阅读说明：本技术 亲水性阴离子交换色谱介质 (Hydrophilic anion exchange chromatography media ) 是由 C·A·波尔 M·贾亚拉曼 于 2020-03-27 设计创作，主要内容包括：阴离子交换固定相包括基质粒子、附接于所述基质粒子的基础缩聚物层、共价附接于所述基础缩聚物层的一个或多个烷基胺缩聚物层,和共价附接于所述烷基胺缩聚物层的终止缩合层。它们的层是由胺和聚氧化乙烯形成,其中所述羟基与所述胺间隔两个碳原子。(The anion exchange stationary phase includes a matrix particle, a base polycondensation layer attached to the matrix particle, one or more alkylamine polycondensation layers covalently attached to the base polycondensation layer, and a terminating polycondensation layer covalently attached to the alkylamine polycondensation layer. Their layers are formed from an amine and polyethylene oxide, wherein the hydroxyl group is separated from the amine by two carbon atoms.)

1. An anion exchange stationary phase comprising:

a) the matrix particles that are negatively charged are,

b) a base polycondensation layer attached to the negatively charged matrix particles, the base polycondensation layer comprising:

1) a quaternary amine,

2) polyethylene oxide, and

3) a hydroxyl group; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms;

c) one or more alkylamine-polycondensation layers covalently attached to the base-polycondensation layer at the quaternary amine of the layer, the alkylamine-polycondensation layers comprising:

1) the amount of the polyethylene oxide to be used,

2) a hydroxyl group; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms, and

3) a quaternary amine;

d) a termination condensation layer covalently attached to the alkylamine polycondensation layer, the termination condensation layer comprising:

1) the amount of the polyethylene oxide to be used,

2) a hydroxyl group; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms, and

3) a quaternary amine, wherein the quaternary amine comprises two alkyl alcohols, wherein the alcohols are separated from the quaternary amine by two carbon atoms.

2. The anion exchange stationary phase of claim 1, wherein one layer of an alkylamine polycondensation is present.

3. The anion exchange stationary phase of claim 1, wherein there are two alkylamine polycondensation layers.

4. The anion exchange stationary phase of claim 1, wherein the quaternary amine in the termination condensation layer comprises an alkyl group.

5. The anion exchange stationary phase of claim 4, wherein the alkyl group is methyl.

6. The anion exchange stationary phase of claim 4, wherein the alkyl group is ethyl.

7. The anion exchange stationary phase of claim 1, wherein the polyethylene oxide has a molecular weight ranging from about 150 to about 1000.

8. The anion exchange stationary phase of claim 1, wherein the polyethylene oxide has a molecular weight ranging from about 400 to about 600.

9. An anion exchange stationary phase formed by the steps of:

a) forming a base condensation layer by reacting a polyethylene glycol diglycidyl ether with a primary amine on the negatively charged matrix particles;

b) forming one or more alkylamine polymer condensation layers on the base condensation layer by performing one or more reaction cycles; wherein the reaction cycle comprises: treatment with polyethylene glycol diglycidyl ether followed by treatment with an alkylamine.

10. The anion exchange stationary phase of claim 9, further comprising the steps of:

c) a termination condensation layer is formed on the alkylamine polymer condensation layer by treatment with a polyethylene glycol diglycidyl ether, followed by treatment with a tertiary amine comprising two alkyl alcohols and an alkyl group.

11. The anion exchange stationary phase of claim 9, further comprising the steps of:

c) a terminating condensation layer is formed on the alkylamine polymer condensation layer by treatment with a polyethylene glycol diglycidyl ether, followed by treatment with a primary or secondary amine, and then with an epoxide.

12. The anion exchange stationary phase of claim 9, wherein one condensation layer of an alkylamine polymer is present.

13. The anion exchange stationary phase of claim 9, wherein there are two condensation layers of the alkylamine polymer.

14. The anion exchange stationary phase of claim 10, wherein the tertiary amine comprising two alkyl alcohols and one alkyl group is methyldiethanolamine.

15. The anion exchange stationary phase of claim 9, wherein the polyethylene glycol diglycidyl ether has a molecular weight ranging from about 150 to about 1000.

16. The anion exchange stationary phase of claim 9, wherein the polyethylene glycol diglycidyl ether has a molecular weight ranging from about 400 to about 600.

