# US 8,273,678 B2 · Highly active catalysts for alkylene oxide polymerization > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,273,678 B2 - Document ID: US8273678B2 - Status: Granted - Kind: B2 - Application number: 12/597,623 - Filed: 2008-02-28 - Published: 2010-08-05 - Granted: 2012-09-25 - Earliest claimed: 2007-04-26 - Assignees: Dow Global Technologies LLC - Inventors: Eric P. Wasserman; Yang Cheng; Lihao Tang - Web page: https://patentgrep.com/patent/US8273678B2 ## CPC - C08G 65/12: containing organo-metallic compounds or metal hydrides - C08G 65/2654: {Aluminium or boron; Compounds thereof} - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract The reaction product of the reaction product of A.) a ligand of the formula (I), wherein R1, R2, R3, and R4 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms, hydrogen, halogen, or alkoxy groups of 1 to 8 carbon atoms; X in each occurrence independently is CR6 with R6 being hydrogen or an alkyl group of 1 to 8 carbon atoms; and R5 is an organic divalent group of 4 to 40 carbon atoms with the proviso that the two nodes X are not bound to the same atom or to vicinal atoms in the group R5; B.) an aluminum compound of the formula AlR7R8R9, wherein R7, R8 and R9 each independently is a C1 to C12 hydrocarbyl group, hydrogen, halogen, or an alkoxy group of 1 to 20 carbon atoms; and C.) a Lewis base selected from the group consisting of amines, phosphines, amides, nitriles, isonitriles, and alcohols is useful as a polymerization catalyst, particularly for the homopolymerization or copolymerization of an alkylene oxide. ## Claims ### Claim 1 A polymerization catalyst comprising the reaction product of A.) a ligand of the formula I, wherein R1, R2, R3, and R4 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms, hydrogen, halogen, or alkoxy groups of 1 to 8 carbon atoms; X in each occurrence independently is CR6 with R6 being hydrogen or an alkyl group of 1 to 8 carbon atoms; and R5 is an organic divalent group of 4 to 40 carbon atoms and optionally substituted with the proviso that the two nodes X are not bound to the same atom or to vicinal atoms in the group R5; and B.) an aluminum compound of the formula AlR7R8R9, wherein R7, R8 and R9 each independently is a C1 to C12 hydrocarbyl group, hydrogen, halogen, or an alkoxy group of 1 to 20 carbon atoms; and C.) a Lewis base selected from the group consisting of amines, phosphines, amides, nitriles, isonitriles, and alcohols. ### Claim 2 (depends on 1) The polymerization catalyst of claim 1 wherein the divalent group R5 is aromatic. ### Claim 3 (depends on 1) The polymerization catalyst of claim 1 wherein the divalent group R5 comprises a heteroatom selected from the group consisting of O, N, S, Se and P. ### Claim 4 (depends on 1) The polymerization catalyst of claim 1 wherein R1 is t-butyl, 1,1,3,3-tetramethylbutyl, 1-methylcyclohexyl, 1-adamantyl, or α, α-dimethylbenzyl. ### Claim 5 (depends on 1) The polymerization catalyst of claim 1 wherein the ligand A) has the formula II wherein R10, R11, R12, R13, and R14 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms or hydrogen, R15 in each occurrence independently is an alkyl group of 1 to 8 carbon atoms or hydrogen, and E is selected from the group consisting of O, S, NR16, PR16 and C(R16)2, wherein R16 in each occurrence independently is a hydrocarbyl substituent of 1 to 8 carbon atoms or hydrogen. ### Claim 6 (depends on 5) The polymerization catalyst of claim 5 wherein R12, R13, R14, and R15 are hydrogen and E is sulfur. ### Claim 7 (depends on 1) The polymerization catalyst of claim 1 wherein the ligand A) has the formula III wherein R17, R18 and R19 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms or hydrogen, R20 is a hydrocarbyl substituent of 1 to 20 carbon atoms, hydrogen or an alkoxy group of 1 to 20 carbon atoms, R21 in each occurrence independently is an alkyl group of 1 to 8 carbon atoms or hydrogen, and R22 is hydrogen or a group OR23, SR23,N(R23)2, or P(R23)2, wherein R23 in each occurrence independently is hydrogen or a hydrocarbyl group of 1 to 8 carbon atoms. ### Claim 8 (depends on 7) The polymerization catalyst of claim 7 wherein R19 in each occurrence independently is hydrogen, R20 is hydrogen, methyl, t-butyl, or methoxy, R21 and R23 in each occurrence independently are the same or different and are hydrogen or methyl and R22 is a hydroxyl or methoxy group. ### Claim 9 (depends on 1) The polymerization catalyst of claim 1 wherein the molar ratio of the aluminum atoms from the aluminum compound (B) to the OH groups from the ligand (A) is from 0.25:1 to 1:1. ### Claim 10 (depends on 1) The polymerization catalyst of claim 1 wherein the molar ratio of the aluminum from the aluminum compound (B) to the Lewis base (C) is from 5:1 to 1.25:1. ### Claim 11 A process for homopolymerization or copolymerization of an alkylene oxide comprising the step of contacting one or more alkylene oxides with a catalytic amount of a reaction product of at least: A.) a ligand of the formula I, wherein R1, R2, R3, and R4 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms, hydrogen, halogen, or alkoxy groups of 1 to 8 carbon atoms; X in each occurrence independently is CR6 with R6 being hydrogen or an alkyl group of 1 to 8 carbon atoms; and R5 is an organic divalent group of 4 to 40 carbon atoms with the proviso that the two nodes X are not bound to the same atom or to vicinal atoms in the group R5; and B.) an aluminum compound of the formula AlR7R8R9, wherein R7, R8 and R9 each independently is a C1 to C12 hydrocarbyl group, hydrogen, halogen, or an alkoxy group of 1 to 20 carbon atoms; and C.) a Lewis base selected from the group consisting of amines, phosphines, amides, nitriles, isonitriles, and alcohols. ### Claim 12 (depends on 11) The process of claim 11 wherein the polymerization is conducted in an aliphatic hydrocarbon medium. ### Claim 13 (depends on 11) The process of claim 11 wherein the alkylene oxide is ethylene oxide. ### Claim 14 (depends on 11) The process of claim 11 wherein the alkylene oxide is propylene oxide.