# US 11,896,953 B2 · HLB copolymers

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- Number: US 11,896,953 B2
- Document ID: US11896953B2
- Status: Granted
- Kind: B2
- Application number: 16/640,575
- Filed: 2018-08-24
- Published: 2020-06-25
- Granted: 2024-02-13
- Earliest claimed: 2017-08-24
- Assignees: Sigma-Aldrich Co.
- Applicants: Sigma-Aldrich Co. LLC
- Inventors: William Betz; Curtis Frantz; Michael Keeler; Michael Ye; Ken Espenschied; Sara Smith; Brittany A. Smith
- Web page: https://patentgrep.com/patent/US11896953B2

## CPC

- B01J 20/261: {obtained by reactions only involving carbon to carbon unsaturated bonds (macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F)}
- B01J 20/264: {derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers}
- B01J 20/267: {Cross-linked polymers}
- B01J 20/28004: {Sorbent size or size distribution, e.g. particle size}
- B01J 20/28019: {Spherical, ellipsoidal or cylindrical}
- B01J 20/28028: {Particles immobilised within fibres or filaments}
- B01J 20/2803: {Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products}
- B01J 20/28057: {Surface area, e.g. B.E.T specific surface area}
- B01J 20/28061: {being in the range 100-500 m2/g}
- B01J 20/28064: {being in the range 500-1000 m2/g}
- B01J 20/28083: {being in the range 2-50 nm, i.e. mesopores}
- B01J 20/28085: {being more than 50 nm, i.e. macropores}
- B01J 20/287: Non-polar phases; Reversed phases
- B01J 20/3042: {Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- B01J 20/3092: {Packing of a container, e.g. packing a cartridge or column (of chromatography columns B01D15/206)}
- B01J 20/3204: {Inorganic carriers, supports or substrates}
- B01J 20/327: {Polymers obtained by reactions involving only carbon to carbon unsaturated bonds}
- B01J 20/3276: {Copolymers}
- B01J 20/3282: {Crosslinked polymers}
- C08F 212/36: Divinylbenzene
- C08F 220/44: Acrylonitrile
- G01N 1/405: {by adsorption or absorption}
- B01D 15/325: {Reversed phase}
- B01J 2220/54: Sorbents specially adapted for analytical or investigative chromatography
- B01J 2220/62: In a cartridge
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)

## Abstract

Polymeric adsorbents useful for solid phase extraction (SPE) comprising a copolymer formed by copolymerizing at least one hydrophobic monomer including divinylbenzene and at least one hydrophilic monomer including acrylonitrile are provided. Also provided are SPE cartridges including a divinylbenzene-acrylonitrile hydrophilic-lipophilic balance adsorbent. Further provided are methods of using a divinylbenzene-acrylonitrile hydrophilic-lipophilic balance adsorbent in conventional and simplified SPE techniques.

## Claims

### Claim 1

A polymeric adsorbent for solid phase extraction (SPE) comprising a copolymer formed by copolymerizing at least one hydrophobic monomer and at least one hydrophilic monomer,
wherein the hydrophobic monomer comprises divinylbenzene and the hydrophilic monomer comprises acrylonitrile
wherein the copolymerization is carried out in the presence of a nonpolar porogen and a polar porogen.

### Claim 2 (depends on 1)

The polymeric adsorbent of claim 1 wherein the nonpolar porogen is selected from the group consisting of toluene, xylenes, benzene, hexane, cyclohexane, pentane, heptane, octane, nonane, decane, dodecane, isooctane, dichloromethane, chloroform, carbon tetrachloride, and combinations thereof.

### Claim 3 (depends on 1)

The polymeric adsorbent of claim 1 wherein the polar porogen is selected from the group consisting of benzyl alcohol, butanol, pentanol, hexanol, heptanol, 4-methyl-2-pentanol, isoamyl alcohol, dodecanol, ethyl acetate, 2-ethylhexanol, cyclohexanol, and combinations thereof.

