# US 7,078,164 B1 · High throughput screen for identifying polymerization catalysts from potential catalysts > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,078,164 B1 - Document ID: US7078164B1 - Status: Granted - Kind: B1 - Application number: 09/596,851 - Filed: 2000-06-19 - Granted: 2006-07-18 - Earliest claimed: 2000-06-19 - Assignees: Symyx Technologies, Inc. - Inventors: Gary M. Diamond; Christopher Goh; Margarete K. Leclerc; Vince Murphy; Howard W. Turner - Web page: https://patentgrep.com/patent/US7078164B1 ## CPC - C08F 110/14: Monomers containing five or more carbon atoms - B01J 2219/00274: Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology - B01J 2219/00738: Organic catalysts - C08F 4/659: Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} - C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+} - C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers - C40B 40/00: Libraries per se, e.g. arrays, mixtures - Y02P 20/582: Recycling of unreacted starting or intermediate materials - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C40B: COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES (in silico combinatorial libraries of nucleic acids, proteins or peptides G16B35/00; in silico combinatorial chemistry G16C20/60) - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract A method is disclosed for screening potential catalysts for polymerization performance. The method includes the steps of reacting a potential catalyst with at least a first monomer under polymerization conditions, determining the polymerization performance of the catalyst with the at least first monomer, and using the determination as a predictor for the polymerization performance of the catalyst for at least a second monomer, wherein the first and second monomers are different from each other and the first monomer is an olefin other than ethylene. The method provides a useful, concrete and tangible result that has particular value for identifying appropriate catalysts for olefin polymerization and copolymerization. ## Claims ### Claim 1 A method of screening potential catalysts for polymerization performance wherein the polymerization performance of the potential catalysts is determined for at least a first monomer as a predictor for the polymerization performance of the potential catalysts for at least a second monomer, the first and second monomers being different from each other and the first monomer being an olefin other than ethylene, the method comprising: concurrently reacting an array of at least 8 potential polymerization catalysts that are different from each other with only the first monomer and not the second monomer under polymerization conditions in a first reaction; determining the polymerization performance of each of the at least 8 potential catalysts reacted with the first monomer in the first reaction; identifying one or more catalysts from the at least 8 potential polymerization catalysts based on the polymerization performance of the catalysts in the first reaction; and reacting the one or more identified catalysts with the first and second monomers under polymerization conditions in a second reaction. ### Claim 2 (depends on 1) A screening method according to claim 1 wherein the step of determining the polymerization performance comprises measuring a characteristic of the reaction products. ### Claim 3 (depends on 1) A screening method according to claim 1 further comprising the step of polymerizing the at least second monomer using the catalyst. ### Claim 4 (depends on 3) A screening method according to claim 3 comprising polymerizing the second monomer in commercial quantities. ### Claim 5 (depends on 1) A screening method according to claim 1 wherein the step of determining the polymerization performance comprises analyzing the polymer using a high throughput chromatography technique. ### Claim 6 (depends on 5) A screening method according to claim 5 comprising analyzing the polymer using size exclusion chromatography. ### Claim 7 (depends on 1) A screening method according to claim 1, wherein the array of potential catalysts comprises a substrate having wells with each of the at least 8 potential catalysts residing in a different well of the substrate. ### Claim 8 (depends on 7) A screening method according to claim 7, wherein the reacting steps further comprise adding other compositions to the wells other than the first or second monomers or the catalysts. ### Claim 9 (depends on 7) A screening method according to claim 7 comprising dispensing the first monomer as a liquid into each reaction vessel that contains one of the potential catalysts prior to the step of reacting the catalyst with the first monomer. ### Claim 10 (depends on 7) A screening method according to claim 7 comprising distributing the first monomer as a gas to each reaction vessel that contains one of the potential catalysts prior to the step of reacting the catalyst with the first monomer. ### Claim 11 (depends on 7) A screening method according to claim 7 further comprising: activating the potential catalysts; and wherein at least a portion of the at least first monomer is provided to each reaction vessel prior to activation of the potential catalysts. ### Claim 12 (depends on 1) A screening method according to claim 1, wherein the step of determining the polymerization performance of the catalysts comprises measuring a property of any polymer sample made during the reaction step, wherein the property is selected from the group consisting of molecular weight, polydispersity index, viscosity, concentration, solvent extractables, solubility, melt flow index, glass transition temperature, melting point, percent crystallinity, density, polymer mass, polymer composition, polymer structure, polymer architecture, and combinations thereof. ### Claim 13 (depends on 1) A screening method according to claim 1, wherein the determination of polymerization performance comprises measuring a property of the reaction mixture from any members of the array, wherein the property is selected from the group consisting of monomer concentration, monomer conversion, ratio of catalyst to monomer, light scattering, viscosity, temperature, visual inspection, intrinsic viscosity, polymer concentration, molecular weight, and combinations thereof. ### Claim 14 (depends on 1) A screening method according to claim 1, wherein the reacting step is carried out to a predetermined point selected from the group consisting of time, monomer consumption, heat of reaction, polymer concentration, viscosity, and molecular weight. ### Claim 15 (depends on 14) A screening method according to claim 14 and further comprising quenching the reaction at the predetermined point. ### Claim 16 (depends on 1) A screening method according to claim 1, wherein the reacting step comprises concurrently reacting each of the at least 8 potential catalysts in the array with the first monomer. ### Claim 17 (depends on 1) A screening method according to claim 1, wherein the determination is used as a predictor for the polymerization activity of the potential catalysts for a co-polymerization of the second monomer with a third monomer. ### Claim 18 (depends on 17) A screening method according to claim 17 and further comprising the step of copolymerizing the second and third monomers. ### Claim 19 (depends on 18) A screening