# US 11,299,561 B2 · Biphasic polymerization processes and ethylene-based polyolefins therefrom > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,299,561 B2 - Document ID: US11299561B2 - Status: Granted - Kind: B2 - Application number: 16/743,824 - Filed: 2020-01-15 - Published: 2020-08-13 - Granted: 2022-04-12 - Earliest claimed: 2019-02-11 - Assignees: ExxonMobil Chemical Patents Inc. - Applicants: ExxonMobil Chemical Patents Inc. - Inventors: Gabor Kiss; Thomas T. Sun - Web page: https://patentgrep.com/patent/US11299561B2 ## CPC - C08F 2/06: Organic solvent - C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers - C08F 2/01: characterised by special features of the polymerisation apparatus used - C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond - C08F 10/02: Ethene - C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+} - C08F 110/02: Ethene - C08F 2400/02: Control or adjustment of polymerization parameters - C08F 2420/10: Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract A continuous process for preparing an ethylene-based polyolefin, the process comprising maintaining a polymerization mixture at a temperature at or above the lower critical phase separation temperature of the polymerization mixture, while, during said step of maintaining, maintaining the polymerization mixture at steady state, where the polymerization mixture is substantially uniform in temperature, pressure, and concentration, where the polymerization mixture includes solvent, monomer including ethylene and optionally monomer copolymerizable with ethylene, a single-site catalyst system, and polymer resulting from the polymerization of the monomer, where the monomer and the polymer are dissolved in the solvent, and where the polymer is an ethylene-based polyolefin having a molecular weight distribution (Mw/Mn) of less than 2.30. ## Claims ### Claim 1 A continuous process for preparing an ethylene-based polyolefin, the process comprising: maintaining a polymerization mixture at a temperature at or above the lower critical phase separation temperature of the polymerization mixture, while, during said step of maintaining, maintaining the polymerization mixture at steady state, where the polymerization mixture is substantially uniform in temperature, pressure, and concentration, where the polymerization mixture includes solvent, monomer including ethylene and optionally monomer copolymerizable with ethylene, a single-site catalyst system, and polymer resulting from the polymerization of the monomer, where the monomer and the polymer are dissolved in the solvent, and where the polymer is an ethylene-based polyolefin having a molecular weight distribution (Mw/Mn) of less than 2.30. ### Claim 2 (depends on 1) The process of claim 1, where said step of maintaining a polymerization mixture includes maintaining the polymerization mixture at a pressure of less than 70 atm. ### Claim 3 (depends on 1) The process of claim 1, where said step of maintaining a polymerization mixture includes maintaining the polymerization mixture at a pressure of less than 50 atm. ### Claim 4 (depends on 1) The process of claim 1, where said step of maintaining a polymerization mixture includes maintaining the polymerization mixture at a temperature greater than 130° C. ### Claim 5 (depends on 1) The process of claim 1, where said step of maintaining a polymerization mixture includes maintaining the polymerization mixture at a temperature greater than 150° C. ### Claim 6 (depends on 1) The process of claim 1, where, during said step of maintaining, maintaining the polymerization mixture at temperature fluctuations of less than 15° C. ### Claim 7 (depends on 1) The process of claim 1, where, during said step of maintaining, maintaining the polymerization mixture at temperature fluctuations of less than 10° C. ### Claim 8 (depends on 1) The process of claim 1, where, during said step of maintaining, maintaining the polymerization mixture at pressure fluctuations of less than 10 atm. ### Claim 9 (depends on 1) The process of claim 1, where, during said step of maintaining, maintaining the polymerization mixture at pressure fluctuations of less than 7 atm. ### Claim 10 (depends on 1) The process of claim 1, where, during said step of maintaining, maintaining the temperature and pressure of the polymerization mixture at a relative percent difference of less than 10%. ### Claim 11 (depends on 1) The process of claim 1, where, during said step of maintaining, maintaining the temperature and pressure of the polymerization mixture at a relative percent difference of less than 6%. ### Claim 12 (depends on 1) The process of claim 1, where the ethylene-based polyolefin has a molecular weight distribution (Mw/Mn) of less than 2.25. ### Claim 13 (depends on 1) The process of claim 1, where the ethylene-based polyolefin has a molecular weight distribution (Mw/Mn) of less than 2.20. ### Claim 14 (depends on 1) The process of claim 1, where the single-site catalyst is prepared by combining a metallocene compound and an activator compound. ### Claim 15 (depends on 1) The process of claim 1, where the polymerization mixture is biphasic liquid-liquid system including a first liquid phase dispersed within a second liquid phase. ### Claim 16 (depends on 15) The process of claim 15, where the first liquid phase is in the form of liquid domains having a diameter of less than 1,000 μm. ### Claim 17 (depends on 16) The process of claim 16, where the first liquid phase is in the form of liquid domains having a diameter of less than 100 μm. ### Claim 18 A method for preparing ethylene-based polyolefin, the method comprising: (i) providing a polymerization vessel; (ii) continuously charging the polymerization vessel with monomer including ethylene and olefin monomer copolymerizable with ethylene, a solvent, and a single-site catalyst system, to thereby form a polymerization mixture; (iii) maintaining the polymerization mixture within the vessel at a temperature at or above the lower critical phase separation temperature of the polymerization mixture; (iv) mixing the polymerization mixture within the vessel so that the temperature, pressure, and concentration of the polymerization mixture within the vessel is substantially uniform; and (v) continuously removing monomer, polymer formed by the polymerization of monomer, solvent, and single-site site catalyst system from the polymerization vessel at a rate substantially constant to the rate of continuously charging monomer, a solvent, and a single-site catalyst system, where the polymer continuously removed from the polymerization mixture is ethylene-based polyolefin having a molecular weight distribution of less than 2.30. ### Claim 19 (depends on 18) The method of claim 18, where said step of maintaining the polymerization mixture within the vessel includes maintaining the polymerization mixture at a temperature greater than 130° C. ### Claim 20 (depends on 18) The method of claim 18, further comprising the step maintaining the polymerization mixture within the vessel at a pressure of less than 70 atm. ### Claim 21 (depends on 18) The method of claim 18, where said step of mixing maintains the polymerization mixture within the vessel at a temperature and pressure at a relative percent difference of less than 10%, and where said step of mixing maintains the concentration of dissolved solids within the polymerization mixture at a relative percent difference of less than 10%. ### Claim 22 (depends on 18) The method of claim 18, where the ethylene-based polyolefin has a molecular weight distribution (Mw/Mn) of less than 2.25. ### Claim 23 (depends on 18) The process of claim 18, where the single-site catalyst is prepared by combining a metallocene compound and an activator compound, and where the polymerization mixture is biphasic liquid-liquid system including a first liquid phase dispersed within a second liquid phase. ### Claim 24 (depends on 23) The process of claim 23, where the first liquid phase is in the form of liquid domains having a diameter of less than 1,000 μm. ### Claim 25 A polymer solution comprising: ethylene-based polyolefin dissolved in solvent at a temperature and pressure above the lower critical separation temperature of the polymer solution, where the ethylene-based polyolefin has a molecular weight distribution, Mw/Mn, of less than 2.3, where the solution is a biphasic solution including a first liquid phase including greater than 10 wt % ethylene-based polyolefin, based on the total weight of the first liquid phase, and a second liquid phase including less than 10,000 ppm ethylene-based polyolefin, based on the total weight of the second liquid phase.