### Claim 4 (depends on 1)

The polymeric adsorbent of claim 1 wherein the nonpolar porogen comprises o-xylene and the polar porogen comprises 4-methyl-2-pentanol.

### Claim 5 (depends on 1)

The polymeric adsorbent of claim 1 wherein the ratio of hydrophobic monomer to hydrophilic monomer is in the range from 10:90 (wt. %) to 90:10 (wt. %).

### Claim 6 (depends on 5)

The polymeric adsorbent of claim 5 wherein the ratio of hydrophobic monomer to hydrophilic monomer is in the range from 30:70 (wt. %) to 70:30 (wt. %).

### Claim 7 (depends on 6)

The polymeric adsorbent of claim 6 wherein the ratio of hydrophobic monomer to hydrophilic monomer is about 63:37 (wt. %).

### Claim 8 (depends on 1)

The polymeric adsorbent of claim 1 wherein the copolymer is poly(divinylbenzene-co-acrylonitrile).

### Claim 9 (depends on 8)

The polymeric adsorbent of claim 8 wherein the ratio of divinylbenzene to acrylonitrile is in the range from about 90:10 (wt. %) to about 10:90 (wt. %).

### Claim 10 (depends on 9)

The polymeric adsorbent of claim 9 wherein the ratio of divinylbenzene to acrylonitrile is in the range from about 25:75 (wt. %) to about 75:25 (wt. %).

### Claim 11 (depends on 10)

The polymeric adsorbent of claim 10 wherein the ratio of divinylbenzene to acrylonitrile is about 63:37 (wt. %).

### Claim 12 (depends on 1)

A porous spherical particle comprising the polymeric adsorbent of claim 1.

### Claim 13 (depends on 12)

The porous spherical particle of claim 12 wherein the porous spherical particle has a diameter in the range from about 20 μm to about 125 μm.

### Claim 14 (depends on 13)

The porous spherical particle of claim 13 wherein the porous spherical particle has a diameter in the range from about 30 μm to about 85 μm.

### Claim 15 (depends on 12)

The porous spherical particle of claim 12 wherein the porous spherical particle has a diameter in the range from about 0.2 μm to about 5 μm.

### Claim 16 (depends on 15)

The porous spherical particle of claim 15 wherein the porous spherical particle has a diameter in the range from about 0.8 μm to about 2 μm.

### Claim 17 (depends on 12)

The porous spherical particle of claim 12 wherein the porous spherical particle has a surface area in the range from about 100 m2/g to 1000 m2/g.

### Claim 18 (depends on 17)

The porous spherical particle of claim 17 wherein the porous spherical particle has a surface area in the range from about 350 m2/g to about 675 m2/g.

### Claim 19 (depends on 12)

The porous spherical particle of claim 12 wherein the porous spherical particle has an average pore diameter in the range from about 50 Å to about 105 Å.

### Claim 20 (depends on 1)

The polymeric adsorbent of claim 1 wherein the polymeric adsorbent is coated on a substrate.

### Claim 21 (depends on 20)

The polymeric adsorbent of claim 20 wherein the substrate is selected from the group consisting of carbon, silica, and metal.

### Claim 22 (depends on 21)

The polymeric adsorbent of claim 21 wherein the substrate is particulate.

### Claim 23 (depends on 21)

The polymeric adsorbent of claim 21 wherein the substrate is a fiber.

### Claim 24 (depends on 1)

A fiber comprising the polymeric adsorbent of claim 1.

### Claim 25 (depends on 24)

The fiber of claim 24 wherein the polymeric adsorbent is coated directly onto the fiber.

### Claim 26 (depends on 24)

The fiber of claim 24 wherein the polymeric adsorbent is porous.

### Claim 27 (depends on 24)

The fiber of claim 24 wherein the polymeric adsorbent is nonporous.

