Process of making aluminum alkyls
View Patent ↗The present invention generally relates to a new process of making a trialkyl aluminum compound in which at least one alkyl group is a primary alkyl derived from an internal olefin or alpha-olefin. The process employs an isomerization/hydroalumination catalyst.
1. An isomerization/hydroalumination catalyst of formula (I):
wherein:
Each of R 1 and R 6 independently is a (C 1 -C 40 )hydrocarbyl;
Each of R 2 , R 3 , R 4 , and R 5 independently is a hydrogen atom or (C 1 -C 40 )hydrocarbyl;
Each L independently is a halo, hydrogen atom, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, (C 1 -C 40 )hydrocarbylC(O)N(H)—, (C 1 -C 40 )hydrocarbylC(O)N((C 1 -C 20 )hydrocarbyl)-, (C 1 -C 40 )hydrocarbylC(O)O—, R K R L N—, R L O—, R L S—, or R K R L P—, wherein each R K and R L independently is a hydrogen atom, (C 1 -C 40 )hydrocarbyl, [(C 1 -C 10 )hydrocarbyl] 3 Si, [(C 1 -C 10 )hydrocarbyl] 3 Si(C 1 -C 10 )hydrocarbyl, or (C 1 -C 40 )heterohydrocarbyl, or R K and R L are taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, wherein each L independently is a monoanionic moiety that is bonded to M; and
Each M independently is a metal, that is nickel, copper, or zinc, the metal being in a formal oxidation state of +2;
Each of the aforementioned (C 1 -C 40 )alkyl, (C 1 -C 10 )hydrocarbyl, (C 1 -C 20 )hydrocarbyl, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, (C 2 -C 40 )hydrocarbylene, and (C 1 -C 40 )heterohydrocarbylene independently is the same as or different than another and independently is unsubstituted or substituted with one or more substituents R S ; and
Each R S independently is halo, polyfluoro, perfluoro, unsubstituted (C 1 -C 18 )hydrocarbyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, oxo (i.e., ═O), R 3 Si—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, wherein each R independently is an unsubstituted (C 1 -C 18 )hydrocarbyl.
2. The isomerization/hydroalumination catalyst as in claim 1 , wherein the isomerization/hydroalumination catalyst of formula (I) is an isomerization/hydroalumination catalyst of formula (I-A):
3. The isomerization/hydroalumination catalyst as in claim 1 , wherein the isomerization/hydroalumination catalyst of formula (I) is an isomerization/hydroalumination catalyst of formula (I-B):
wherein R 6C independently is a hydrogen atom or (C 1 -C 3 )alkyl, and each of R 6A and R 6B independently is a hydrogen atom or (C 1 -C 3 )alkyl, or R 6A and R 6B are taken together to form diradical of formula: —C(H)═C(H)—C(H)═C(H)—.
4. The isomerization/hydroalumination catalyst as in claim 1 , wherein the isomerization/hydroalumination catalyst of formula (I) is an isomerization/hydroalumination catalyst of formula (I-C):
wherein there are from 0 to 5 R 1A and each R 1A independently is a hydrogen atom or (C 1 -C 3 )alkyl.
5. The isomerization/hydroalumination catalyst as in claim 1 , wherein the isomerization/hydroalumination catalyst of formula (I) is an isomerization/hydroalumination catalyst of formula (I-D):
wherein there are from 0 to 5 R 1A and each R 1A independently is a hydrogen atom or (C 1 -C 3 )alkyl.
6. The isomerization/hydroalumination catalyst as in claim 1 , wherein each of R 2 , R 3 , and R 4 independently is a hydrogen atom or methyl.
7. The isomerization/hydroalumination catalyst as in claim 1 , wherein R 5 is a hydrogen atom, (C 1 -C 6 )alkyl, or (C 6 -C 10 )aryl.
8. The isomerization/hydroalumination catalyst as in claim 1 , wherein each of R 1 and R 6 independently is (C 1 -C 6 )alkyl or (C 6 -C 10 )aryl.
9. An isomer isomerization/hydroalumination catalyst of formula (II):
wherein:
R 6 independently is a (C 1 -C 40 )hydrocarbyl;
Each of R 2 , R 3 , R 4 , and R 5 independently is a hydrogen atom or (C 1 -C 40 )hydrocarbyl;
Each L independently is a halo, hydrogen atom, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, (C 1 -C 40 )hydrocarbylC(O)N(H)—, (C 1 -C 40 )hydrocarbylC(O)N((C 1 -C 20 )hydrocarbyl)-, (C 1 -C 40 )hydrocarbylC(O)O—, R K R L N—, R L O—, R L S—, or R K R L P—, wherein each R K and R L independently is a hydrogen atom, (C 1 -C 40 )hydrocarbyl, [(C 1 -C 10 )hydrocarbyl] 3 Si, [(C 1 -C 10 )hydrocarbyl] 3 Si(C 1 -C 10 )hydrocarbyl, or (C 1 -C 40 )heterohydrocarbyl, or R K and R L are taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, wherein each L independently is a monoanionic moiety that is bonded to M; and
Co is cobalt in a formal oxidation state of +2;
Each of the from 1 to 5 R 1A independently is a (C 1 -C 40 )alkyl that is unsubstituted or substituted with one or more substituents R S or any two adjacent R 1A are taken together to form diradical of formula: —C(H)═C(H)—C(H)═C(H)— and the remainder of R 1A are hydrogen atoms;
Each of the aforementioned (C 1 -C 40 )alkyl, (C 1 -C 10 )hydrocarbyl, (C 1 -C 20 )hydrocarbyl, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, (C 2 -C 40 )hydrocarbylene, and (C 1 -C 40 )heterohydrocarbylene independently is the same as or different than another and independently is unsubstituted or substituted with one or more substituents R S ; and
Each R S independently is halo, polyfluoro, perfluoro, unsubstituted (C 1 -C 18 )hydrocarbyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, oxo (i.e., ═O), R 3 Si—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, wherein each R independently is an unsubstituted (C 1 -C 18 )hydrocarbyl.
