Granted Patent B2

US 12,528,892 · App. 17/906,394 · Granted Jan 20, 2026

Inventors: Lubin Luo (Houston, TX); Nikola S. Lambic (Houston, TX); Jo Ann M. Canich (Houston, TX)

Assignee: ExxonMobil Chemical Patents Inc.

C08F4/65927C07F17/00C08F4/62093C08F2410/01C08F2420/01C08F2420/08

Abstract

Claims (149)

1 . A method comprising:

reacting (a) transition metal coordination catalyst complex comprising a transition metal linked to at least one anionic donor ligand and at least one leaving group having a non-carbon atom directly linked to the transition metal, (b) an aluminum alkyl, and (c) a fluoride salt at 0° C. to 85° C., wherein a molar ratio of aluminum of the aluminum alkyl to fluoride of the fluoride salt is 1:15 to 1:3, in a non-polar solvent to yield an alkylated transition metal coordination catalyst complex.

2 . The method of claim 1 , wherein the non-polar solvent is selected from the group consisting of: butane, isobutene, pentane, isopentane, hexane, isohexane, heptane, octane, decane, benzene, toluene, xylene, and any combination thereof.

3 . The method of claim 1 , wherein a molar ratio of the transition metal coordination catalyst complex to the aluminum alkyl is 1:1 to 1:3.

4 . The method of claim 1 , wherein a molar ratio of aluminum of the aluminum alkyl to fluoride of the fluoride salt is 1:10 to 1:3.

5 . The method of claim 1 , wherein reacting occurs for 15 minutes to 36 hours.

6 . The method of claim 1 , wherein the fluoride salt is selected from the group consisting of NaF, KF, MgF 2 , CaF 2 , and any combination thereof.

7 . The method of claim 1 , further comprising:

after reacting, adding additional fluoride salt to precipitate unreacted aluminum alkyl.

8 . The method of claim 1 , wherein the alkylated transition metal coordination catalyst complex has a molar ratio of di-alkylated to mono-alkylated of 100:0 to 70:30.

9 . The method of claim 1 , wherein the molar ratio of rac:meso in the alkylated transition metal coordination catalyst complex is 100:0 to 90:10.

10 . The method of claim 1 , wherein the transition metal coordination catalyst complex is (a.i) one or more metallocenes, (a.ii) one or more post-metallocenes, or (a.iii) one or more metallocenes in combination with one or more post-metallocenes.

11 . The method of claim 1 , wherein the transition metal coordination catalyst complex is represented by the formula: Cp A Cp B M′X′ n , wherein each Cp A and Cp B is independently selected from cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, one or both Cp A and Cp B may contain heteroatoms, and one or both Cp A and Cp B may be substituted by one or more R″ groups; M′ is selected from groups group 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 atoms and lanthanide group atoms; X′ is a leaving group with a non-carbon atom directly linking to the M′ center; n is 1 or 2; each R″ is independently selected from alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, a heteroatom-containing group, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, ether, and thioether, where two or more R″ groups may form mono- or multi-nuclear cyclic groups.

12 . The method of claim 1 , wherein the transition metal coordination catalyst complex is represented by the formula: Cp A (T)Cp B M′X′ n , and wherein each Cp A and Cp B is bound to M′ and (T) and each Cp A and Cp B is independently selected from cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, one or both Cp A and Cp B may contain heteroatoms, and one or both Cp A and Cp B may be substituted by one or more R″ groups; M′ is selected from groups group 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 atoms and lanthanide group atoms; X′ is a leaving group with a non-carbon atom directly linking to the M′ center; n is 1 or 2; each R″ is independently selected from alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, a heteroatom-containing group, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, ether, and thioether, where two or more R″ groups may form mono- or multi-nuclear cyclic groups; and (T) is a bridging group bound to Cp A and Cp B .

13 . The method of claim 1 , wherein the transition metal coordination catalyst complex is represented by represented by Formula (Ia):

wherein:

M is a Group 4 metal;

T is a bridging group;

each of X 1 and X 2 is a leaving group with a non-carbon atom directly linking to the M′ center;

R 1 is hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , where R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;

R 3 is an unsubstituted C 4 -C 62 cycloalkyl, a substituted C 4 -C 62 cycloalkyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, or a substituted C 4 -C 62 heteroaryl;

each of R 2 and R 4 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;

each of R 5 , R 6 , R 7 , and R 8 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, or one or more of R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 can be joined to form a substituted or unsubstituted C 4 -C 62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; and

J 1 and J 2 are joined to form a substituted or unsubstituted C 4 -C 62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof.