17. A method of separating a sample using an anion exchange stationary phase comprising:

a) negatively charged matrix particles;

b) a base polycondensation layer attached to the negatively charged matrix particles, the base polycondensation layer comprising:

1) a quaternary amine,

2) polyethylene oxide, and

3) a hydroxyl group; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms;

c) one or more alkylamine polycondensation layers covalently attached to the base polycondensation layer at the quaternary amine of the layer, the alkylamine polycondensation layers comprising:

1) the amount of the polyethylene oxide to be used,

2) a hydroxyl group; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms, and

3) a quaternary amine;

d) a termination condensation layer covalently attached to the alkylamine polycondensation layer, the termination condensation layer comprising:

1) the amount of the polyethylene oxide to be used,

2) a hydroxyl group; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms, and

3) a quaternary amine, wherein the quaternary amine comprises two alkyl alcohols, wherein the alcohols are separated from the quaternary amine by two carbon atoms;

the method comprises the following steps:

flowing an eluent through a chromatography column containing the anion exchange stationary phase, wherein the eluent comprises a hydroxide;

separating at least one analyte from a sample injected into the chromatographic column; and

detecting the at least one analyte with a detector.

Background

Chromatography is a widely used analytical technique for chemical analysis and separation of molecules. Chromatography involves the separation of one or more analyte species from other matrix components present in a sample. The stationary phase of the chromatography column is typically selected such that there is an interaction with the analyte. Such interactions may be ionic, hydrophilic, hydrophobic, or a combination thereof. For example, the stationary phase may be derivatized with ionic moieties that desirably bind to the ionic analyte and matrix components at varying levels of affinity. The mobile phase permeates through the stationary phase and competes with the analyte and matrix components for binding to the ionic portion. Mobile phase or eluent is a term used to describe a liquid solvent or buffer solution that is pumped through a chromatography column. During this competition, analyte and substrate components will elute from the stationary phase over time and are subsequently detected in the detector. Examples of some typical detectors are conductivity detectors, UV-VIS spectrophotometers and mass spectrometers. Chromatography has developed over the years as a powerful analytical tool that helps create a healthier, cleaner, safer environment in which complex sample mixtures can be separated and analyzed for various industries, such as water quality, environmental monitoring, food analysis, pharmaceutical and biotechnology.

Disclosure of Invention

The anion exchange stationary phase comprises negatively charged matrix particles, a base polycondensation layer attached to the negatively charged matrix particles, one or more alkylamine polycondensation layers covalently attached to the base polycondensation layer at the layer of quaternary amines, and an optional terminating polycondensation layer covalently attached to the alkylamine polycondensation layer. The base polycondensation layer includes quaternary amine, polyethylene oxide and hydroxyl; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms. The alkylamine polycondensation layer comprises polyethylene oxide, hydroxyl; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms, and a quaternary amine. The termination condensation layer comprises polyethylene oxide, hydroxyl; wherein at least a portion of the hydroxyl groups are separated from the quaternary amine by two carbon atoms, and a quaternary amine, wherein the quaternary amine comprises two alkyl alcohols, wherein the alcohols are separated from the quaternary amine by two carbon atoms.

The anion exchange stationary phase is formed by reacting polyethylene glycol diglycidyl ether with a primary amine on a negatively charged substrate particle to form a base condensation layer. One or more alkylamine polymer condensation layers are then formed on the base condensation layer by performing one or more reaction cycles. The reaction cycle involves treatment with polyethylene glycol diglycidyl ether followed by treatment with an alkyl amine.

The anion exchange stationary phase is formed by reacting polyethylene glycol diglycidyl ether with a primary amine on a negatively charged substrate particle to form a base condensation layer. One or more alkylamine polymer condensation layers are then formed on the base condensation layer by performing one or more reaction cycles. The reaction cycle involves treatment with polyethylene glycol diglycidyl ether followed by treatment with an alkyl amine. A termination condensation layer is formed on the alkylamine polymer condensation layer by treatment with polyethylene glycol diglycidyl ether, followed by treatment with a tertiary amine including two alkyl alcohols and an alkyl group.

