Polymerization initiating system and method to produce highly reactive olefin functional polymers

Patent metadata

Field	Value
Publication number	US-9631038-B2
Application number	US-201314052490-A
Country	US
Kind code	B2
Filing date	Oct 11, 2013
Priority date	Oct 11, 2013
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

A method for producing highly reactive olefin polymers wherein at least 50 mol. % of the polymer chains have terminal double bonds, and a novel polymerization initiating system for accomplishing same.

First claim

What is claimed is:

1. A process for the preparation of polybutene having an exo-olefin content of at least 50 mol %, which process comprises complexing a Lewis acid catalyst with an oxygen and/or sulfur-containing Lewis base in a solvent selected from liquid, apolar, non-halogenated aliphatic solvents, or and liquid aromatic solvents, contacting isobutene or an isobutene-containing monomer mixture, with the resulting Lewis acid/Lewis base complex, in a substantially or completely apolar polymerization medium, and initiating polymerization of said isobutene or an isobutene-containing monomer mixture with an initiator, wherein said Lewis acid catalyst is a Lewis acid of the formula MR″ m Y n , wherein M is a metal selected from Al, Fe, Ga, Hf, Zr or W; R″ is a hydrocarbyl group; Y is halogen; m is 0 or an integer of 1 to 5, n is an integer of 1 to 6 and m+n is equal to the valency of metal M, with the proviso that, when M is Al, m is 1 and when said solvent is a liquid, apolar, non-halogenated aliphatic solvent, m is at least 1; and the initiator is a compound of the formula RX, wherein X is a halide; R is a hydrocarbyl group that forms a stable carbocation, and wherein the carbon linking group R to group X is tertiary, benzylic or allylic.

2. The process of claim 1 , wherein M is Al, Ga or Fe, and R″ is a C 1 to C 8 alkyl group.

3. The process of claim 1 , wherein M is Al or Fe.

4. The process of claim 1 , wherein Y is Cl or Br.

5. The process of claim 1 , wherein said Lewis base is selected from acyclic dihydrocarbyl ethers, wherein each hydrocarbyl group is independently selected from C 1 to C 12 hydrocarbyl, cyclic ethers having a 5 to 7 membered cyclic group, dihydrocarbyl ketones, wherein each hydrocarbyl group is independently selected from C 1 to C 12 hydrocarbyl, C 1 to C 12 aliphatic alcohols, C 1 to C 12 aliphatic aldehydes, acyclic aliphatic hydrocarbyl esters wherein the hydrocarbyl group is selected from C 1 to C 12 hydrocarbyl, cyclic aliphatic esters having a 5 to 7 membered cyclic group, dialkyl sulfides, wherein each alkyl group is independently selected from C 1 to C 12 alkyl, dihydrocarbyl thiocarbonyl compounds, wherein each hydrocarbyl group is independently selected from C 1 to C 12 hydrocarbyl, or mixtures thereof.

6. The process of claim 5 , wherein said Lewis base is selected from acyclic dialkyl ethers, wherein each alkyl group is independently selected from C 1 to C 4 alkyl, cyclic ethers having a 5 to 7 membered cyclic group, dialkyl ketones, wherein each alkyl group is independently selected from C 1 to C 4 alkyl, C 1 to C 4 aliphatic alcohols, C 1 to C 4 aliphatic aldehydes, acyclic aliphatic hydrocarbyl esters wherein the hydrocarbyl group is selected from C 1 to C 4 alkyl, cyclic aliphatic esters having a 5 to 7 membered cyclic group, dialkyl sulfides, wherein each alkyl group is independently selected from C 1 to C 4 alkyl, dialkyl thiocarbonyl compounds, wherein each alkyl group is independently selected from C 1 to C 4 alkyl, or mixtures thereof.

7. The process of claim 5 , wherein said Lewis base is a dihydrocarbyl ether or dihydrocarbyl ketone, wherein each hydrocarbyl group is independently selected from C 1 to C 8 hydrocarbyl, wherein one or each of said hydrocarbyl groups of said dihydrocarbyl ether or dihydrocarbyl ketone is substituted with an electron-withdrawing group.

8. The process of claim 7 , wherein said electron-withdrawing group is a halogen atom.

9. The process of claim 8 , wherein said halogen atom is chlorine.

10. The process of claim 5 , wherein said hydrocarbyl groups of said Lewis bases are branched or straight-chained C 1 to C 4 alkyl groups.

