Alkyl Ammonium (Fluoroaryl)borate Activators

• US 20190330394A1
• Filed: 04/25/2019
• Published: 10/31/2019
• Est. Priority Date: 04/26/2018
• Status: Abandoned Application

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Faler, Catherine A., Whalley, Margaret T., Atienza, Crisita Carmen H., Hagadorn, John R.
• Application Number:
  US16/394,174
• Publication Number:
  US 20190330394A1
• Time in Patent Office: Days
• CPC Class Codes: C07C 211/48 N-alkylated amines
• CPC Class Codes: C07C 211/64 having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07F 5/027 Organoboranes and organoborohydrides
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/34 Melting point [Tm]
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

The present disclosure provides borate activators, catalyst systems comprising borate activators, and methods for polymerizing olefins using borate activators. The borate activator compounds are represented by Formula (I): [R¹R²R³EH]⁺[BR⁴R⁵R⁶R⁷]⁻, wherein: E is nitrogen or phosphorous; R¹ is an electron deficient aromatic group; each of R² and R³ is independently C₁-C₄₀ alkyl, C₅-C₂₂-aryl, wherein each of R¹, R², and R³ is independently unsubstituted or substituted with at least one of halide, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₅ arylalkyl, and C₆-C₂₅ alkylaryl, wherein R¹, R², and R³ together comprise 15 or more carbon atoms; and each of R⁴, R⁵, R⁶, and R⁷ is aryl (such as phenyl or naphthyl), wherein at least one of R⁴, R⁵, R⁶, and R⁷ is substituted with one or more fluorine atoms.

Claims

1. A compound represented by Formula (AI):

[R¹R²R³EH]^d+[M^k+Q_n]^d−

 

 

(AI)

wherein;

E is nitrogen or phosphorous (preferably nitrogen);

d is 1, 2 or 3;

k is 1, 2, or 3;

n is 1, 2, 3, 4, 5, or 6;

n−

k=d;

R¹ is electron deficient aromatic group;

each R², and R³ is independently C₁-C₄₀ linear alkyl or C₅-C₅₀-aryl, wherein each of R² and R³ is independently unsubstituted or substituted with at least one of halide, C₁-C₅₀ alkyl, C₅-C₅₀ aryl, C₆-C₃₅ arylalkyl, or C₆-C₃₅ alkylaryl, wherein R¹, R², and R³ together comprise 15 or more carbon atoms;

M is an element selected from group 13 of the Periodic Table of the Elements, preferably B or Al; and

each Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical, provided that when each Q is perfluorophenyl, then R¹ is not methyl, and R² and R³ are not C₁₈ alkyl.

2. The compound of claim 1 wherein the compound is represented by Formula (I):

[R¹R²R³EH]⁺[BR⁴R⁵R⁶R⁷]⁻

 

 

(I)

wherein;

E is nitrogen or phosphorous (preferably nitrogen);

R¹ is electron deficient aromatic group,

each of R² and R³ is independently C₁-C₄₀ alkyl, C₅-C₂₂-aryl, wherein each of R¹, R², and R³ is independently unsubstituted or substituted with at least one of halide, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₅ arylalkyl, and C₆-C₂₅ alkylaryl, wherein R¹, R², and R³ together comprise 15 or more carbon atoms;

each of R⁴, R⁵, R⁶, and R⁷ is aryl (such as phenyl or naphthyl), wherein at least one of R⁴, R⁵, R⁶, and R⁷ is substituted with from one or more fluorine atoms.

3. The compound of claim 2, wherein at least one of R⁴, R⁵, R⁶, and R⁷ is naphthyl substituted with seven fluorine atoms.

4. The compound of claim 2, wherein each of R⁴, R⁵, R⁶, and R⁷ is phenyl substituted with from one to five fluorine atoms.

5. The compound of claim 2, wherein each of R⁴, R⁵, R⁶, and R⁷ is naphthyl substituted with seven fluorine atoms.

6. The compound of claim 1, wherein R¹, R², and R³ together comprise 17 or more carbon atoms.

7. The compound of claim 1, wherein R¹, R², and R³ together comprise 20 or more carbon atoms.

8. The compound of claim 1, wherein R¹, R², and R³ together comprise 25 or more carbon atoms.

9. The compound of claim 1, wherein R¹, R², and R³ together comprise 35 or more carbon atoms.

10. The compound of claim 1, wherein R¹ is a phenyl group that is substituted with one, two, three, four or five halogen and/or haloalkyl groups and each of R² and R³ is independently C₁-C₄₀ linear alkyl, or C₅-C₂₂-aryl, wherein each of R² and R³ is independently unsubstituted or substituted with at least one C₁-C₁₀ alkyl.

11. The compound of claim 1, wherein R¹ is a phenyl group, that is substituted with one, two, three, four or five groups selected from fluoro, chloro, bromo, iodo, and trifluoromethyl and each of R² and R³ is independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-butadecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, cyclohexylmethyl, and n-icosyl.