The anion exchange stationary phase is formed by reacting polyethylene glycol diglycidyl ether with a primary amine on a negatively charged substrate particle to form a base condensation layer. One or more alkylamine polymer condensation layers are then formed on the base condensation layer by performing one or more reaction cycles. The reaction cycle involves treatment with polyethylene glycol diglycidyl ether followed by treatment with an alkyl amine. A terminating condensation layer is formed on the alkylamine polymer condensation layer by treatment with a polyethylene glycol diglycidyl ether, followed by treatment with a primary or secondary amine, and then with an epoxide.

These and other objects and advantages will become apparent from the accompanying drawings and the description thereof.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments and, together with the general description given above and the detailed description given below, serve to explain the principles of the disclosure.

FIG. 1 illustrates various chemical structures of reagents that can be used to form condensation polymers and condensation reaction products of anion exchange resins.

Figure 2 shows a schematic representation of the base polycondensation layer attached to negatively charged matrix particles.

FIG. 3 shows a schematic of a first polyethylene diepoxide covalently attached to a base condensation polymer and forming pendant epoxy groups to form a first polyethylene oxide diepoxide condensation reaction product.

Figure 4 shows a schematic of amine groups covalently attached to the pendant epoxy groups of a first polyethylene oxide diepoxide condensation reaction product to form a first amine condensation reaction product.

Figure 5 shows a schematic of a second polyethylene diepoxide covalently attached to an amine group of a first amine condensation reaction product to form a second polyethylene oxide diepoxide condensation reaction product.

Figure 6 shows a schematic of Methyldiethanolamine (MDEA) covalently attached to the pendant epoxy group of a second polyethylene oxide diepoxide condensation reaction product to form an MDEA condensation reaction product.

Figure 7 shows a schematic of amine groups covalently attached to the pendant epoxy groups of a second polyethylene oxide diepoxide condensation reaction product to form a second amine condensation reaction product.

Figure 8 shows a schematic of a third ethylene oxide covalently attached to amine groups of a second amine condensation reaction product to form a third ethylene oxide diepoxide condensation reaction product.

Figure 9 shows a schematic of amine groups covalently attached to the pendant epoxy groups of a third ethylene oxide diepoxide condensation reaction product to form a third amine condensation reaction product.

Figure 10 shows chromatography of the anion standard solution performed on examples A, B and C.

FIG. 11 shows a chromatogram of a standard solution of polythionate performed on example A.

FIG. 12 shows a chromatogram of a standard solution of polythionate performed on example B.

FIG. 13 shows a chromatogram of a standard solution of polythionate performed on example C.

Figure 14 shows a chromatogram of a polarizable anion standard solution performed on example a.

Figure 15 shows a chromatogram of a polarizable anion standard solution performed on example B.

Figure 16 shows chromatograms of chlorine and sulfate containing soil samples performed for example B.

Detailed Description

An anion exchange stationary phase comprising negatively charged matrix particles, a base condensate layer attached to the negatively charged matrix particles, one or more alkylamine condensate layers, and a stop condensate layer.

The anion exchange stationary phase can be used in chromatography to separate polarizable, hydrophobic anions from polythionates. Examples of polarizable, hydrophobic anions are p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 1-naphthol-4-sulfonic acid, naphthalene-trisulfonic acid, FDC yellow #5, FDC yellow #6 and FDC Red # 40. In addition, samples containing perchlorate and sulfate-eluting perchlorate were chromatographed prior to sulfate, allowing detection of the detector before it was saturated with sulfate. Most commercially available anion exchange phases are not capable of separating perchlorate and sulfate containing samples because perchlorate elutes at the tail of the sulfate peak, making analysis difficult, especially when high concentrations of sulfate are present in the sample.

Polarizable hydrophobic analyte anions having negatively charged components and hydrophobic components may be difficult to separate on an anion exchange chromatography column. Such analytes tend to stick to the anion exchange chromatography column and do not elute from the column, making ion exchange chromatography difficult and sometimes impossible. Furthermore, polarizable hydrophobic analytes with polyanionic charges (e.g., polythionates) may be even more difficult to elute from anion exchange chromatography columns. The anion exchange stationary phase described herein enables the separation of these polarizable hydrophobic analytes.

