# US 11,027,257 B2 · Polycalixarene materials, methods of making same, and uses thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,027,257 B2 - Document ID: US11027257B2 - Status: Granted - Kind: B2 - Application number: 16/035,616 - Filed: 2018-07-14 - Published: 2019-01-17 - Granted: 2021-06-08 - Earliest claimed: 2017-07-14 - Assignees: New York University in Abu Dhabi Corporation - Applicants: New York University in Abu Dhabi Corporation - Inventors: Ali Trabolsi; Dinesh Shetty - Web page: https://patentgrep.com/patent/US11027257B2 ## CPC - B01J 20/267: {Cross-linked polymers} - B01J 20/28061: {being in the range 100-500 m2/g} - B01J 20/28064: {being in the range 500-1000 m2/g} - B01J 20/28066: {being more than 1000 m2/g} - C02F 1/285: {using synthetic organic sorbents} - C08G 8/12: with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol - C08J 3/24: Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) - C02F 2101/308: {Dyes; Colorants; Fluorescent agents} - C02F 2101/32: Hydrocarbons, e.g. oil - C08J 2361/10: Phenol-formaldehyde condensates - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) ## Abstract Provided are porous polymeric materials, methods of making same, and methods of using same. The porous polymeric materials include crosslinked calixarene moieties. The porous polymeric materials can be added to a sample and absorb/adsorb pollutants present in the sample. The absorbed/adsorbed pollutant can further be isolated from the porous polymeric material. The porous polymeric materials can be recycled. ## Claims ### Claim 1 A porous polymeric material comprising a plurality of calixarene moieties crosslinked by one or more crosslinking moieties, wherein the calixarene has the following structure: wherein R is at each occurrence in the polymeric material independently H, Na+, K+, Cs+, Li+; a polyether group or a polythioether group, or a combination thereof, two R groups are linked by a polyether moiety or polythioether moiety. ### Claim 2 (depends on 1) The porous polymeric material of claim 1, wherein the calixarene is chosen from substituted or unsubstituted calix[4]arene moieties, substituted or unsubstituted calix[6]arene moieties, substituted or unsubstituted calix[8]arene moieties, and combinations thereof. ### Claim 3 (depends on 1) The porous polymeric material of claim 1, wherein the one or more crosslinking moieties have 5 to 40 carbons and comprise one or more C5-C30 aromatic moiety and, optionally, one or more C2 alkynyl moieties. ### Claim 4 (depends on 3) The porous polymeric material of claim 3, wherein the aromatic moiety comprises one or more fused-ring moiety and/or one or more biaryl moiety. ### Claim 5 (depends on 1) The porous polymeric material of claim 1, wherein the crosslinking moiety has the following structure: —Ar—(R2)x—, wherein Ar is independently at each occurrence in the polymeric material comprises one or more C5-C20 aryl moiety; R2 are independently at each occurrence in the polymeric material a C2 alkynyl moiety or —B(—(O)—)2 moiety; and x is 2, 3, 4, 5, 6, 7, or 8. ### Claim 6 (depends on 5) The porous polymeric material of claim 5, wherein the crosslinking moiety has the following structure: —R1—Ar—R2—, wherein R1 and R2 are independently at each occurrence in the polymeric material a C2 alkynyl moiety. ### Claim 7 (depends on 6) The porous polymeric material of claim 6, wherein the crosslinking moiety further comprises one or more aryl linking moiety that is covalently bound to two or more aryl moieties. ### Claim 8 (depends on 7) The porous polymeric material of claim 7, wherein the crosslinking linking moiety is selected from the group consisting of: C1-C6 aliphatic moieties, —S(O)—, phosphorous atom, nitrogen atom, C5-C30 aryl or heteroaryl moieties, and combinations thereof. ### Claim 9 (depends on 1) The porous polymeric material of claim 1, wherein in the one or more crosslinking moieties is/are selected from the group consisting of: and combinations thereof, wherein Ar is independently at each occurrence in the porous polymeric material comprises one or more C5-C20 aryl moiety; or or a combination thereof, wherein Ar is independently at each occurrence in the porous polymeric material comprises one or more C5-C30 aryl moiety. ### Claim 10 (depends on 1) The porous polymeric material of claim 1, wherein the porous polymeric material is mesoporous and/or microporous, has