Aluminoxane compositions, their preparation, and their use in catalysis
View Patent ↗Aluminoxane compositions derived from aluminoxane source, halogen source, and Lewis base are provided. Such compositions are useful for activating catalysts for olefin polymerization.
1. A composition comprising individual components of:
a) aluminoxane source;
b) halogen source; and
c) Lewis base,
wherein said aluminoxane source is combined with said Lewis base before combining with said halogen source;
and wherein said halogen source is:
(i) a halohydrocarbon of the formula R n CX 4−n , where n=1-3, X is fluorine, and wherein R is, independently, a hydrogen atom or a hydrocarbyl group having from one to about twenty carbon atoms;
(ii) a halohydrocarbon of the formula: ArG n , wherein Ar is an aromatic hydrocarbon ring system containing up to about 25 carbon atoms, G is —CX 3 , —CX 2 R 1 , or —CX(R 1 ) 2 , X is, fluorine, R 1 is, independently, a hydrogen atom or C 1-4 alkyl group; and n is 1 to 5;
(iii) a siloxane having at least one hydrocarbyl group containing from about 1 to 30 carbon atoms, wherein at least one of the hydrocarbyl groups contains at least one labile fluorine atom;
(iv) a silane of the formula R′ n SiX 4−n , wherein n=1-3, X is fluorine, and wherein R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms;
(v) a tin compound of the formula R′ n SnX 4−n , wherein n=1-3, X is fluorine, and wherein R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms; or
(vi) a hydrocarbyl aluminum halide of the formula R″ m AlX 3−m , wherein m=1 or 2, where X is fluorine, and wherein R″ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms.
2. The composition of claim 1 wherein the aluminoxane source comprises one or more of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
3. The composition of claim 1 , wherein the Lewis base comprises one or more of mono-dentate donor and multi-dentate donor.
4. The composition of claim 1 , wherein the Lewis base comprises octamethyltrisiloxane.
5. The composition of claim 1 , wherein the Lewis base comprises NMeR 2 2 , and each R 2 is independently hydrogen atom or hydrocarbyl group having up to about 24 carbon atoms.
6. A composition derived from at least:
a) aluminoxane source comprising up to about 30 mol % fluorine atoms relative to Al atoms; and
h) Lewis base,
wherein said halogen atoms in said aluminoxane source is provided by a halogen source, wherein said halogen source is:
(i) a halohydrocarbon of the formula R n CX 4−n , wherein n=1-3, X is fluorine, and wherein R is, independently, a hydrogen atom or a hydrocarbyl group having from one to about twenty carbon atoms;
(ii) a halohydrocarbon of the formula: ArG n , wherein Ar is an aromatic hydrocarbon ring system containing up to about 25 carbon atoms, G is —CX 3 , —CX 2 R 1 , or —CX(R 1 ) 2 , X is fluorine, R 1 is, independently, a hydrogen atom or C 1-4 alkyl group; and n is 1 to 5;
(iii) a siloxane having at least one hydrocarbyl group containing from about 1 to 30 carbon atoms, wherein at least one of the hydrocarbyl groups contains at least one labile fluorine atom;
(iv) a silane of the formula R′ n SiX 4−n , wherein n=1-3, X is fluorine, and wherein R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms;
(v) a tin compound of the formula R′ n SnX 4−n , wherein n=1-3, X is fluorine, and wherein R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms; or
(vi) a hydrocarbyl aluminum halide of the formula R″ m AlX 3−m , wherein m =1 or 2, where X is fluorine, and wherein R″ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms.
7. A method of preparing a composition comprising combining individual components of:
a) aluminoxane source;
b) halogen source; and
c) Lewis base,
wherein said aluminoxane source is combined with said Lewis base before combining with said halogen source; and wherein said halogen source is:
(i) a halohydrocarbon of the formula R n CX 4−n , wherein n=1-3, X is fluorine, and wherein R is, independently, a hydrogen atom or a hydrocarhyl group having from one to about twenty carbon atoms;
(ii) a halohydrocarbon of the formula: ArG n , wherein Ar is an aromatic hydrocarbon ring system containing up to about 25 carbon atoms, G is —CX 3 , —CX 2 R 1 , or —CX(R 1 ) 2 , X is fluorine, R 1 is, independently, a hydrogen atom or C 1-4 alkyl group; and n is 1 to 5;
(iii) a siloxane having at least one hydrocarbyl groups containing from about 1 to 30 carbon atoms, wherein at least one of the hydrocarbyl groups contains at least one labile fluorine atom;
(iv) a silane of the formula R′SiX 4−n , wherein n=1-3, X is fluorine, and wherein R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms;
(v) a tin compound of the formula R′SnX 4−n , wherein n=1-3, X is fluorine, and wherein R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms; or
(vi) a hydrocarbyl aluminum halide of the formula R R″ m AlX 3−m , wherein m=1 or 2, where X is fluorine, and wherein R″ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms.