The negatively charged matrix particles can be any inert polymeric matrix particles that are chemically stable under the conditions of intended use (e.g., pH 0 to 14). The polymeric particles may be based on a Divinylbenzene (DVB) crosslinking monomer and a carrier resin monomer, wherein the carrier resin monomer may be an Ethylvinylbenzene (EVB) monomer, a styrene monomer, and combinations thereof. The mole percentage of DVB may be 55% and the EVB may be 45%. The carrier resin particles may range in diameter from about 1 micron to about 20 microns, such as from about 2 microns to about 10 microns, and from about 3 microns to about 7 microns. The surface area of the support resin particles may range from about 20m²G to about 800m²A/g, e.g. about 20m²G to about 500m²G, about 20m²G to about 100m²Per g, and about 20m²G to about 30m²(ii) in terms of/g. The carrier resin particles may have a pore size ranging from about 100 angstroms to about 5000 angstroms, such as from about 500 angstroms to about 4000 angstroms, such as from about 500 angstroms to about 3000 angstroms, such as from about 500 angstroms to about 2000 angstroms, such as from about 1000 angstroms to about 4000 angstroms, such as from about 1000 angstroms to about 3000 angstroms, such as from about 1000 angstroms to about 2000 angstroms.

In some embodiments, the negatively charged matrix particles may comprise one or more oversized matrix particlesPorous particles (SMP). SMPs are available from commercial sources including agilent PLRP-s1000A and Waters Styragel HR4-HR 6. The diameter of the ultra-large pore particles can be 4-6 μm, and the surface area is 20-30m²Per g, pore diameter of

And a molar percentage of divinyl benzene crosslinking of 55% and ethyl vinyl benzene of 45%.

In some embodiments, the polymeric matrix particles can be based on other aromatic vinyl monomers, such as alpha-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, vinylnaphthalene, and combinations thereof. The polymeric matrix particles may also be based on unsaturated monomers and copolymers of the above aromatic vinyl monomers and unsaturated monomers. In some embodiments, such monomers are copolymerized with aromatic vinyl crosslinking monomers (e.g., divinylbenzene), although other aromatic vinyl crosslinking monomers such as trivinylbenzene, divinylnaphthalene, and combinations thereof may also be contemplated.

The polymeric matrix particles may be sulfonated to create a negative charge on at least the surface of the particles. For example, particles made with 45% DVB and 55% EVB can be sulfonated by treatment with glacial acetic acid and concentrated sulfuric acid. In some embodiments, the polymeric matrix is grafted with acrylic acid and a water-soluble free radical initiator to introduce negatively charged carboxylate groups, as described in U.S. patent No. 9,132,364, which is incorporated by reference.

The base polycondensation layer is attached to the negatively charged matrix particles by reacting the polyethylene glycol diglycidyl ether with a primary amine in the presence of the negatively charged matrix particles. The base polycondensate is attached to the negatively charged matrix particles by electrostatic interaction. The negatively charged matrix particles may be contained in the reaction column as a packed bed. A solution of polyethylene glycol diglycidyl ether and a primary amine can be flowed through the reaction column to form a base polycondensation layer on the negatively charged substrate particles. In some embodiments, a base condensation layer is formed in the reaction slurry, wherein the polyethylene glycol diglycidyl ether reacts with the primary amine in the presence of the negatively charged matrix particles. The solid matrix particles may be washed and subsequently used in a subsequent step.

Examples of alkyl amines in the base polycondensation layer include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl. In some embodiments, the alkylamine in the base polycondensation layer is methylamine. In some embodiments, the alkylamine in the base polycondensation layer is ethylamine.

Polyethylene glycol diglycidyl ether is reacted with an amine to form polyethylene oxide. The molecular weight of the polyoxyethylene moiety is from about 150 to about 1000, such as from about 150 to about 800, from about 150 to about 600, from about 150 to about 500, from about 200 to about 800, from about 200 to about 600, from about 300 to about 800, from about 300 to about 600, and from about 400 to about 600. The molecular weight of this polymer fraction is the number average molecular weight in grams/mole. In some embodiments, the molecular weight of the polyoxyethylene moiety is about the same as the molecular weight of the polyethylene glycol diglycidyl ether used to form the polyoxyethylene moiety.

In some embodiments, the molar ratio of polyethylene glycol diglycidyl ether to primary amine is about 1: 1. In some embodiments, the ratio of polyethylene glycol diglycidyl ether to primary amine is greater or less to more or less crosslink the base polycondensation layer.