11. The process of claim 7 , wherein said hydrocarbyl groups of said Lewis bases are branched or straight-chained C 1 to C 4 alkyl groups.

12. The process of claim 1 , wherein said solvent is a liquid, apolar, non-halogenated aliphatic solvent, and m>1.

13. The process of claim 1 , wherein said solvent is a liquid, aromatic solvent selected from benzene, chlorobenzene, toluene or xylene.

14. The process of claim 13 , wherein said solvent is toluene or xylene.

15. The process of claim 1 , wherein said apolar polymerization medium is selected from saturated C 4 hydrocarbons, unsaturated C 4 hydrocarbons, or mixtures thereof.

16. The process of claim 1 , wherein said isobutene or an isobutene-containing monomer mixture is selected from pure isobutene; a C 4 refinery cut containing between about 5% and about 50% butene-1, between about 2% and about 40% butene-2, between about 2% and about 60% iso-butane, between about 2% and about 20% n-butane, and up to about 0.5% butadiene, wherein all percentages are by mass, based on the total mass of the C 4 refinery cut; or mixtures of pure isobutene and said C 4 refinery cut.

17. The process of claim 1 , wherein said complex is contacted with said isobutene or an isobutene-containing monomer at a concentration of millimoles of Lewis acid-Lewis base complex per liter of medium of from about 0.2 mM to about 200 mM.

18. The process of claim 1 , wherein said Lewis acid and said Lewis base are complexed by dissolving the Lewis acid in said solvent to form a solution, and then adding said Lewis base to said solution.

19. The process of claim 14 , wherein said solvent is selected from xylene or toluene, and said Lewis Acid and said Lewis base are complexed by dissolving the Lewis base in said solvent to form a solution, and then adding said Lewis acid to said solution.

20. The process of claim 1 , wherein the polymerization process is conducted continuously.

21. The process of claim 1 , wherein said polybutene product has an exo-olefin content of at least 70 mol %.

22. The process of claim 1 , wherein said Lewis acid is selected from MeAlCl 2 , EtAlCl 2 , iso-BuAlCl 2 or n-BuAlCl 2 ; said Lewis base is a dihydrocarbyl ether, wherein each hydrocarbyl group is independently selected from C 1 to C 8 hydrocarbyl, and wherein one or each of said hydrocarbyl groups of said dihydrocarbyl ether is substituted with chlorine; said solvent is selected from benzene or toluene and said Lewis acid and said Lewis base is complexed by dissolving the Lewis base in said solvent to form a solution, and then adding said Lewis acid to said solution in an amount such that the molar ratio of Lewis acid to Lewis base in the complex is from about 1:1 to about 1:1.7.

23. The process of claim 1 , wherein said Lewis acid is selected from MeAlCl 2 , EtAlCl 2 , iso-BuAlCl 2 or n-BuAlCl 2 , and said solvent is selected from benzene and toluene and said Lewis acid and said Lewis base are complexed by dissolving the Lewis base in said solvent to form a solution, and then adding said Lewis acid to said solution in an amount such that the molar ratio of Lewis acid to Lewis base in the complex is from about 1:1 to about 1:1.7.

24. A catalyst-initiator system for catalyzing the polymerization of isobutene or an isobutene-containing monomer mixture in a substantially or completely apolar polymerization medium to provide a polybutene product having an exo-olefin content of at least 50 mol %, wherein said catalyst consists essentially of a Lewis acid catalyst complexed with an oxygen and/or sulfur containing Lewis base in a solvent selected from liquid, apolar, non-halogenated aliphatic solvents, or liquid aromatic solvents, wherein said Lewis base is a dihydrocarbyl ketone, wherein each hydrocarbyl group of said dihydrocarbyl keton

Assignees

• Univ Massachusetts
• Infineum Int Ltd

Inventors

• Faust Rudolf
• Kumar Rajeev
• Emert Jacob

Classifications

• C08F110/10 Primary

  Isobutene · CPC title

• C08F4/80

  selected from iron group metals or platinum group metals · CPC title

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F4/70

  Iron group metals, platinum group metals or compounds thereof · CPC title

• C08F4/12

  of boron, aluminium, gallium, indium, thallium or rare earths · CPC title