring having a trivalent phosphorus atom and an SO 3 M group located at substituent positions adjacent to one another, wherein M is selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NR 4 and PR 4 wherein R is a hydrogen atom or a substituted or unsubstituted hydrocarbyl radical having 1 to 15 carbon atoms and each R can be alike or different or (b) a trivalent phosphorus atom connected through a group having the formula ##STR36## to an SO 3 M group wherein A is an oxygen atom, an NH radical, or an NR radical; R 2 and R 3 are hydrogen atoms or a substituted or unsubstituted hydrocarbyl radical h having 1 to 6 carbon atoms and can be alike or different; x is an integer 0 or 1; y is an integer from 1 to 3; and R and M are as defined above.

Claim 3

The catalyst precursor defined in claim 1 wherein the transition metal compound is a hydrated salt.

Claim 4

The catalyst precursor defined in claim 2 wherein the hydrated salt is selected from the group consisting of halides, sulfonates, tetrafluoroborates, and mixtures thereof.

Claim 5

The catalyst precursor defined in claim 2 wherein the transition metal is nickel.

Claim 6

The catalyst precursor defined in claim 1 wherein the organophosphorus-sulfonate ligand is in the alkali metal salt form.

Claim 7

The catalyst precursor defined in claim 1 wherein the ligand is an ortho-phosphorus sulfonate represented by the following structural formula: ##STR37## wherein R 4 , R 5 , R 6 are hydrogen atoms or substituted or unsubstituted hydrocarbyl radicals having 1 to 20 carbon atoms and can be alike or different; R 4 and R 5 can be connected to form a heterocyclic radical; and M is as set forth above.

Claim 8

The catalyst precursor defined in claim 1 wherein the ligand is an alkylene-phosphinosulfonate represented by the following structural formula: ##STR38## wherein R 2 , R 3 , A, M, x, and y are as set forth above, and R 4 and R 5 are hydrogen atoms or substituted or unsubstituted hydrocarbyl radicals having 1 to 20 carbon atoms, can be alike or different, and can be connected to form a heterocyclic radical.

Claim 9

The catalyst precursor defined in claim 6 wherein R 4 , R 5 , and R 6 , are selected from the group consisting of hydrogen atoms or alkyl, aryl, alkoxy, aroxy, amino, or amido radicals, or mixtures thereof.

Claim 10

The catalyst precursor defined in claim 7 wherein R 4 and R 5 are selected from the group consisting of hydrogen atoms or alkyl, aryl, alkoxy, aroxy, amino, or amido radicals, or mixtures thereof.

Claim 11

The reaction product of the catalyst precursor defined in claim 1 and a catalyst activator, capable of activating the reaction product under oligomerization reaction conditions, said catalyst activator being present in an amount sufficient to activate the reaction product thus converting the reaction product into an oligomerization catalyst.

Claim 12

The reaction product of the catalyst precursor defined in claim 1 and a catalyst activator in an amount sufficient to activate the reaction product thus converting the reaction product into an oligomerization catalyst, said catalyst activator being capable, under oligomerization reaction conditions, of transferring a hydride or an alkyl, alkenyl, alkynyl, or aryl group from itself to the transition metal/liqand complex formed by the reaction of the transition metal compound with the ligand and bonding the group to the transition metal.

Claim 13

The reaction product defined in claim 11 wherein the catalyst activator is selected from the group consisting of borohydrides, aryl boranes, BH 3 , mono-, di-, and trialkyl boranes, aryl borates, tri and tetra coordinate organoaluminum compounds, aluminum hydrides, tri and tetra alkyl boron compounds, organozinc compounds, and mixtures thereof.

Claim 14

The reaction product defined in claim 12 wherein the catalyst activator is a borohydride selected from the group consisting of alkali metal borohydrides, quaternary ammonium borohydrides, alkali metal alkoxyborohydrides, phenoxyborohydrides, or amidoborohydrides, and mixtures thereof.

Claim 15

The reaction product defined in claim 12 wherein the catalyst activator is selected from the group consisting of aryl boranes, aryl borates, BH 3 , mono-, di-, and trialkyl boranes, and mixtures thereof.