One or more alkylamine polymer condensation layers are attached to the base polycondensation layer. The first alkylamine polymer condensation layer is formed by performing a reaction cycle of reacting the base polycondensation layer with polyethylene glycol diglycidyl ether, followed by treatment with an alkylamine. The second alkylamine polymer condensation layer may be formed on the first alkylamine polymer condensation layer through a second reaction cycle. Additional layers may be formed by performing additional reaction cycles. A schematic representation of the first reaction cycle is shown in fig. 3 and 4, where fig. 3 shows the product after treatment with polyethylene glycol diglycidyl ether, and fig. 4 shows the product after treatment with an alkyl amine. In some embodiments, the alkylamine polymer condensation layer is formed by passing a solution of polyethylene glycol diglycidyl ether and a primary amine through a reaction column containing the base condensation layer. In some embodiments, the alkylamine polymer condensation layer is formed in a slurry with a base polycondensation layer.

In some embodiments, only one condensation layer of the alkylamine polymer is present. In some embodiments, there are two condensation layers of alkylamine polymer. In some embodiments, there are from one to five alkylamine polymer condensation layers. Each layer is formed by performing a reaction cycle.

In some embodiments, the alkylamine in the alkylamine polymer condensation layer is selected from methylamine, ethylamine, ammonia, ethanolamine, 1-amino-2, 3-propanediol, and glucosamine. In some embodiments, the alkylamine in the alkylamine polymer condensation layer is methylamine. In some embodiments, the alkylamine in the alkylamine polymer condensation layer is ethylamine. In some embodiments, the alkylamine in each alkylamine polymer condensation layer need not be the same. In some embodiments, the alkylamine is a mixture of alkylamines.

Polyethylene glycol diglycidyl ether is reacted with an amine to form polyethylene oxide. The molecular weight of the polyoxyethylene moiety is from about 150 to about 1000, such as from about 150 to about 800, from about 150 to about 600, from about 150 to about 500, from about 200 to about 800, from about 200 to about 600, from about 300 to about 800, from about 300 to about 600, and from about 400 to about 600. The molecular weight of this polymer fraction is the number average molecular weight. In some embodiments, the molecular weight of the polyoxyethylene moiety is about the same as the molecular weight of the polyethylene glycol diglycidyl ether used to form the polyoxyethylene moiety.

In some embodiments, the molar ratio of polyethylene glycol diglycidyl ether to primary amine is about 1: 1. In some embodiments, the ratio of polyethylene glycol diglycidyl ether to primary amine is greater or less to more or less crosslink the base polycondensation layer.

The terminal condensation layer is similar to the alkylamine polymer condensation layer except that it is an outer layer. It is formed by reacting a condensation layer of an alkylamine polymer with a polyethylene glycol diglycidyl ether, followed by treatment with an alkylamine. The alkylamine need not be the same alkylamine used to form the alkylamine polymer condensation layer. In some embodiments, the termination condensation layer is formed by passing a solution of polyethylene glycol diglycidyl ether and a primary amine through a reaction column containing one or more condensation layers of an alkylamine polymer. In some embodiments, the termination condensation layer is formed in a slurry having one or more alkylamine polymer condensation layers.

In some embodiments, the alkylamine used to form the termination condensation layer is a tertiary amine. Examples of tertiary amines include, but are not limited to, Methyldiethanolamine (MDEA), dimethylethanolamine, N, N '-dimethyl-1-amino-2, 3-propanediol, and N, N' -dimethylglucamine. In some embodiments, the tertiary amine is MDEA. In some embodiments, the tertiary amine is formed by reaction with a primary amine that is subsequently treated to form the tertiary amine, such as by ethylene oxide or glycidol. In some embodiments, the alkylamine comprises one or more hydroxyl groups that are separated from the amine by two carbon atoms. In some embodiments, the alkylamine comprises two hydroxyl groups separated from the amine by two carbon atoms.

