Chain growth reaction process
View Patent ↗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.
1. A process for the preparation of zinc alkyl compounds having a statistical distribution of chain lengths comprising contacting a C 2 to C 26 alpha-olefin or mixtures thereof, with a chain growth catalyst system at a temperature in the range from 20° to 200° C., wherein the chain growth catalyst system employs a transition metal complex is selected from the group consisting of
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], or Pd[II], X represents an atom or group covalently or ionically bonded to the transition metal M; Y 1 is C or P(R c ); Y 2 is —O(R 7 ), —O (in which case the bond from O to M is covalent), —C(R b )O, —C(R b )═N(R 7 ), —P(R b )(R d )═N(R 7 ) or —P(R b )(R d )═O; R a , R b , R c , R d , R 5 and R 7 are each independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl or SiR′ 3 where each R′ is independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and any adjacent R′ groups bonded to the same Si atom may be joined together to form a ring; G is a direct bond between Y 1 and Y 2 , or is a bridging group, which optionally contains a third atom linked to M when q is 1; 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 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], or Pd[II], X represents an atom or group covalently or ionically bonded to the transition metal M; R a , R b , R x , and R 5 are each independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl or SiR′ 3 where each R′ is independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and any adjacent R′ groups bonded to the same Si atom ma 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 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], or Cu[II]; X represents an atom or group covalently or ionically bonded to the transition metal M; R a , R b , R 5 and R 7 are each independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl or SiR′ 3 where each R′ is independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and R a and R b 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; and
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], or 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; Y 1 is C or P(R c ), A 1 to A 3 are each independently N or P or CR, with the proviso that at least one is CR; and R, R c , R 4 , R 5 , R 6 and R 7 are each independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl or SiR′ 3 where each R′ is independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;
and wherein the statistical distribution is a Poisson distribution, a Schultz-Flory distribution, or a distribution intermediate of a Poisson distribution and a Schultz-Flory distribution.
2. A process as claimed in claim 1 wherein the olefin is a C 2 to C 16 linear alpha-olefin.
3. A process as claimed in claim 1 or 2 wherein the process is carried out as a homogeneous liquid phase reaction in the presence of inert hydrocarbon diluent.
4. A process as claimed in claim 3 wherein the diluent is toluene or heptanes.
5. A process as claimed in claim 3 wherein the process is carried out as a continuous process.
6. A process as claimed in claim 1 wherein the process is carried out as a slurry process.
7. A process as claimed in claim 1 wherein the process is carried out as a gas phase process.
8. A process as claimed in claim 1 wherein the one or more complexes is supported on a support material.
9. A process as claimed in claim 8 wherein the support material is selected from silica, silica/alumina, magnesium chloride, zeolites, alumina zirconia, a polymer, or a prepolymer.
10. A process as claimed in claim 1 wherein Y 1 is C, and A 1 to A 3 are each independently CR, or A 1 and A 3 are both N and A 2 is CR, or one of A 1 to A 3 is N and the others are independently CR.
11. A process according to claim 1 wherein Y 1 is C, and A 1 to A 3 are each independently CR, and R 5 is represented by the group “P” and R 7 is represented by the group “Q” as follows:
wherein R 19 to R 28 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; when any two or more of R 4 , R 6 and R 19 to R 28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents.
12. A process as claimed in claim 1 wherein the chain growth catalyst system is selected from 2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl 2 or 2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl 2 .
13. A process as claimed in claim 1 wherein the optional activator for the chain growth catalyst system is selected from organoaluminium compounds or hydrocarbylboron compounds.
14. A process as claimed in claim 1 wherein the mole ratio of transition metal to zinc alkyl is between 1×10 −7 and 1×10 −1 .
15. A process as claimed in claim 1 wherein the catalyst is activated by incubation in aluminoxane solution for about 5 minutes at 20° C. prior to addition to the zinc alkyl.