8. The method of claim 7 , wherein the Lewis base comprises (i) NMeR 2 2 , and each R 2 is independently hydrogen atom or hydrocarbyl group having up to about 24 carbon atoms, or (ii) OMTS.
9. A method of preparing a composition comprising combining at least:
a) aluminoxane source comprising up to about 30 mol % halogen atoms relative to Al atoms; and
b) Lewis base,
wherein said halogen atoms in said aluminoxane source is provided by a halogen source, wherein said halogen source is:
(i) a halohydrocarbon of the formula R n CX 4−n , wherein n=1-3, X is fluorine, and wherein R is, independently, a hydrogen atom or a hydrocarbyl group having from one to about twenty carbon atoms;
(ii) a halohydrocarbon of the formula: ArG n , wherein Ar is an aromatic hydrocarbon ring system containing up to about 25 carbon atoms, G is —CX 3 , —CX 2 R 1 , or —CX(R 1 ) 2 , X is fluorine R 1 is, independently, a hydrogen atom or C 1-4 alkyl group; and n is 1 to 5;
(iii) a siloxane having at least one hydrocarbyl group containing from about 1 to 30 carbon atoms, wherein at least one of the hydrocarbyl groups contains at least one labile fluorine atom;
(iv) a silane of the formula R′ n SiX 4−n ,wherein n=1-3, X is fluorine, and wherein R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms;
(v) a tin compound of the formula R′ n SnX 4−n , wherein n=1-3, X is fluorine, and wherein R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms; or
(vi) a hydrocarbyl aluminum halide of the formula R″ m AlX 3−m , wherein m=1 or 2, where X is fluorine, and wherein R″ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms.
10. A method of polymerizing monomer comprising combining composition of claim 1 transition metal component, and monomer.
11. The composition of claim 1 , wherein the halogen source is alpha,alpha,alpha-trifluorotoluene, alpha,alpha-difluorotoluene or alpha-fluorotoluene.
12. The method of claim 7 , wherein the halogen source is alpha,alpha,alpha-trifluorotoluene, alpha,alpha-difluorotoluene or alpha-fluorotoluene.
13. The method of claim 7 , wherein the Lewis base comprises octamethyltrisiloxane.
14. A catalyst for olefin polymerization comprising the composition of claim 1 and a transition metal component.
15. The catalyst of claim 14 , where the transition metal component has the formula ML a X n-a ;
wherein M represents any metal atom from the lanthanide or actinide series or from the transition metals in Group 3 to 10 of the Periodic Table;
wherein L represents groups having ligands suitable for either Ziegler-Natta type catalyst precursor, or metallocene type catalyst precursor, or non-metallocene single-site catalyst precursor;
wherein X represents halogen, alkoxy, aryloxy, amide or hydrocarbyl group having 1 to about 20 carbon atoms;
and wherein a represents a numeral satisfying the expression 0<a≦n; and n represents the valence of the metal atom M.
16. The composition of claim 15 , wherein M is Ti, Zr, Hf, V, Nb, Cr, Mo, Fe, or Ni; and L is a metallocene type catalyst precursor or non-metallocene single-site catalyst precursor.
17. The composition of claim 6 , wherein said aluminoxane source comprising up to about 30 mol % halogen atoms relative to Al atoms is fluorinated methylaluminoxane (F-MAO), fluorinated ethylaluminoxane (F-EAO), or fluorinated isobutylaluminoxane (F-IBAO).
18. A method of polymerizing a monomer comprising combining the composition of claim 6 with a transition metal component and a monomer.
19. A catalyst for olefin polymerization comprising the composition of claim 6 and a transition metal component.