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

Patent metadata

Field	Value
Publication number	US-10167352-B1
Application number	US-201715635460-A
Country	US
Kind code	B1
Filing date	Jun 28, 2017
Priority date	Jun 28, 2017
Publication date	Jan 1, 2019
Grant date	Jan 1, 2019

Abstract

A method for producing highly reactive olefin polymers wherein at least 50 mol. % of the polymer chains have terminal double bonds, from an impurity-containing isobutylene or a mixed C4 hydrocarbyl feedstock containing isobutylene in which the water content of the feedstock is controlled to be at least equal to the content of polar impurities in the feedstock, and less than the concentration at which the water causes a decrease in vinylidene end-group selectivity.

First claim

What is claimed is:

1. A process for the preparation of polybutene having an exo-olefin content of at least 50 mol. % from an impure isobutene or an isobutene-containing monomer feedstock containing from about 5 ppm to about 500 ppm of polar impurities, which process comprises contacting said impure isobutene or isobutene-containing feedstock, with a Lewis acid catalyst complexed with a Lewis base, in a substantially or completely apolar polymerization medium, and initiating polymerization of said isobutene or isobutene-containing feedstock with an initiator, wherein said Lewis acid catalyst is a Lewis acid of the formula R′AlCl 2 , wherein R′ is a hydrocarbyl group; said Lewis base is a dihydrocarbyl ether wherein each hydrocarbyl group is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms and one or both hydrocarbyl groups of the dihydrocarbyl ether are substituted with an electron withdrawing group and the initiator is a compound of the formula RX, wherein X is a halide; R is a hydrocarbyl group capable of forming a stable carbocation, and wherein the carbon linking group R to group X is tertiary, benzylic or allylic; wherein the amount of water in said feedstock is controlled to be between an amount at least equal to the molar amount of polar impurities in said feedstock, and less than 5 mM per liter of feedstock.

2. The process of claim 1 , wherein R′ is an alkyl group having 1 to 12 carbons.

3. The process of claim 1 , wherein said Lewis base is dihydrocarbyl ether wherein each hydrocarbyl group is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms and one or both hydrocarbyl groups of the dihydrocarbyl ether are substituted with a chlorine atom.

4. The process of claim 3 , wherein said Lewis base is dihydrocarbyl ether wherein each hydrocarbyl group is independently selected from alkyl groups having 1 to 4 carbon atoms and one or both hydrocarbyl groups of the dihydrocarbyl ether are substituted with a chlorine atom.

5. The process of claim 1 , wherein the Lewis acid and Lewis base are complexed in a solvent selected from a liquid, apolar, non-halogenated aliphatic solvent or a liquid, aromatic solvent.

6. The process of claim 5 , wherein said solvent is hexane, toluene or xylene.

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

8. The process of claim 1 , wherein said isobutene or isobutene-containing feedstock is selected from pure isobutene; a C 4 refinery cut containing between about 20-50% isobutene, between 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; and mixtures of pure isobutene and said C 4 refinery cut.

9. The process of claim 1 , wherein said isobutene or isobutene-containing feedstock contains from about 5 ppm to about 200 ppm of polar impurities.

10. The process of claim 1 , wherein the amount of water in said feedstock is controlled to be an amount between an amount at least equal to two times the molar amount polar of impurities in said feedstock, and less than 5 mM per liter of feedstock.

11. The process of claim 10 , wherein the amount of water in said feedstock is controlled to be an amount between an amount at least equal to three times the amount polar impurities in said feedstock, and less than 5 mM per liter of feedstock.

12. The process of claim 1 , wherein the amount of water in said feedstock is controlled to be an amount of from about 0.05 mM to less than 5 mM per liter of feedstock.

13. The process of claim 12 , wherein the amount of water in said feedstock is controlled to be an amount of from about 0.2 to about 2 mM per liter of feedstock.

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

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

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

17. The process of claim 1 , wherein said polybutene product has a number average molecular weight (M n ) of from about 400 Daltons to about 4000 Daltons.

Assignees

• Univ Massachusetts
• Infineum Int Ltd

Inventors

• Dimitrov Philip
• Severt Richard J
• Skourlis Thomas
• Weber Jeremy
• Emert Jacob
• Faust Rudolf

Classifications

• C08F110/10 Primary

  Isobutene · CPC title

• C08F210/10

  Isobutene · CPC title

• C08F10/10 Primary

  Isobutene · CPC title

• C08F4/14

  Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen · CPC title

• C08F4/022

  Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts · CPC title