12. The compound of claim 1, wherein R¹ is selected from 4-fluorophenyl, 4-(trifluoromethyl)phenyl, 3-fluorophenyl, 3-(trifluoromethyl)phenyl, and 3-chlorophenyl.

13. The compound of claim 1, wherein R¹ is F₃C-phenyl or F-phenyl, R² is C₁₀-C₄₀ alkyl, and R³ is C₁₀-C₄₀ alkyl.

14. The compound of claim 1, wherein the cation, [R¹R²R³EH]⁺, is selected from the group consisting of:

N,N-didodecyl-2,3,4,5,6-pentafluorobenzenaminium,

N,N-didodecyl-3,5-difluorobenzenaminium,

N,N-didodecyl-3,5-bis(trifluoromethyl)benzenaminium,

N,N-bis(cyclohexylmethyl)-2,3,4,5,6-pentafluorobenzenaminium,

N,N-bis(cyclohexylmethyl)-3,5-bis(trifluoromethyl)benzenaminium,

N,N-bis(cyclohexylmethyl)-4-(trifluoromethyl)benzenaminium,

N,N-bis(cyclohexylmethyl)-4-fluorobenzenaminium, and

N,N-didodecyl-4-(trifluoromethyl)anilium.

15. The compound of claim 1, wherein the cation, [R¹R²R³EH]⁺, is selected from the group consisting of N,N-bis(cyclohexylmethyl)-4-(trifluoromethyl)benzenaminium, N,N-bis(cyclohexylmethyl)-4-fluorobenzenaminium, and N,N-didodecyl-4-(trifluoromethyl)anilium.

16. A catalyst system comprising a catalyst and the activator compound of claim 1.

17. The catalyst system of claim 16, further comprising a support material.

18. The catalyst system of claim 17, wherein the support material is selected from Al₂O₃, ZrO₂, SiO₂, SiO₂/Al₂O₃, SiO₂/TiO₂, silica clay, silicon oxide/clay, or mixtures thereof.

19. The catalyst system of claim 16, wherein the catalyst is represented by formula (II) or formula (III):

20. The catalyst system of claim 16, wherein the catalyst is C₂ symmetrical.

21. The catalyst system of claim 16, wherein the catalyst is rac-dimethylsilyl-bis(indenyl)hafnium dimethyl.

22. The catalyst system of claim 16, wherein the catalyst is one or more of:

bis(1-methyl, 3-n-butyl cyclopentadienyl) M(R)₂;

dimethylsilyl bis(indenyl)M(R)₂;

bis(indenyl)M(R)₂;

dimethylsilyl bis(tetrahydroindenyl)M(R)₂;

bis(n-propylcyclopentadienyl)M(R)₂;

dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;

dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;

dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;

dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;

μ

-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂;

μ

-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;

μ

-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(15-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R)₂;

where M is selected from Ti, Zr, and Hf; and

R is selected from halogen or C₁ to C₅ alkyl.

23. The catalyst system of claim 16, wherein the catalyst is represented by Formula (BI), Formula (BII), or Formula (BIII):

24. The catalyst system of claim 16, wherein the catalyst is represented by Formula (CI):

25. The catalyst system of claim 16, wherein the catalyst is represented by Formula (IV):

26. The catalyst system of claim 16, wherein the catalyst is represented by Formula (VII):

27. The catalyst system of claim 16, wherein the catalyst is represented by Formula (VIII):

28. The catalyst system of claim 16, wherein the catalyst is represented by Formula (XI):

29. The catalyst system of claim 16, wherein the catalyst is represented by Formula (XII) or (XIII):

30. A method of polymerizing olefins to produce at least one polyolefin, the method comprising contacting at least one olefin with the catalyst system of claim 16 and obtaining a polyolefin.

31. The method of claim 30, wherein the at least one olefin is propylene and the polyolefin is isotactic polypropylene.

32. A method of polymerizing olefins to produce at least one polyolefin, the method comprising contacting two or more different olefins with the catalyst system claim 16 and obtaining a polyolefin.

33. The method of claim 32, wherein the two or more olefins are ethylene and propylene.

34. The method of claim 32, wherein the two or more olefins further comprise a diene.

35. The method of claim 32, wherein the polyolefin has an Mw of from about 50,000 to about 300,000 g/mol and a melt temperature of from about 120°

C. to about 140°

C.

36. The method of claim 32, wherein the polyolefin has an Mw of from about 100,000 to about 300,000 g/mol and a melt temperature of from about 125°

C. to about 135°

C.

37. The method of claim 30, wherein the method is performed in gas phase or slurry phase.

38. The method of claim 30, wherein the method is performed in solution phase.

39. A solution comprising the compound of claim 1, and an aliphatic solvent.

40. The solution of claim 39, where aromatic solvents, such as toluene, are absent.

41. A solution comprising the catalyst system of claim 16, and an aliphatic solvent where, optionally, aromatic solvents are absent.

42. A composition comprising the catalyst system of claim 23, and an aliphatic solvent, where aromatic solvents are absent.