10. The isomerization/hydroalumination catalyst as in claim 9 , wherein the isomerization/hydroalumination catalyst of formula (II) is an isomerization/hydroalumination catalyst of formula (II-A):
11. The isomerization/hydroalumination catalyst as in claim 1 , wherein the isomerization/hydroalumination catalyst of formula (II) is an isomerization/hydroalumination catalyst of formula (II-B):
wherein R 6C independently is a hydrogen atom or (C 1 -C 3 )alkyl, and each of R 6A and
R 6B independently is a hydrogen atom or (C 1 -C 3 )alkyl.
12. The isomerization/hydroalumination catalyst as in claim 9 , wherein the isomerization/hydroalumination catalyst of formula (II) is an isomerization/hydroalumination catalyst of formula (II-C):
wherein R 6C independently is a hydrogen atom or (C 1 -C 3 )alkyl, and each of R 6A and
R 6B independently is a hydrogen atom or (C 1 -C 3 )alkyl.
13. The isomerization/hydroalumination catalyst as in claim 9 , wherein each of R 2 , R 3 , and R 4 independently is a hydrogen atom or methyl.
14. The isomerization/hydroalumination catalyst as in claim 9 , wherein R 5 is a hydrogen atom, (C 1 -C 6 )alkyl, or (C 6 -C 10 )aryl.
15. The isomerization/hydroalumination catalyst as in claim 9 , wherein the isomerization/hydroalumination catalyst is any one of formulas (1) to (5):
16. A process for preparing a trialkyl aluminum compound, the process comprising a step of contacting together ingredients comprising ingredients (a), (b), and (c):
(a) a precursor trialkyl aluminum of formula (A):
wherein of the three R A in formula (A), two R A independently are (C 1 -C 40 )alkyl and one
R A independently is (C 2 -C 40 )alkyl;
(b) an internal olefin of formula (B):
H 3 C—(CH 2 ) x —CH═CH—(CH 2 ) y —CH 3 (B),
wherein each of x and y independently is an integer of from 0 to 50, or
an alpha-olefin of formula (E):
CH 2 ═CH 2 —(CH 2 ) z CH 3 (E),
wherein z is an integer equal to the sum of 1+x+y; or
a mixture comprising the internal olefin of formula (B) and the alpha-olefin of formula (E); and
(c) a catalytic amount of an isomerization/hydroalumination catalyst of formula (I):
wherein:
Each of R 1 and R 6 independently is a (C 1 -C 40 )hydrocarbyl;
Each of R 2 , R 3 , R 4 , and R 5 independently is a hydrogen atom or (C 1 -C 40 )hydrocarbyl;
Each L independently is a halo, hydrogen atom, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, (C 1 -C 40 )hydrocarbylC(O)N(H)—, (C 1 -C 40 )hydrocarbylC(O)N((C 1 -C 20 )hydrocarbyl)-, (C 1 -C 40 )hydrocarbylC(O)O—, R K R L N—, R L O—, R L S—, or R K R L P—, wherein each R K and R L independently is a hydrogen atom, (C 1 -C 40 )hydrocarbyl, [(C 1 -C 10 )hydrocarbyl] 3 Si, [(C 1 -C 10 )hydrocarbyl] 3 Si(C 1 -C 10 )hydrocarbyl, or (C 1 -C 40 )heterohydrocarbyl, or R K and R L are taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, wherein each L independently is a monoanionic moiety that is bonded to M; and
Each M independently is a metal that is iron, cobalt, nickel, copper, or zinc, the metal being in a formal oxidation state of +2;
Each of the aforementioned (C 1 -C 40 )alkyl, (C 1 -C 10 )hydrocarbyl, (C 1 -C 20 )hydrocarbyl, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, (C 2 -C 40 )hydrocarbylene, and (C 1 -C 40 )heterohydrocarbylene independently is the same as or different than another and independently is unsubstituted or substituted with one or more substituents R S ; and
Each R S independently is halo, polyfluoro, perfluoro, unsubstituted (C 1 -C 18 )hydrocarbyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, oxo (i.e., ═O), R 3 Si—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, wherein each R independently is an unsubstituted (C 1 -C 18 )hydrocarbyl;
wherein the contacting step is performed under (trialkyl aluminum compound)-forming conditions and prepares a trialkyl aluminum compound of formula (D):
wherein at least one R D is a primary alkyl group derived from the internal olefin of formula (B) or derived from the alpha-olefin of formula (E), and any remaining R D independently are (C 1 -C 40 )alkyl.
17. The process as in claim 16 , wherein each M independently is the metal that is iron, nickel, copper, or zinc.
18. The process as in claim 17 , wherein M is iron.
19. The process as in claim 16 , wherein M is cobalt.