14 . The method of claim 1 , wherein the transition metal coordination catalyst complex is represented by one or more of:

15 . The method of claim 1 , wherein the alkylated transition metal coordination catalyst complex is one or more of:

bis(cyclopentadienyl)M c R n ,

bis(n-butylcyclopentadienyl)M c R n ,

bis(pentamethylcyclopentadienyl)M c R n ,

bis(1-methyl-3-n-butylcyclopentadienyl)M c R n ,

bis(tetrahydro-1-indenyl)M c R n ,

(n-propyl cyclopentadienyl)(pentamethyl cyclopentadienyl)M c R n ,

dimethylsilylbis(tetrahydroindenyl)M c R n ,

dimethylsilyl bis(2-methylindenyl)M c R n ,

dimethylsilyl bis(2-methylfluorenyl)M c R n ,

dimethylsilyl bis(2-methyl-5,7-propylindenyl)M c R n ,

dimethylsilyl bis(2-methyl-4-phenylindenyl)M c R n ,

dimethylsilyl bis(2-ethyl-5-phenylindenyl)M c R n ,

dimethylsilyl bis(2-methyl-4-biphenylindenyl)M c R n ,

dimethylsilylene bis(2-methyl-4-carbazolylindenyl)M c R n ,

rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)M c R n ,

diphenylmethylene (cyclopentadienyl)(fluoreneyl)M c R n ,

bis(methylcyclopentadienyl)M c R n ,

rac-dimethylsiylbis(2-methyl,3-propyl indenyl)M c R n ,

dimethylsilylbis(indenyl)M c R n ,

rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)M c R n ,

1, 1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl) (3,8-di-tertiary-butyl-1-fluorenyl)M c R n ,

bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-t-butylfluorenyl)M c R n ,

bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)M c R n ,

bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)M c R n ,

bis(n-propylcyclopentadienyl)M c R n ,

bis(n-pentylcyclopentadienyl)M c R n ,

(n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)M c R n ,

bis[(2-trimethylsilylethyl)cyclopentadienyl]M c R n ,

bis(trimethylsilyl cyclopentadienyl)M c R n ,

dimethylsilylbis(n-propylcyclopentadienyl)M c R n ,

dimethylsilylbis(n-butylcyclopentadienyl)M c R n ,

bis(1-n-propyl-2-methylcyclopentadienyl)M c R n ,

(n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)M c R n ,

bis(indenyl)M c R n ,

dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M c R n ,

dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M c R n ,

1,1′-bis(4-triethylsilylphenyl)(methylene)(cyclopentadienyl)(fluorenyl)M c R n ;

μ-(CH 3 ) 2 Si(cyclopentadienyl)(1-adamantylamido)M c R n ,

μ-(CH 3 ) 2 Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M c R n ,

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-adamantylamido)M c R n ,

μ-(CH 3 ) 2 C(tetramethylcyclopentadienyl)(1-adamantylamido)M c R n ,

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M c R n ,

μ-(CH 3 ) 2 Si(fluorenyl)(1-tertbutylamido)M c R n ,

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M c R n ,

μ-(C 6 H 5 ) 2 C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M c R n ,

μ-(CH 3 ) 2 Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M c R n ,

where n is 2, M c is Ti, Zr, or Hf, and each R is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, n-pentyl, cyclopentyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, and cyclohexyl.

16 . The method of claim 1 , wherein the alkylated transition metal coordination catalyst complex is one or more of:

bis(cyclopentadienyl)zirconium dimethyl,

bis(n-butylcyclopentadienyl)zirconium dimethyl,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

bis(pentamethylcyclopentadienyl)hafnium dimethyl,

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dimethyl,

bis(tetrahydro-1-indenyl)zirconium dimethyl,

(n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dimethyl,

dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,

dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl,

μ-(CH 3 ) 2 Si(cyclopentadienyl)(1-adamantylamido)titanium dimethyl,

μ-(CH 3 ) 2 Si(3-tertbutylcyclopentadienyl)(1-adamantylamido) titanium dimethyl,

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-adamantylamido) titanium dimethyl,

μ-(CH 3 ) 2 C(tetramethylcyclopentadienyl)(1-adamantylamido) titanium dimethyl,

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-tertbutylamido) titanium dimethyl,

μ-(CH 3 ) 2 Si(fluorenyl)(1-tertbutylamido)titanium dimethyl,

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium dimethyl,

μ-(C 6 H 5 ) 2 C(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium dimethyl,