method according to claim 18 comprising copolymerizing the second and third monomers in commercial quantities. ### Claim 20 (depends on 1) A method according to claim 1 wherein the first monomer is an α-olefin. ### Claim 21 (depends on 20) A method according to claim 20 wherein the first monomer is selected from the group consisting of 1-octene, 1-hexene, 1-heptene, 1-nonene, and 1 decene. ### Claim 22 (depends on 1) A screening method according to claim 1 wherein at least the first monomer is represented by the formula: wherein FG is a halogen or a functional group that contains at least one heteroatom. ### Claim 23 A screening method for high throughput screening of potential catalysts for polymerization performance for at least a second monomer, comprising: concurrently reacting a plurality of potential catalysts arrayed on a substrate with a first monomer and not the second monomer in a first reaction, the first and second monomers being different from each other and the first monomer being an olefin other than ethylene; determining a property of any polymer sample or polymerization mixture made during the first reaction at a rate of one hour or less per potential catalyst, identifying one or more catalysts from the potential polymerization catalysts based on the properties of the samples from the first reaction; and reacting the one or more identified catalysts with the first and second monomers under polymerization conditions in a second reaction. ### Claim 24 (depends on 23) A screening method according to claim 23 comprising: concurrently reacting at least 24 potential catalysts; and determining properties at a rate of about 20 minutes or less per potential catalyst. ### Claim 25 (depends on 23) A screening method according to claim 23 wherein the step of determining the polymerization performance comprises measuring a characteristic of the reaction products. ### Claim 26 (depends on 23) A screening method according to claim 23 wherein the step of determining a property comprises measuring the concentration of the polymer formed using the catalyst. ### Claim 27 (depends on 23) A screening method according to claim 23 wherein the step of determining a property comprises measuring the polydispersity index of the polymer formed using the catalyst. ### Claim 28 (depends on 23) A screening method according to claim 23 wherein the step of determining a property comprises analyzing the polymer using a high throughput chromatography technique. ### Claim 29 (depends on 28) A screening method according to claim 28 comprising analyzing the polymer using size exclusion chromatography. ### Claim 30 (depends on 23) A screening method according to claim 23, wherein the step of determining a property comprises measuring a property of any polymer sample made during the reaction step, wherein the property is selected from the group consisting of molecular weight, polydispersity index, viscosity, concentration, solvent extractables, solubility, melt flow index, glass transition temperature, melting point, percent crystallinity, density, polymer mass, polymer composition, polymer structure, polymer architecture, and combinations thereof. ### Claim 31 (depends on 23) A screening method according to claim 23, wherein the step of determining a property comprises measuring a property of the polymerization reaction mixture from any members of the array, wherein the property is selected from the group consisting of monomer concentration, monomer conversion, ratio of catalyst to monomer, light scattering, viscosity, temperature, visual inspection, intrinsic viscosity, polymer concentration, molecular weight, and combinations thereof. ### Claim 32 (depends on 23) A screening method according to claim 23, wherein the concurrent reactions are carried out to a predetermined point selected from the group consisting of time, monomer consumption, heat of reaction, polymer concentration, viscosity, and molecular weight. ### Claim 33 (depends on 32) A screening method according to claim 32 and further comprising concurrently quenching the reaction at the predetermined point. ### Claim 34 (depends on 23) A screening method according to claim 23, wherein the determination is used as a predictor for the polymerization activity of the potential catalysts for a co-polymerization of the second monomer with at least a third monomer. ### Claim 35 (depends on 34) A screening method according to claim 34 and further comprising the step of copolymerizing the at least second and third monomers. ### Claim 36 (depends on 35) A screening method according to claim 35 comprising copolymerizing the at least second and third monomers in commercial quantities. ### Claim 37 (depends on 23) A method according to claim 23 wherein the first monomer is an olefin other than ethylene. ### Claim 38 (depends on 23) A method according to claim 23 wherein the first monomer is 1-octene, 1-hexene, 1-heptene, 1-nonene, and 1 decene. ### Claim 39 (depends on 23) A screening method according to claim 23, wherein the first monomer is represented by a formula selected from the group consisting of: wherein each R is independently selected from the group consisting of halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, substituted heteroaryl, alkoxy, sityl, boryl, phosphino, amino, thio, seleno and combinations thereof; and FG is halogen or a functional group that contains at least one heteroatom. ### Claim 40 A method of screening potential catalysts for polymerization performance wherein the polymerization performance of the potential catalysts is determined for at least a first monomer as a predictor for the polymerization performance of the potential catalysts for at least a second monomer, the first and second monomers being different from each other and the first monomer being an olefin other than ethylene, the method comprising: concurrently reacting an array of at least 8 potential polymerization catalysts that are different from each other with at least the first monomer and not the second monomer under polymerization conditions in a first reaction; determining the polymerization performance of each of the potential catalysts with the at least first monomer in the first reaction by analyzing products of the first reaction; and polymerizing the first and second monomers as copolymers or higher-order polymers in a second reaction using one of the catalysts in the array based upon the polymerization performance of the catalyst. ### Claim 41 (depends on 1) A screening method according to claim 1, wherein the polymerization performance of the identified catalysts for the first reaction has a figure of merit for a particular property. ### Claim 42 (depends on 1) A screening method according to claim 1, further comprising determining the polymerization performance of each of the one or more catalysts reacted with the first and second monomers in the second reaction. ### Claim 43 (depends on 23) A screening method according to claim 23, wherein the polymer samples produced by the identified catalysts for the first reaction have a figure of merit for a particular property. ### Claim 44 (depends on 23) A screening method according to claim 23, further comprising determining a property of any polymer sample or polymerization mixture made during the second reaction at a rate of one hour or less per potential catalyst.