Claim 16

The reaction product defined in claim 12 wherein the catalyst activator is selected from the group consisting of tri- or tetra coordinate aluminum compounds, aluminum hydrides, tri- or tetra alkyl boron compounds, and organozinc compounds.

Claim 17

An oligomerization catalyst comprising the reaction product of (i) a transition metal compound wherein the transition metal is selected from the group consisting of nickel, chromium, cobalt, iron, and copper, and mixtures thereof; (ii) in the event that (a) the transition metal is not in the oxidation state of 0 or (b) the transition metal compound does not have a hydride or an alkyl, alkenyl, alkynyl, or aryl group bonded to the transition metal, a catalyst activator, capable of activating the catalyst under oligomerization reaction conditions, said catalyst activator being present in sufficient amount to activate the catalyst; and (iii) at least one organophosphorus sulfonate ligand containing (a) at least one benzene ring having a trivalent phosphorus atom located at one position on the benzene ring and an SO 3 M group located at a position on the benzene ring ortho thereto, or at least one benzene ring having a trivalent phosphorus atom connected through a methylene group to a first position on the benzene ring and an SO 3 M group connected through a methylene group to a second position on the benzene ring ortho to the first position, or at least one bridging or fused aromatic ring system having a trivalent phosphorus atom and an SO 3 M group, each located on the same or different aromatic ring in the system at substituent positions adjacent to one another, or at least one aromatic ring, other than a benzene ring, or heteroaromatic ring, each ring having a trivalent phosphorus atom and an SO 3 M group located at substituent positions adjacent to one another, wherein M is selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NR 4 and PR 4 wherein R is a hydrogen atom or a substituted or unsubstituted hydrocarbyl radical having 1 to 15 carbon atoms and each R can be alike or different or (b) a trivalent phosphorus atom connected through a group having the formula ##STR39## to an SO 3 M group wherein A is an oxygen atom, an NH radical, or an NR radical; R 2 and R 3 are hydrogen atoms or a substituted or unsubstituted hydrocarbyl radical having 1 to 6 carbon atoms and can be alike or different; x is an integer 0 or 1; y is an integer from 1 to 3; and R and M are as defined above.

Claim 18

An oligomerization catalyst comprising the reaction product of (i) a transition metal compound wherein the transition metal is selected from the group consisting of nickel, chromium, cobalt, iron, and copper, and mixtures thereof; (ii) in the event that (a) the transition metal is not in the oxidation state of 0 or (b) the transition metal compound does not have a hydride or an alkyl, alkenyl, alkynyl, or aryl group bonded to the transition metal, a catalyst activator, capable of activating the catalyst under oligomerization reaction conditions, said catalyst activator being present in sufficient amount to activate the catalyst; and (iii) at least one organophosphorus sulfonate ligand containing (a) at least one benzene ring having a trivalent phosphorus atom located at one position on the benzene ring and an SO 3 M group located at a position on the benzene ring ortho thereto, or at least one benzene ring having a trivalent phosphorus atom connected through a methylene group to a first position on the benzene ring and an SO 3 M group connected through a methylene group to a second position on the benzene ring ortho to the first position, or at least one bridging or fused aromatic ring system having a trivalent phosphorus atom and an SO 3 M group, each located on the same or different aromatic ring in the system at substituent positions adjacent to one another, or at least one aromatic ring, other than a benzene ring, or heteroaromatic ring, each ring having a trivalent phosphorus atom and an SO 3 M group located at substituent positions adjacent to one another, wherein M is selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NR 4 and PR 4 wherein R is a hydrogen atom or a substituted or unsubstituted hydrocarbyl radical having 1 to 15 carbon atoms and each R can be alike or different or (b) a trivalent phosphorus atom connected through a group having the formula ##STR39## to an SO 3 M group wherein A is an oxygen atom, an NH radical, or an NR radical; R 2 and R 3 are hydrogen atoms or a substituted or unsubstituted hydrocarbyl radical having 1 to 6 carbon atoms and can be alike or different; x is an integer 0 or 1; y is an integer from 1 to 3; and R and M are as defined above.