Polyethylene glycol diglycidyl ether is reacted with an amine to form polyethylene oxide. The molecular weight of the polyoxyethylene moiety is from about 150 to about 1000, such as from about 150 to about 800, from about 150 to about 600, from about 150 to about 500, from about 200 to about 800, from about 200 to about 600, from about 300 to about 800, from about 300 to about 600, and from about 400 to about 600. The molecular weight of this polymer fraction is the number average molecular weight. In some embodiments, the molecular weight of the polyoxyethylene moiety is about the same as the molecular weight of the polyethylene glycol diglycidyl ether used to form the polyoxyethylene moiety.

In some embodiments, the molar ratio of polyethylene glycol diglycidyl ether to primary amine is about 1: 1. In some embodiments, the ratio of polyethylene glycol diglycidyl ether to primary amine is greater or less to more or less crosslink the base polycondensation layer.

FIG. 1 illustrates various chemical structures of reagents that can be used to form condensation polymers and condensation reaction products of anion exchange resins. The reagents in figure 1 are polyethylene glycol diglycidyl ether 102, methylamine 104, and Methyldiethanolamine (MDEA) 106.

Fig. 2 shows a schematic representation of a base polycondensation layer 200 attached to negatively charged matrix particles. The base polycondensate contains quaternary amine, polyethylene oxide and hydroxyl group. The base polycondensation layer 200 can be formed from a primary amine and a polyethylene glycol diglycidyl ether, such as methylamine 104 and polyethylene glycol diglycidyl ether 102 (see fig. 1). Although the base polymer layer is depicted as linear, some amine groups may be quaternized and form part of branched or crosslinked moieties. The base layer 200 can be formed in the presence of negatively charged polymeric particles, wherein the base layer is associated and/or partially bound to the negatively charged polymeric particles, as shown in fig. 2. Referring to fig. 2-5 and 7, R may be an alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, and hexyl. Term y can be a value in the range of about 2 to about 20, such as about 6 to about 12. The value of the term x may be a value in the range of about 10 to about 100, such as about 20 to about 40.

FIG. 3 shows a schematic of a first polyethylene diepoxide covalently attached to a base condensation polymer and forming pendant epoxy groups to form a first polyethylene oxide diepoxide condensation reaction product. This is the product formed from the first step of the reaction cycle to form the alkylamine polymer condensation layer.

Figure 4 shows a schematic of amine groups covalently attached to the pendant epoxy groups of a first polyethylene oxide diepoxide condensation reaction product to form a first amine condensation reaction product. This is the product formed from the second step of the reaction cycle to form the alkylamine polymer condensation layer.

Figure 5 shows a schematic of a second polyethylene diepoxide covalently attached to an amine group of a first amine condensation reaction product to form a second polyethylene oxide diepoxide condensation reaction product. This is the product formed from the first step of the second reaction cycle to form the alkylamine polymer condensation layer, or it is the product formed from the first step to form the terminated condensation layer.

Figure 6 shows a schematic of Methyldiethanolamine (MDEA) covalently attached to the pendant epoxy group of a second polyethylene oxide diepoxide condensation reaction product to form an MDEA condensation reaction product. This is the product of the second step formation which forms the termination condensation layer. In this case, the alkylamine used is MDEA. The wavy line may represent adjacent chemical moieties, such as the base condensation polymer 200 and at least a portion of the one or more alkyl amine condensation polymer layers.

Figure 7 shows a schematic of amine groups covalently attached to the pendant epoxy groups of a second polyethylene oxide diepoxide condensation reaction product to form a second amine condensation reaction product. This is the product formed from the second step of the second reaction cycle to form the second condensation layer of the dialkylamine polymer.

Figure 8 shows a schematic of a third ethylene oxide covalently attached to amine groups of a second amine condensation reaction product to form a third ethylene oxide diepoxide condensation reaction product. This is the product formed from the first step of the third reaction cycle to form the third alkyl amine polymer condensation layer, or the product formed from the first step to form the termination condensation layer.

Figure 9 shows a schematic of amine groups covalently attached to the pendant epoxy groups of a third ethylene oxide diepoxide condensation reaction product to form a third amine condensation reaction product. This is the product of the second step formation which forms the termination condensation layer. In this case, the alkylamine used is methylamine.