a Brunauer-Emmett-Teller (BET) surface area of 100 m2/g to 5000 m2/g, is amorphous, exhibits a surface tension of 120 degrees to 180 degrees, is insoluble in aqueous solvents, or a combination thereof. ### Claim 11 (depends on 1) A method of preparing a porous polymeric material of claim 1, comprising reacting one or more calixarene compounds having a plurality of reactive groups with one or more crosslinking compounds comprising i) at least two terminal alkyne groups or ii) at least two boronic acid groups and/or boronate ester groups in the presence of a metal catalyst, wherein the porous polymeric material is formed. ### Claim 12 (depends on 11) The method of claim 11, wherein the calixarene compound is a substituted calix[4]arene, a substituted calix[6]arene, a substituted calix[8]arene, or a combination thereof. ### Claim 13 (depends on 11) The method of claim 11, wherein the one or more calixarene compounds are selected from the group consisting of tetrabromo-calix[4]arene-tetrol (5,11,17,23-tetrabromo-25,26,27,28-tetrahydroxycalix[4]arene), hexabromo-calix[6]arene-hexol, octabromo-calix[8]arene-octol, p-sulfonatocalix[4,6,8]arenes, thia-crown-calix[4,6,8]arenes, and combinations thereof. ### Claim 14 (depends on 11) The method of claim 11, wherein the one or more crosslinking compounds are selected from the group consisting of 1,4-diethynylbenzene, 1,3,5-triethynylbenzene, 1,3,6,8-tetraethynylpyrene, di-, tri- and tetra-ethynyl derivatives of substituted and/or unsubstituted phenyl moieties, biphenyl moieties, heteroaryl moieties, and combinations thereof. ### Claim 15 (depends on 11) The method of claim 11, wherein the stoichiometric ratio of the reactive groups of the one or more calixarene compounds and crosslinking compounds is 1:1. ### Claim 16 (depends on 11) The method of claim 11, wherein the polymeric material comprises a plurality of phenoxy groups and the polymeric material is contacted with a lithium source and a lithiated polymeric material is formed or the polymeric material is contacted with a metal source and a metalated polymeric material is formed. ### Claim 17 (depends on 1, 11) An article of manufacture comprising the porous polymeric material of claim 1 or a porous polymeric material made by the method of claim 11. ### Claim 18 (depends on 17) The article of manufacture of claim 17, wherein the article of manufacture is a column or filter cartridge. ### Claim 19 (depends on 1, 11, 17) A method of i) purifying a sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 1, a polymeric material made by the method of claim 11, or the article of manufacture of claim 17, whereby at least 80% of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material, and optionally, reusing the porous material from which at least part of the one or more pollutants have been removed; ii) determining the presence or absence of compounds in a sample comprising: a) contacting the sample with the porous polymeric material of claim 1, a porous polymeric material made by the method of claim 11, or the article of manufacture of any one of claim 17 for an incubation period; b) separating the porous polymeric material from a) from the sample; and c) heating the porous polymeric material from b) or contacting the porous polymeric material from b) with a solvent such that at least a portion of the compounds are the released by the porous polymeric material; and d) determining the presence or absence of any compounds, wherein the presence of one or more compounds correlates to the presence of the one or more compounds in the sample, or isolating the compounds; iii) removing compounds from a sample comprising: a) contacting the sample with the porous polymeric material of claim 1, a polymeric material made by the method of claim 11, or the article of manufacture of claim 17 for an incubation period such that at least some of the compounds are sequestered in the polymer; b) separating the porous polymeric material from a) from the sample; c) heating the porous polymeric material from b) or contacting the porous polymeric material from b) with a solvent such that at least part of the compounds are released by the porous polymeric material; and d) optionally, isolating at least a portion of the compounds; e) optionally, repeating steps a-d with the porous material from c) from which at least part of the compounds have been released.