Claim 19

An oligomerization catalyst comprising the reaction product of (i) a transition metal compound wherein the transition metal is selected from the group consisting of nickel, chromium, cobalt, iron, and copper, and mixtures thereof; (ii) in the event that (a) the transition metal is not in the oxidation state of 0 or (b) the transition metal compound does not have a hydride or an alkyl, alkenyl, alkynyl, or aryl group bonded to the transition metal, a catalyst activator in sufficient amount to activate the catalyst, said catalyst activator consisting of a compound or compounds capable of transferring, under oligomerization reaction conditions, a hydride or an alkyl, alkenyl, alkynyl, or aryl group from itself to the transition metal/ligand complex formed by the reaction of the transition metal compound with the ligand and bonding the group to the transition metal; and (iii) at least one organophosphorus sulfonate ligand containing (a) at least one benzene ring having a trivalent phosphorus atom located at one position on the benzene ring and an SO 3 M group located at a position on the benzene ring ortho thereto, or at least one benzene ring having a trivalent phosphorus atom connected through a methylene group to a first position on the benzene ring and an SO 3 M group connected through a methylene group to a second position on the benzene ring ortho to the first position, or at least one bridging or fused aromatic ring system having a trivalent phosphorus atom and an SO 3 M group, each located on the same or different aromatic ring in the system at substituent positions adjacent to one another, or at least one aromatic ring, other than a benzene ring, or heteroaromatic ring, each ring having a trivalent phosphorus atom and an SO 3 M group located at substituent positions adjacent to one another, wherein M is selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NR 4 and PR 4 wherein R is a hydrogen atom or a substituted or unsubstituted hydrocarbyl radical having 1 to 15 carbon atoms and each R can be alike or different or (b) a trivalent phosphorus atom connected through a group having the formula ##STR40## to an SO 3 M group wherein A is an oxygen atom, an NH radical, or an NR radical; R 2 and R 3 are hydrogen atoms or a substituted or unsubstituted hydrocarbyl radical having 1 to 6 carbon atoms and can be alike or different; x is an integer 0 or 1; y is an integer from 1 to 3; and R and M are as defined above.

Claim 20

An oligomerization catalyst comprising the reaction product of (i) a transition metal compound wherein the transition metal is selected from the group consisting of nickel, chromium, cobalt, iron, and copper, and mixtures thereof; (ii) in the event that (a) the transition metal is not in the oxidation state of 0 or (b) the transition metal compound does not have a hydride or an alkyl, alkenyl, alkynyl, or aryl group bonded to the transition metal, a catalyst activator in sufficient amount to activate the catalyst, said catalyst activator consisting of a compound or compounds capable of transferring, under oligomerization reaction conditions, a hydride or an alkyl, alkenyl, alkynyl, or aryl group from itself to the transition metal/ligand complex formed by the reaction of the transition metal compound with the ligand and bonding the group to the transition metal; and (iii) at least one organophosphorus sulfonate ligand containing (a) at least one benzene ring having a trivalent phosphorus atom located at one position on the benzene ring and an SO 3 M group located at a position on the benzene ring ortho thereto, or at least one benzene ring having a trivalent phosphorus atom connected through a methylene group to a first position on the benzene ring and an SO 3 M group connected through a methylene group to a second position on the benzene ring ortho to the first position, or at least one bridging or fused aromatic ring system having a trivalent phosphorus atom and an SO 3 M group, each located on the same or different aromatic ring in the system at substituent positions adjacent to one another, or at least one aromatic ring, other than a benzene ring, or heteroaromatic ring, each ring having a trivalent phosphorus atom and an SO 3 M group located at substituent positions adjacent to one another, wherein M is selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NR 4 and PR 4 wherein R is a hydrogen atom or a substituted or unsubstituted hydrocarbyl radical having 1 to 15 carbon atoms and each R can be alike or different or (b) a trivalent phosphorus atom connected through a group having the formula ##STR40## to an SO 3 M group wherein A is an oxygen atom, an NH radical, or an NR radical; R 2 and R 3 are hydrogen atoms or a substituted or unsubstituted hydrocarbyl radical having 1 to 6 carbon atoms and can be alike or different; x is an integer 0 or 1; y is an integer from 1 to 3; and R and M are as defined above.

