CATIONIC POLYMERIZATION OF OLEFINS USING GREEN ACIDS

• US 20190330395A1
• Filed: 04/25/2019
• Published: 10/31/2019
• Est. Priority Date: 04/25/2018
• Status: Active Grant

• Current Assignee: Stewart P. Lewis
• Original Assignee: Stewart P. Lewis
• Inventors: LEWIS, Stewart P.
• Granted Patent: US 10,766,982 B2
• Time in Patent Office: Days
• CPC Class Codes: C08F 110/10 Isobutene
• CPC Class Codes: C08F 2410/01 Additive used together with the catalyst, excluding compounds containing Al or B
• CPC Class Codes: C08F 4/12 of boron, aluminium, gallium, indium, thallium or rare earths

Abstract

A processes for effecting the cationic polymerization of olefins in a controlled manner that includes the step of contacting olefin monomers and a catalytically effective amount of an initiating composition containing (A) a recyclable aluminum, gallium, or indium perfluorinated organosulfonate, (B) a solubilizing agent, (C) an initiator selected from the group consisting of (i) carbocation synthons, (ii) halogenium ion synthons, (iii) Brønsted acids, and (iv) silicenium ion synthons, and optionally (D) a nucleophilic additive. The invention further includes a process for recycling aluminum, gallium, or indium perfluorinated organosulfonates that includes the steps of aqueous extraction and dehydration. A novel initiator system is also disclosed.

Claims

1. A process for cationically polymerizing olefin monomers in a controlled manner in a reaction mixture, the cationic polymerization process comprising:

contacting olefin monomers and a catalytically effective amount of an initiating composition containing (A) a recyclable coinitiator, (B) a solubilizing agent, (C) an initiator, and optionally, (D) a nucleophilic additive, to form a reaction medium;

wherein the recyclable coinitiator (A) is selected from aluminum, gallium, and indium perfluorinated organosulfonates of the formula (I);

2. The process of claim 1, wherein the solubilizing agent (B) is selected from the group consisting of alcohols, ethers, ketones, aldehydes, esters, carboxylic acids, anhydrides, acyl halides, amides, amines, nitriles, thiols, thioethers, sulfoxides, disulfides, nitro, sulfonyl, carbonyl, and thiocarbonyl.

3. The process of claim 1, wherein the X of formula (II) or (III) is selected from the group consisting of a halogen, ester, acyl halide, ether, alcohol, and acid group.

4. The process of claim 1, wherein the optional nucleophilic additive is selected from the group consisting of ethers, ketones, esters, amides, pyridines, phosphines, sulfoxides, amides, amines, and tetraalkylammonium salts.

5. The process of claim 1, wherein olefin monomers are selected from the group consisting of ethylene, propylene, 1-butene, isobutylene, 2-methyl-1-butene, butadiene, isoprene, piperylene, 2,3-dimethylbutadiene, 2,4-dimethyl-1,3-pentadiene, cyclopentadiene, methylcyclopentadiene, limonene, myrcene, 1,3-cyclohexadiene, alpha and beta pinene, alpha-methyl styrene, styrene, p-methyl styrene, vinyl-toluene (and its isomers), divinylbenzene, indene, coumarone, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 4-vinylbenzyl chloride, styrylethyltimethoxysilane, and styrylethyltrichlorosilane.

6. The process of claim 1, wherein the recyclable aluminum, gallium, and indium perfluorinated organosulfonates is selected from the group consisting of aluminum trifluoromethanesulfonate, gallium trifluoromethanesulfonate, indium trifluoromethanesulfonate, aluminum perfluorooctanesulfonate, gallium perfluorooctanesulfonate, indium perfluorooctanesulfonate, aluminum pentafluorophenyl sulfonate, gallium pentafluorophenyl sulfonate, indium pentafluorophenyl sulfonate, aluminum 1-perfluoronaphthyl sulfonate, gallium 1-perfluoronaphthylsulfonate, indium 1-perfluoronaphthyl sulfonate, aluminum 2-perfluoronaphthyl sulfonate, gallium 2-perfluoronaphthyl sulfonate, indium 2-perfluoronaphthyl sulfonate, aluminum 2-perfluorobiphenyl sulfonate, gallium 2-perfluorobiphenyl sulfonate, indium 2-perfluorobiphenyl sulfonate, aluminum 3-perfluorobiphenyl sulfonate, gallium 3-perfluorobiphenyl sulfonate, indium 3-perfluorobiphenyl sulfonate, aluminum 4-perfluorobiphenyl sulfonate, gallium 4-perfluorobiphenylsulfonate, indium 4-perfluorobiphenylsulfonate, aluminum 3,5-bis(trifluoromethyl)phenyl sulfonate, gallium 3,5-bis(trifluoromethyl)phenyl sulfonate, and indium 3,5-bis(trifluoromethyl)phenylsulfonate.

7. The process of claim 1, wherein the solubilizing agent, initiator, and nucleophilic additive are the same molecule.

8. The process of claim 1, wherein, following completion of polymerization, the recyclable coinitiator is removed by aqueous extraction and subsequently reactivated by dehydration.

9. The process according to claim 1, wherein the cationic polymerization of the olefin monomer occurs in at least one polymerization step phase selected from the group consisting of bulk, suspension, gas phase, and combinations thereof.

10. The process according to claim 1, wherein the cationic polymerization occurs in a controlled manner such that it produces well-defined polymers.

11. A homogeneous initiator system for use with a reaction mixture in the cationic polymerization of olefins, the initiator system comprising:

(A) a recyclable coinitiator selected from aluminum, gallium, and indium perfluorinated organosulfonates of the formula (I);

12. The homogeneous initiator system of claim 11, wherein the solubilizing agent (B) is selected from the group consisting of alcohols, ethers, ketones, aldehydes, esters, carboxylic acids, anhydrides, acyl halides, amides, amines, nitriles, thiols, thioethers, sulfoxides, disulfides, nitro, sulfonyl, carbonyl, and thiocarbonyl.

13. The homogeneous initiator system of claim 11, wherein the X of formula (II) or (III) is selected from the group consisting of a halogen, ester, acyl halide, ether, alcohol, and acid group.

14. The homogeneous initiator system of claim 11, wherein the optional nucleophilic additive is selected from the group consisting of ethers, ketones, esters, amides, pyridines, phosphines, sulfoxides, amides, amines, and tetraalkylammonium salts.