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 composition comprising a plurality of zinc alkyl compounds and one or more complexes selected from a group 3-10 transition metal, a group 3 main group metal, a lanthanide or an actinide complex, and optionally a suitable activator, wherein the mole ratio of said one or more complexes to said plurality of zinc alkyl compounds is from about 1×10 −6 to 1×10 −2 and wherein alkyl groups of the plurality of zinc alkyl compounds follow a Poisson distribution of chain lengths for chain lengths up to about 200 carbon atoms.
2. A composition as claimed in claim 1 wherein at least one of the one or more complexes contains a neutral, monoanionic or dianionic ligand which can be mondentate, bidentate, tridentate or tetradentate and which comprises at least one N, P, O or S atom.
3. A composition as claimed in claim 1 wherein at least one or more complexes comprises a metallocene having one or more unsubstituted or substituted cyclopentadienyl or cyclopentadienyl moieties in combination with a group 3-6 transition metal, a group 3 main group metal, a lanthanide or an actinide.
4. A composition as claimed in claim 3 wherein the metallocene is represented by the general formula (C p ) m MR n R′ p wherein at least one C p is selected from cyclopentadienyl ring, indenyl, a benzindenyl, or fluorenyl, M is a Group 4, 5 or 6 transition metal, a lanthanide or an actinide; R and R′ are independently selected from halogen, hydrocarbyl group, or hydrocarboxyl groups having 1-20 carbon atoms or combinations thereof; and m=1−3, n=0−3, p=0−3, and the sum of m+n+p equals the oxidation state of M.
5. A composition as claimed in claim 3 wherein the metallocene is represented by the general formula:
(C 5 R′ m ) p R″ s (C 5 R′ m ) Me Q 3-p-x , or
R″ s (C 5 R′ m ) 2 Me Q′
wherein Me is a Group 4, 5 or 6 transition metal, a lanthanide or an actinide; at least one C 5 R′ m is a substituted cyclopentadienyl; each R′, which can be the same or different is hydrogen, alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two carbon atoms joined together to form a part of a substituted or unsubstituted ring or rings having 4 to 20 carbon atoms; R″ is one or more of or a combination of a carbon, a germanium, a silicon, a phosphorous or a nitrogen atom containing radical bridging two (C 5 R′ m ) rings, or bridging one (C 5 R′ m ) ring to M, when p=0, x=1 otherwise “x” is always equal to 0, each Q which can be the same or different, is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having up to 20 carbon atoms, halogen, or alkoxides, Q′ is an alkylidene radical having up to 20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2, and when s is 1, m is 4 and p is 1.
6. A composition as claimed in claim 3 wherein the metallocene is selected from: bis(pentamethylcyclopentadienyl) zirconium dichloride, bis(pentamethylcyclopentadienyl) hafnium dichloride, bis(tetramethylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (tetramethylcyclopentadienyl)(t-butylamido)(dimethylsilane) titanium dimethyl, or (pentamethylcyclopentadienyl)(cyclopentadienyl) zirconium dichloride.
7. A composition as claimed in claim 1 wherein at least one of the one or more complexes 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], 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 ones 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.
8. A composition as claimed in claim 1 wherein at least one of the one or more complexes 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], 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 ones 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.
9. A composition as claimed in claim 1 wherein at least one of the one or more complexes 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], 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.
10. A composition as claimed in claim 1 wherein at least one of the one or more complexes 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], 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.
11. A composition as claimed in claim 10 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.
12. A composition as claimed in claim 10 , wherein Y 1 is C, A 1 to A 3 are each 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.
13. A composition as claimed in claim 1 wherein at least one of the one or more complexes comprises a complex selected from 2,6-diacetylpyridinebis (2,4,6-trimethylanil)FeCl 2 or 2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl 2 .
14. A composition as claimed in claim 1 wherein the one or more complexes comprise two such complexes.
15. A composition as claimed in claim 14 wherein the complex comprises a mixture of 2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl 2 complex and 2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl 2 complex, or a mixture of 2,6-diacetylpyridinebis(2,6-diisopropylanil)CoC 1 2 and 2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl 2 .
16. A composition as claimed in claim 1 wherein one or more of the complexes is supported on a support material.
17. A composition as claimed in claim 16 wherein the support material is selected from silica, silica/alumina, magnesium chloride, zeolites, alumina or zirconia, a polymer or a prepolymer.
18. A composition as claimed in claim 1 including an activator, wherein the activator is an organoaluminium compound.
19. A composition as claimed in claim 18 wherein the organoaluminium compound is selected from trimethylaluminium, triethylaluminium, tributylaluminium, tri-n-octylaluminium, ethylaluminium dichloride, diethylaluminium chloride or alumoxanes.
20. A composition as claimed in claim 1 including an activator, wherein the activator is a hydrocarbylboron compound.
21. A composition as claimed in claim 20 wherein the hydrocarbylboron compound is dimethylphenylammonium tetraphenylborate, trityl tetraphenylborate, triphenylboron, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate, H 30 (OEt 2 ) 2 [(bis-3,5-trifluoromethyl)phenyl]borate, trityl tetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl) boron.