It should be noted that the hydroxyl group, separated from the quaternary amine by two carbon atoms, makes the hydroxyl group more acidic. The hydroxyl groups spaced from the quaternary amine anion exchange sites by the two carbon spacers (which may be referred to as beta positions or beta hydroxyl groups) are more acidic than the hydroxyl groups spaced by three carbon spacers (gamma positions), four carbon spacers (positions), or hydroxyl groups further away relative to the quaternary amine anion exchange sites. The pKa of the beta hydroxyl group is believed to be about 13.9, which makes it about 100 times more acidic than the hydroxyl group, which is not nearly as acidic as the quaternary amine group. As an example, the model compound choline can be used to illustrate the increased acidity of the beta hydroxyl group relative to the quaternary amine. The hydroxyl group of choline has a pKa of 13.9, much lower than ethanol, which does not have a close quaternary amine. The pKa of the hydroxyl group of ethanol is 15.9. The deprotonated and negatively charged beta hydroxyl groups are stabilized by the adjacent positive charge of the quaternary amine group, thus leading to increased acidity. The deprotonated hydroxyl group can act as a stronger reactant for opening the epoxide ring of the glycidyl group and also for affecting the binding of anions to the quaternary amine anion exchange site.

The term "amine" herein means a primary, secondary, tertiary or tertiary amine unless otherwise statedA quaternary amine. Which is a nitrogen attached to at least one alkyl group. One or more alkyl groups may be substituted with hydroxy (e.g., -CH)₂CH₂OH、-CH₂CH₂CH₂OH、-CH₂CHCH₂OH and-CH₂CH₂CHCH₂OH). If the alcohol is separated from the quaternary amine by two carbon atoms, this means that there are two covalently linked carbon atoms (e.g., H) between the nitrogen and the alcohol₂NCH₂CH₂OH、HN(CH₂CH₂OH)₂、N(CH₂CH₂OH)₃、H₂NCH₂CHOHCH₃、HN(CH₂CHOHCH₃)₂)。

Unless otherwise specified, the term "alkyl" alone or as part of another substituent means herein a straight or branched chain or cyclic hydrocarbon group, or combinations thereof, which may be fully saturated, mono-or polyunsaturated and may include a number of the specified carbon atoms (i.e., C)₁-C₁₀Meaning one to ten carbons) of a divalent or polyvalent group. Examples of saturated hydrocarbon groups include, but are not limited to, groups such as methyl, ethyl, n-propyl (e.g., -CH)₂-CH₂-CH₃，-CH₂-CH₂-CH₂-), isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, cyclohexyl, (cyclohexyl) methyl, cyclopropylmethyl, for example, the radicals n-pentyl, n-hexyl, n-heptyl, homologs and isomers of n-octyl and the like. Unsaturated alkyl is alkyl having one or more double or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, ethenyl, 2-propenyl, butenyl, 2-isopentenyl, 2- (butadienyl), 2, 4-pentadienyl, 3- (1, 4-pentadienyl), ethynyl, 1-and 3-propynyl, 3-butynyl, and higher carbon homologs and isomers. Unless otherwise indicated, the term "alkyl" is also meant to encompass those alkyl derivatives defined in more detail below, such as "heteroalkyl. Alkyl groups limited to hydrocarbyl groups are referred to as "higher alkyl groups". The term "alkyl" may also mean "alkylene" or "alkyldiyl" and, in those instances where alkyl is a divalent group, alkylidene.

In this contextThe term "alkylene" or "alkyldiyl" by itself or as part of another substituent means a divalent group derived from an alkyl group, such as, but not limited to, -CH₂CH₂CH₂- (propylene or propane-1, 3-diyl) and also includes groups described below as "heteroalkylene". Typically, the alkyl (or alkylene) group will have from 1 to about 30 carbon atoms, preferably from 1 to about 25 carbon atoms, more preferably from 1 to about 20 carbon atoms, even more preferably from 1 to about 15 carbon atoms and most preferably from 1 to about 10 carbon atoms. "lower alkyl", "lower alkylene" or "lower alkyl diyl" is a shorter chain alkyl, alkylene or alkyl diyl group, typically having about 10 or less carbon atoms, 8 or less carbon atoms, about 6 or less carbon atoms or about 4 or less carbon atoms.