μ-(CH 3 ) 2 Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)titanium dimethyl,

rac-dimethylsilyl-bis(indenyl)hafnium dimethyl,

1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl) (3,8-di-tertiary-butyl-1-fluorenyl)hafnium dimethyl,

dimethylsilyl bis(tetrahydroindenyl)zirconium dimethyl,

dimethylsilyl bis(indenyl)zirconium dimethyl,

dimethylsilyl bis(indenyl)hafnium dimethyl,

bis(indenyl)zirconium dimethyl,

bis(indenyl)hafnium dimethyl,

dimethylsilyl bis(tetrahydroindenyl)zirconium dimethyl,

bis(n-propylcyclopentadienyl)zirconium dimethyl,

dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,

dimethylsilyl bis(2-methylindenyl)zirconium dimethyl,

dimethylsilyl bis(2-methylfluorenyl)zirconium dimethyl,

dimethylsilyl bis(2-methylindenyl)hafnium dimethyl,

dimethylsilyl bis(2-methylfluorenyl)hafnium dimethyl,

dimethylsilyl bis(2-methyl-5,7-propylindenyl)zirconium dimethyl,

dimethylsilyl bis(2-methyl-4-phenylindenyl)zirconium dimethyl,

dimethylsilyl bis(2-ethyl-5-phenylindenyl)zirconium dimethyl,

dimethylsilyl bis(2-methyl-4-biphenylindenyl)zirconium dimethyl,

dimethylsilylene bis(2-methyl-4-carbazolylindenyl)zirconium dimethyl,

rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)hafnium dimethyl,

diphenylmethylene (cyclopentadienyl)(fluoreneyl)hafnium dimethyl,

bis(methylcyclopentadienyl)zirconium dimethyl,

rac-dimethylsiylbis(2-methyl,3-propyl indenyl)hafnium dimethyl,

dimethylsilylbis(indenyl)hafnium dimethyl,

dimethyl rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)hafnium dimethyl,

rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)hafnium dimethyl,

1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)hafnium dimethyl (bridge is considered the 1 position),

bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-t-butylfluorenyl)hafnium dimethyl,

bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl,

bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)hafnium dimethyl,

bis(n-propylcyclopentadienyl)hafnium dimethyl,

bis(n-butylcyclopentadienyl)hafnium dimethyl,

bis(n-pentylcyclopentadienyl)hafnium dimethyl,

(n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)hafnium dimethyl,

bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,

bis(trimethylsilyl cyclopentadienyl)hafnium dimethyl,

dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,

dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,

bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl,

(n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium dimethyl,

bis(n-propylcyclopentadienyl)hafnium dimethyl,

bis(n-butylcyclopentadienyl)hafnium dimethyl,

bis(n-pentylcyclopentadienyl)hafnium dimethyl,

(n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)hafnium dimethyl,

bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,

bis(trimethylsilyl cyclopentadienyl)hafnium dimethyl,

dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,

dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,

bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl,

(n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium dimethyl, and

dimethylsilyl(3-n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dimethyl.

17 . The method of claim 1 , wherein the alkylated transition metal coordination catalyst complex is one or more of:

18 . The method of claim 1 , wherein the transition metal coordination catalyst complex is selected from the group consisting of: bisphenolate complexes; diphenolate complexes; oxadiazolylphenolate complexes; diethylenetriamine complexes; oxybis(ethylamine) complexes; pyridyldiamido complexes; quinolinyldiamido complexes; cyclopentadienyl-amidinate complexes; and iron pyridyl bis(imine) complexes; or any combination thereof, including any combination with metallocene complexes.

19 . A method comprising:

reacting (a) transition metal coordination catalyst complex comprising a transition metal linked to at least one anionic donor ligand and at least one leaving group having a non-carbon atom directly linked to the transition metal, wherein the transition metal coordination catalyst complex is selected from the group consisting of: bisphenolate complexes; diphenolate complexes; oxadiazolylphenolate complexes; diethylenetriamine complexes; oxybis(ethylamine) complexes; pyridyldiamido complexes; quinolinyldiamido complexes; cyclopentadienyl-amidinate complexes; and iron pyridyl bis(imine) complexes; or any combination thereof, including any combination with metallocene complexes; (b) an aluminum alkyl, and (c) a fluoride salt at 0° C. to 85° C. in a non-polar solvent to yield an alkylated transition metal coordination catalyst complex.

20 . The method of claim 19 , wherein a molar ratio of aluminum of the aluminum alkyl to fluoride of the fluoride salt is 1:10 to 1:3.

Continuity (2)

References Cited (54)