Process to make non-coordinating anion type activators in aliphatic and alicyclic hydrocarbon solvents

Patent metadata

Field	Value
Publication number	US-11117908-B2
Application number	US-201916394186-A
Country	US
Kind code	B2
Filing date	Apr 25, 2019
Priority date	Apr 26, 2018
Publication date	Sep 14, 2021
Grant date	Sep 14, 2021

Abstract

The present disclosure provides borate activators comprising cations having linear alkyl groups, catalyst systems comprising, and processes for polymerizing olefins using such activators. Specifically, the present disclosure provides polymerization activator compounds which may be prepared in, and which are soluble in aliphatic hydrocarbon and alicyclic hydrocarbon solvents.

First claim

We claim:

1. A process to produce an activator compound comprising:
i) contacting a compound according to formula (A) with a compound having the general formula M-(BR4R5R6R7) in a solvent including isohexane, hexane, or n-hexane, or a combination thereof, at a reaction temperature ranging from 30° C. to 20° C., and for a period of time sufficient to produce a mixture comprising the activator compound according to formula (I) and a salt having the formula M(X); wherein formula (A) is represented by:

wherein formula (I) is represented by:

wherein in each of formulae (A) and (I):
each of R 1 and R 2 is independently a hydrogen or a C 1 -C 40 linear alkyl, with R 8 , R 9 , R 10 , R 11 , and R 12 being independently C 1 -C 40 linear alkyl and not hydrogen;
R 1 , R 2 , R 8 , R 9 , R 10 , R 11 , and R 12 together comprise 15 or more carbon atoms;
each of R 4 , R 5 , R 6 , and R 7 comprises an aromatic hydrocarbon having from 6 to 24 carbon atoms;
at least one of R 4 , R 5 , R 6 , and R 7 is substituted with one or more fluorine atoms;
X is halogen; and
M is a Group 1 metal;

and
wherein a 1 millimole per liter mixture of the activator compound in n-hexane, isohexane, hexane, or a combination thereof, forms a clear homogeneous solution at 25° C.

2. The process of claim 1 , wherein at least one of R 4 , R 5 , R 6 , and R 7 comprises a perfluoro substituted phenyl moiety, a perfluoro substituted naphthyl moiety, a perfluoro substituted biphenyl moiety, a perfluoro substituted triphenyl moiety, or a combination thereof.

3. The process of claim 1 , wherein R 4 , R 5 , R 6 , and R 7 are perfluoro substituted phenyl radicals and R 2 is not a C 1 -C 40 linear alkyl.

4. The process of claim 1 , wherein R 4 , R 5 , R 6 , and R 7 are perfluoro substituted naphthyl radicals.

5. The process of claim 1 , wherein R 1 , R 2 , R 8 , R 9 , R 10 , R 11 , and R 12 together comprise 20 or more carbon atoms.

6. The process of claim 1 , wherein R 1 , R 2 , R 8 , R 9 , R 10 , R 11 , and R 12 together comprise 30 or more carbon atoms.

7. The process of claim 1 , wherein two of more of R 1 , R 2 , R 8 , R 9 , R 10 , R 11 , and R 12 are each a C 10 -C 40 linear alkyl radical.

8. The process of claim 1 , wherein two or more of R 1 , R 2 , R 8 , R 9 , R 10 , R 11 , and R 12 are each a C 10 -C 22 linear alkyl radical.

9. The process of claim 1 , wherein two or more of R 1 , R 2 , and R 10 are each a C 10 -C 40 linear alkyl and R 8 and R 12 are hydrogen.

10. The process of claim 1 , wherein two or more of R 1 , R 2 , and R 10 are each a C 10 -C 22 linear alkyl and R 8 and R 12 are hydrogen.

11. The process of claim 1 , wherein at least one of R 8 , R 9 , R 10 , R 11 , and R 12 is a linear alkyl radical comprising 6 or more carbon atoms.

12. The process of claim 1 , wherein R 8 and R 12 are hydrogen and R 10 is a linear alkyl radical comprising 6 or more carbon atoms.

13. The process of claim 1 , wherein R 1 is methyl and each of R 2 and R 10 is C 6 -C 40 linear alkyl radical.

14. The process of claim 1 , further comprising the step of filtering the mixture to remove the salt to produce a clear homogeneous solution comprising the activator compound according to formula (I) and optionally removing at least a portion of the solvent.

15. The process of claim 1 , wherein the period of time is less than or equal to about 24 hours.

16. The process of claim 1 , wherein the period of time is less than or equal to about 2 hours.

17. The process of claim 1 , wherein a 5 millimole per liter mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25° C.

18. The process of claim 1 , wherein a 10 millimole per liter mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25° C.

19. The process of claim 1 , wherein a 20 millimole per liter mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25° C.

20. The process of claim 1 where aromatic solvents are absent.

21. The process of claim 1 , wherein the solvent includes isohexane.

22. The process of claim 1 , wherein the solvent includes n-hexane.

23. A process of polymerizing olefins to produce at least one polyolefin, the process comprising:
i) contacting a compound according to formula (A) with a compound having the general formula M-(BR 4 R 5 R 6 R 7 ) in a solvent including isohexane, hexane, or n-hexane, or a combination thereof, at a reaction temperature ranging from 30° C. to 20° C. and for a period of time sufficient to produce a mixture comprising an activator compound according to formula (I) and a salt having the formula M(X); wherein formula (A) is represented by:

wherein formula (I) is represented by:

wherein in each of formulae (A) and (I):
each of R 1 and R 2 is independently a hydrogen or a C 1 -C 40 linear alkyl, with R 8 , R 9 , R 10 , R 11 , and R 12 being independently C 1 -C 40 linear alkyl and not hydrogen;
R 1 , R 2 , R 8 , R 9 , R 10 , R 11 , and R 12 together comprise 15 or more carbon atoms;
each of R 4 , R 5 , R 6 , and R 7 comprises an aromatic hydrocarbon having from 6 to 24 carbon atoms;
at least one of R 4 , R 5 , R 6 , and R 7 is substituted with one or more fluorine atoms;
X is halogen; and
M is a Group 1 metal;
ii) filtering the mixture to remove the salt to produce a clear homogeneous solution comprising the activator compound according to formula (I) and optionally removing at least a portion of the solvent;
iii) combining the activator and a catalyst to form a catalyst system, and
iv) contacting at least one olefin with the catalyst system and obtaining the polyolefin; wherein a 1 millimole per liter mixture of the activator compound in hexane, n-hexane, isohexane, or a combination thereof, forms a clear homogeneous solution at 25° C.

24. The process of claim 23 , wherein the at least one olefin is propylene and the polyolefin is isotactic polypropylene.

25. The process of claim 23 , wherein the at least one olefin is two or more different olefins.

26. The process of claim 23 , wherein the at least one olefin is both ethylene and propylene.

27. The process of claim 23 , wherein the at least one olefin comprises a diene.

28. The process of claim 25 where aromatic solvents are absent.

29. The process of claim 23 , wherein the solvent includes isohexane.

30. The process of claim 23 , wherein the solvent includes n-hexane.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Faler Catherine A
• Whalley Margaret T
• Hagadorn John R

Classifications

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C07C211/64

  having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F210/06

  Propene · CPC title