Hydrocarbon sorbent materials

Abstract

Sorbent polymers which are selective to taking up hydrocarbons are provided for separating hydrocarbons from fluids and taking up hydrocarbons from off of and intermixed with solid materials. The hydrocarbons may at least partially be expressed out of and recovered from the polymer by squeezing. The polymers may be re-used for picking up additional hydrocarbons. Methods for producing and using the polymers are also provided.

1 . A sorbent comprising cross-linked units having a structure of formula:
   —[XY n ]— m  
   wherein:
 X comprises a multivalent C 5  to C 50  cycloalkyl, multivalent C 5  to C 50  heterocycloalkyl, multivalent C 5  to C 50  aryl, multivalent C 5  to C 50  heteroaryl, or combinations thereof; 
 Y comprises a divalent C 5  to C 30  cycloalkyl, divalent C 5  to C 30  heterocycloalkyl, divalent C 5  to C 30  aryl, divalent C 5  to C 30  heteroaryl, or combinations thereof; 
 n is an integer of 2 to 10; and 
 m is an integer greater than or equal to 2. 
   
     
     
         2 . The sorbent of  claim 1 , wherein:
 n is 2, 3 or 4;   the cross-linked units are substantially planar;   X comprises a multivalent C 8  to C 50  polycyclic aryl or multivalent C 8  to C 50  polycyclic heteroaryl; and   Y comprises a polyphenyl having 2, 3, or 4 phenyl groups.   
     
     
         3 - 10 . (canceled) 
     
     
         11 . The sorbent of  claim 1 , wherein each X comprises cyclopentane, benzene, azulene, naphthalene, acenaphthylene, biphenylene, acenaphthene, anthracene, phenanthrene, pyrene, tetracene, triphenylene, phenanthrene, corannulene, perylene, coronene, bisanthrene, terrylene, ovalene, circumpyrene, [10]annulene, [14]annulene, [18]annulene, piperidine, oxane, thiane, pyridine, pyran, or thiopyran. 
     
     
         12 . The sorbent of  claim 1 , wherein each Y comprises two or more phenyl groups connected by a covalent bond, —O—, —S—, —NR—, —PR—, —POR—, C 1 -C 4  alkyl, C 2 -C 4  alkenyl, C 2 -C 4  alkynyl, or combinations thereof, wherein R at each instance is —H, —OH, or C 1 -C 4  alkyl. 
     
     
         13 . The sorbent of  claim 1 , wherein:
 X comprises pyrene and Y comprises biphenyl;   each pyrene is bonded to a biphenyl at one or more of positions 1, 3, 6, and 8; and   each biphenyl is bonded to X at one or more of positions 4 and 4′.   
     
     
         14 . The sorbent of  claim 1 , having a repeating structure: 
       
         
           
           
               
               
           
         
       
     
     
         15 . The sorbent of  claim 1 , having a repeating structure: 
       
         
           
           
               
               
           
         
       
     
     
         16 . A method for synthesizing a sorbent, the method comprising crosslinking multivalent components to form a cross-linked composition having a regular repeating structure of formula:
   —[XY n ]— m  
   wherein:
 X is the multivalent component; 
 Y is a cross-linking component; 
 n is an integer of 2 to 10; and 
 m is an integer greater than or equal to 2. 
   
     
     
         17 . The method of  claim 16 , wherein:
 the multivalent component comprises C 5  to C 50  cycloalkyls, C 5  to C 50  heterocycloalkyls, C 5  to C 50  aryls, or C 5  to C 50  heteroaryls, or combinations thereof; and   the cross-linking component comprises a covalent bond, a divalent component, or combinations thereof.   
     
     
         18 . The method of  claim 16 , wherein the cross-linking component is a divalent component and the cross-linking comprises contacting the multivalent component and the divalent component in the presence of a transmettalation catalyst. 
     
     
         19 . The method of  claim 18 , wherein the catalyst is tetrakis(triphenylphosphine)-palladium(0), tris-(dibenzylidene-acetone)-dipalladium(0), bis-(tri-t-butylphosphine)-palladium, tetrakis-(triphenylarsine)-palladium(0), dichlorobis-(triphenylphosphine)-palladium(II), benzylchlorobis-(triphenylphosphine)-palladium(II), paladacycle catalysts, Bis(1,5-cyclooctadiene)nickel(0) or combinations thereof. 
     