### Claim 28 (depends on 24)

The fiber of claim 24 wherein the polymeric adsorbent is a spherical particle.

### Claim 29 (depends on 28)

The fiber of claim 28 further comprising an adhesive, wherein the adhesive is selected from the group consisting of epoxy resins, polydimethylsiloxane, polysilazane, acrylic resins, phenol formaldehyde resins, polyvinyl acetate, yellow carpenter's glue, polyvinylpyrrolidone, polyester resin, resorcinol resin, urea-resin glue, and combinations thereof.

### Claim 30 (depends on 28)

The fiber of claim 28 further comprising a binder, wherein the binder is selected from the group consisting of polyacrylonitrile, polytetrafluoroethylene, gelatin, cellulose, cellulose derivatives, polyvinylpyrrolidone, starch, sucrose, polyethylene glycol, and combinations thereof.

### Claim 31 (depends on 1)

A cartridge comprising a polymeric adsorbent of claim 1.

### Claim 32 (depends on 31)

The cartridge of claim 31 wherein the polymeric adsorbent comprises porous spherical particles.

### Claim 33 (depends on 1)

A method for removing one or more solutes from a solution, comprising the step of contacting the solution with a polymeric adsorbent of claim 1, wherein the solute is adsorbed onto the polymer.

### Claim 34 (depends on 33)

The method of claim 33 wherein the solution comprises a polar solvent.

### Claim 35 (depends on 34)

The method of claim 34 wherein the polar solvent is an aqueous solvent.

### Claim 36 (depends on 35)

The method of claim 35 wherein the aqueous solvent has a pH in the range from 1 to 14.

### Claim 37 (depends on 36)

The method of claim 36 wherein the aqueous solvent has a pH less than 7.

### Claim 38 (depends on 34)

The method of claim 34 wherein the polar solvent is an organic solvent.

### Claim 39 (depends on 33)

The method of claim 33 wherein the solution has more than 10 solutes.

### Claim 40 (depends on 33)

The method of claim 33 wherein the solutes include at least one protein.

### Claim 41 (depends on 33)

The method of claim 33 wherein the solutes include at least one pharmaceutically relevant analyte.

### Claim 42 (depends on 33)

The method of claim 33 wherein the solutes include at least one phospholipid.

### Claim 43 (depends on 33)

The method of claim 33 wherein the solutes include at least one protein and at least one phospholipid.

### Claim 44 (depends on 33)

The method of claim 33 wherein at least about 75% of the solutes are removed from the solution with a recovery of at least 50%.

### Claim 45 (depends on 44)

The method of claim 44 wherein at least about 90% of the solutes are removed from the solution with a recovery of at least about 70%.

### Claim 46 (depends on 1)

A method for selective removal of a plurality of solutes from a sample comprising the step of
providing a polymeric adsorbent of claim 1;
contacting the sample with the polymeric adsorbent; wherein the solutes are adsorbed by the polymeric solvent; then
washing the polymeric adsorbent;
wherein some solutes remain adsorbed to the polymeric adsorbent after the wash step and some solutes are removed from the polymeric adsorbent during the wash step;
wherein the solutes are selected from the group consisting of proteins, phospholipids, inorganic salts, combinations thereof, and any other unwanted components.

### Claim 47 (depends on 46)

The method of claim 46 wherein at least 90% of the solutes are adsorbed to the polymeric adsorbent in the contacting step.

### Claim 48

A polymeric adsorbent for solid phase extraction (SPE) comprising a poly(divinylbenzene-co-acrylonitrile) copolymer having a porous structure including micropores and mesopores,
wherein the polymeric adsorbent is formed by copolymerizing divinylbenzene and acrylonitrile in the presence of a nonpolar porogen and a polar porogen.

### Claim 49 (depends on 48)

The polymeric adsorbent of claim 48 wherein the nonpolar porogen comprises o-xylene and the polar porogen comprises 4-methyl-2-pentanol.