Claim 21

The catalyst defined in claim 17 wherein the ligand contains at least one benzene ring having a trivalent phosphorus atom located at one position on the benzene ring and an SO 3 M group located at a position on the benzene ring ortho thereto.

Claim 22

The catalyst defined in claim 17 wherein the ligand contains at least one benzene ring having a trivalent phosphorus atoms connected through a methylene group to a first position on the benzene ring and an SO 3 M group connected through a methylene group to a second position on the benzene ring.

Claim 23

The catalyst defined in claim 17 wherein the ligand contains at least one bridging or fused aromatic ring system having a trivalent phosphorus atom and an SO 3 M group, each located on a different aromatic ring in the system at substituent positions adjacent to one another.

Claim 24

The catalyst defined in claim 17 wherein the ligand contains at least one aromatic ring, other than a benzene ring, or heteroaromatic ring, each ring having a trivalent phosphorus atom and an SO 3 M group located at substituent positions adjacent to one another.

Claim 25

The catalyst defined in claim 17 wherein the catalyst activator is selected from the group consisting of borohydrides, aryl boranes, BH 3 , mono-, di-, and trialkyl boranes, aryl borates, tri and tetra coordinate organoaluminum compounds, aluminum hydrides, tri and tetra alkyl boron compounds, organozinc compounds, and mixtures thereof.

Claim 26

The catalyst defined in claim 17 wherein the transition metal compound is a hydrated salt.

Claim 27

The catalyst defined in claim 23 wherein the hydrated salt is selected from the group consisting of halides, sulfonates, tetrafluoroborates, and mixtures thereof.

Claim 28

The catalyst defined in claim 23 wherein the transition metal is nickel.

Claim 29

The catalyst defined in claim 22 wherein the catalyst activator is a borohydride selected from the group consisting of alkali metal borohydrides, quaternary ammonium borohydrides, alkali metal alkoxyborohydrides, phenoxyborohydrides, or amidoborohydrides, and mixtures thereof.

Claim 30

The catalyst defined in claim 22 wherein the catalyst activator is selected from the group consisting of aryl boranes, BH 3 , mono-, di-, and trialkyl boranes, aryl borates, and mixtures thereof.

Claim 31

The catalyst defined in claim 22 wherein the catalyst activator is selected from the group consisting of tri or tetra coordinate organoaluminum compounds, aluminum hydrides, tri or tetra alkyl boron compounds, and organozinc compounds.

Claim 32

The catalyst defined in claim 28 wherein the catalyst activator is triethylaluminum.

Claim 33

The catalyst defined in claim 17 wherein the organophosphorus-sulfonate ligand is in the alkali metal salt form.

Claim 34

The catalyst defined in claim 17 wherein the ligand is an ortho-phosphorus sulfonate represented by the following structural formula: ##STR41## wherein R 4 , R 5 , R 6 are hydrogen atoms or substituted or unsubstituted hydrocarbyl radicals having 1 to 20 carbon atoms and can be alike or different; R 4 and R 5 can be connected to form a heterocyclic radical; and M is as set forth above.

Claim 35

The catalyst defined in claim 17 wherein the ligand is an alkylene-phosphinosulfonate represented by the following structural formula: ##STR42## wherein R 2 , R 3 , A, M, x, and y are as set forth above, and R 4 and R 5 are hydrogen atoms or substituted or unsubstituted hydrocarbyl radicals having 1 to 20 carbon atoms, can be alike or different, and can be connected to form a heterocyclic radical.

Claim 36

The catalyst defined in claim 31 wherein R 4 , R 5 , and R 6 are selected from the group consisting of hydrogen atoms or alkyl, aryl, alkoxy, aroxy, amino, or amido radicals, or mixtures thereof.

Claim 37

The catalyst defined in claim 32 wherein R 4 and R 5 are selected from the group consisting of hydrogen atoms or alkyl, aryl, alkoxy, aroxy, amino, or amido radicals, or mixtures thereof.