     
         20 . The method of  claim 18 , wherein:
 the cross-linking comprises a Suzuki Coupling;   the multivalent component comprises a pyrene having a halogen at each of positions 1, 3, 6, 8; and   the divalent component comprises a divalent arylboron.   
     
     
         21 . The method of  claim 16 , wherein the multivalent component is 1,3,6,8-tetrabromopyrene, the divalent component is 4,4′-biphenyldiboronic acid bis(pinacol), and the cross-linking comprises:
 combining 1,3,6,8-tetrabromopyrene with 4,4′-biphenyldiboronic acid bis(pinacol) at a molar ratio of about, a solvent, a base and a transmettalation catalyst to form a mixture; and 
 forming the cross-linked composition in the mixture. 
 
     
     
         22 . The method of  claim 21 , wherein:
 the solvent comprises dimethyl formamide, dimethyl sulfoxide, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, dimethoxyethane, diethyl carbonate, diethyl ether, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxy ethane, 1,3-dioxolane, methyl formate, 2-methyl tetrahydrofuran, 3-methoxy-oxaziridine-2-one, sulfolane, tetrahydrofuran, or combinations thereof; and   the base comprises potassium carbonate, sodium hydride, sodium bicarbonate, pyrrolidinopyridine, pyridine, triethylamine, tributylamine, trimethylamine, dimethylaminopyridine, diisopropylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, sodium hydroxide, N-ethyldiisopropylamine, N-(methylpolystyrene)-4-(methylamino)pyridine, potassium bis(trimethylsilyl)-amide, sodium bis(trimethylsilyl)amide, potassium tert-butoxide, lithium diisopropylamide, lithium 2,2,6,6-tetramethylpiperidine, butyllithium or combinations thereof.   
     
     
         23 . The method of  claim 21 , further including:
 combining the 1,3,6,8-tetrabromopyrene and 4,4′-biphenyldiboronic acid bis(pinacol) at a molar ratio of about 1:2 to form a first mixture;   introducing the solvent to the first mixture at a molar ratio of about 680:1 solvent to 4,4′-biphenyldiboronic acid bis(pinacol) to form a second mixture;   introducing a base and a transmetallation catalyst to the second mixture to form a third mixture, wherein a molar ratio of base to 4,4′-biphenyldiboronic acid bis(pinacol) is about 10:1 and a molar ratio of tetrakis(triphenylphosphine)-palladium(0) to 4,4′-biphenyldiboronic acid bis(pinacol) is about 0.1:1; and   reacting the third mixture for a period of time sufficient for forming the sorbent in the third mixture.   
     
     
         24 . The method of  claim 23 , wherein the cross-linking further comprises:
 purging the first mixture with an inert gas, or degassing the first mixture, or combinations thereof, the inert gas comprising nitrogen, neon, argon, krypton, xenon, radon, or combinations thereof;   degassing the second mixture;   degassing the third mixture and purging the third mixture with an inert gas comprising nitrogen, neon, argon, krypton, xenon, radon, or combinations thereof;   heating the third mixture to a temperature of about 100° C. to about 160° C., or stirring the third mixture, or combinations thereof;   performing the cross-linking for about 12 hours to about 40 hours;   filtering the cross-linked composition from the first mixture followed by at least one of:
 washing the cross-linked composition with water, methanol, dichloromethane or any combination thereof; 
 purifying the cross-linked composition by a soxhlet extraction with methanol, a soxhlet extraction with dichloromethane, a soxhlet extraction with toluene, a soxhlet extraction with tetrahydrofuran, or any combination thereof; and 
 drying the cross-linked composition in a vacuum at a temperature of about 50° C. to about 60° C. 
   
     
     
         25 . The method of  claim 16 , wherein:
 the multivalent components each comprise the same multivalent component; and   the cross-linking component comprises a covalent bond.   
     
     
         26 . The method of  claim 25 , wherein:
 the cross-linking is a Yamamoto-Type Ullman Cross-Coupling reaction;   the multivalent component is 1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene; and   the cross-linking comprises contacting the 1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrenes in the presence of catalyst bis(1,5-cyclooctadiene)nickel(0).   
     
     
         27 . A method for extracting hydrophobic material, the method comprising:
 contacting a composition containing at least one hydrophobic material with a sorbent having a structure of formula —[XY n ]— m  wherein:
 X comprises a multivalent component comprising a C 5  to C 50  cycloalkyl, C 5  to C 50  heterocycloalkyl, C 5  to C 50  aryl, C 5  to C 50  heteroaryl, or combinations thereof; 
 Y comprises a divalent component comprising a C 5  to C 30  cycloalkyl, C 5  to C 30  heterocycloalkyl, C 5  to C 30  aryl, C 5  to C 30  heteroaryl, or combinations thereof; 
 n is an integer of 2 to 10; and 
   m is an integer greater than or equal to 2;   wherein the at least one hydrophobic material is taken up by the sorbent by at least one of adsorption and absorption; and   separating the sorbent with at least one hydrophobic material from the composition.   
     
     
         28 . The method of  claim 27 , further comprising removing at least a portion of the at least one hydrophobic material from the sorbent and repeating the steps of contacting, separating, and removing. 
     
     
         29 . The method of  claim 28 , wherein the removing comprises at least one of:
 applying pressure to force hydrophobic material from the sorbent, wherein at least about 60% of the hydrophobic material is removable by applying pressure;   heating the sorbent and applying pressure to force hydrophobic material from the sorbent, wherein at least about 90% of the hydrophobic material is removable by applying heat and pressure;   heating the sorbent to at least one of: vaporize the hydrophobic material and burn the hydrophobic material; and   immersing the sorbent in a solvent to dissolve the at least one hydrophobic material.   
     
     
         30 . The method of  claim 27 , wherein:
 the composition containing the at least one hydrophobic material is a liquid, a gas, a solid, or a combination thereof;   the at least one hydrophobic material comprises liquid hydrocarbon selected from petroleum products, oil, gasoline, kerosene, diesel fuel, jet fuel, hexane, ethanol, methanol, pentane and combinations thereof; and   the method further comprises:
 removing at least a portion of the at least one hydrophobic material from the sorbent; and 
 repeating the steps of contacting, separating, and removing. 
   
     
     
         31 . The method of  claim 27 , wherein:
 the composition containing the at least one hydrophobic material is a surface of a solid;   the contacting comprises dispersing the sorbent onto the surface; and   the separating comprises at least one of lifting the sorbent from the surface, dumping the sorbent off of the surface, sweeping the sorbent from the surface, and vacuuming the sorbent from the surface.   
     
     
         32 . The method of  claim 27 , wherein:
 the composition containing at least one hydrophobic material is water of an ocean or lake;   the at least one hydrophobic material is crude oil; and   the method comprises:
 contacting the water and the at least one hydrocarbon with the sorbent; 
 taking up the crude oil from the water into the sorbent; and 
 separating the sorbent having the taken-up crude oil from the water by at least one of: scooping the sorbent from the water, suctioning the sorbent from the water, sedimentation and decanting of the water from the sorbent, and filtering the sorbent from the water. 
   
     
     
         33 . A filter for extracting at least one hydrophobic material from a fluid, the filter comprising:
 a sorbent having a structure of formula —[XY n ]— m  wherein:
 X comprises a multivalent component comprising a C 5  to C 50  cycloalkyl, C 5  to C 50  heterocycloalkyl, C 5  to C 50  aryl, C 5  to C 50  heteroaryl, or combinations thereof; 
 Y comprises a divalent component comprising a C 5  to C 30  cycloalkyl, C 5  to C 30  heterocycloalkyl, C 5  to C 30  aryl, C 5  to C 30  heteroaryl, or combinations thereof; 
 n is an integer of 2 to 10; and 
 m is an integer greater than or equal to 2. 
   
     
     
         34 . The filter of  claim 33 , wherein:
 X comprises a multivalent C 5  to C 50  aryl having at least one axis of symmetry;   Y comprises a para-polyphenyl having 2, 3, or 4 phenyl groups; and   the sorbent has a repeating structure:   
       
         
           
           
               
               
           
         
       
     
     
         35 . The filter of  claim 33 , wherein the sorbent has a repeating structure: 
       
         
           
           
               
               
           
         
       
     
     
         36 . The filter of  claim 33 , wherein:
 the filter is re-usable;   the filter is configured and arranged to at least one of:
 filter at least one hydrophobic material from a liquid; and 
 filter at least one hydrophobic material from a gas; and 
   the method further comprises a support structure for retaining the sorbent, the support structure comprising at least one of:
 a fiber mat having sorbent adhered thereto; 
 an open cell polymer foam having sorbent incorporated therein; 
 a fabric having sorbent adhered thereto; and 
 a housing for retaining a bed of sorbent therein, the housing comprising at least one fluid permeable member for flow of fluid into the housing and into contact the sorbent.