The term "alkylidene" as employed herein by itself or as part of another substituent means a divalent radical derived from an alkyl group, such as but not limited to CH₃CH₂CH₂Is (propylidene). Typically, the alkylidene group will have from 1 to about 30 carbon atoms, preferably from 1 to about 25 carbon atoms, more preferably from 1 to about 20 carbon atoms, even more preferably from 1 to about 15 carbon atoms and most preferably from 1 to about 10 carbon atoms. "lower alkyl", "lower alkylidene" are shorter chain alkyl, alkylidene groups, typically having about 10 or fewer carbon atoms, 8 or fewer carbon atoms, about 6 or fewer carbon atoms, or about 4 or fewer carbon atoms.

The terms "alkoxy", "alkylamino" and "alkylthio" (or thioalkoxy) are used herein in their conventional sense and refer to those alkyl groups attached to the remainder of the molecule via an oxygen atom, an amino group or a sulfur atom, respectively.

Unless otherwise indicated, the term "heteroalkyl," alone or in combination with another term, herein means a stable straight or branched chain or cyclic hydrocarbon group, or combinations thereof, consisting of the specified number of carbon atoms and at least one heteroatom selected from the group consisting of: o, N, Si, S and B, and wherein the nitrogen and sulfur atoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized. One isOr multiple heteroatoms O, N, B, S and Si can be placed at any internal position of the heteroalkyl group or at a position where the alkyl group is attached to the remainder of the molecule. Examples include, but are not limited to-CH₂-CH₂-O-CH₃、-CH₂-CH₂-NHCH₃、-CH₂-CH₂-N(CH₃)-CH₃、-CH₂-S-CH₂-CH₃、-CH₂-CH₂,-S(O)-CH₃、-CH₂-CH₂-S(O)2-CH₃、-CH＝CH-O-CH₃、-Si(CH₃)₃、-CH₂-CH＝N-OCH₃and-CH ═ CH-N (CH)₃)-CH₃. Up to two heteroatoms may be consecutive, e.g. -CH₂-NH-OCH₃and-CH₂-O-Si(CH₃)₃. Similarly, the term "heteroalkylene" alone or as part of another substituent means a divalent group derived from a heteroalkyl group, such as, but not limited to, -CH₂-CH₂-S-CH₂-CH₂-and-CH₂-S-CH₂-CH₂-NH-CH₂-. For heteroalkylene groups, heteroatoms can also occupy either or both of the chain ends (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, and the like). Optionally, for alkylene and heteroalkylene linking groups, the formula writing direction of the linking group does not indicate the orientation of the linking group. For example of the formula-CO₂R ' -optionally represents-C (O) OR ' and-OC (O) R '.

Unless otherwise indicated, the terms "cycloalkyl" and "heterocycloalkyl" herein by themselves or in combination with other terms mean the cyclic forms of "alkyl" and "heteroalkyl," respectively. In addition, for heterocycloalkyl, a heteroatom may occupy a position where the heterocycle is attached to the rest of the molecule. Examples of cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like. Examples of heterocycloalkyl include, but are not limited to, 1- (1,2,5, 6-tetrahydropyridyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, 1-piperazinyl, 2-piperazinyl, and the like.

Unless otherwise specified, the terms "halo" or "halogen" herein, alone or as part of another substituent, mean a fluorine, chlorine, bromine or iodine atom. Additionally, terms such as "haloalkyl" are meant to encompass monohaloalkyl and polyhaloalkyl. For example, the term "halo (C)₁-C₄) Alkyl is meant to include, but is not limited to, trifluoromethyl, 2,2, 2-trifluoroethyl, 4-chlorobutyl, 3-bromopropyl, and the like.

Unless otherwise indicated, the term "aryl" herein means a polyunsaturated aromatic substituent which may be a single ring or multiple rings (preferably 1 to 3 rings) fused together or covalently linked. The term "heteroaryl" refers to aryl (or ring) containing one to four heteroatoms selected from N, O, S, Si and B, wherein the nitrogen and sulfur atoms are optionally oxidized, and one or more nitrogen atoms are optionally quaternized. The heteroaryl group may be attached to the rest of the molecule through a heteroatom. Non-limiting examples of aryl and heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-benzothiazolyl, Purinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinoxalyl, 5-quinoxalyl, 3-quinolyl and 6-quinolyl. The substituents for each of the above-indicated aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below.

For brevity, the term "aryl" as used herein when used in combination with other terms (e.g., aryloxy, arylsulfenoxy, arylalkyl) includes aryl and heteroaryl rings as defined above. Thus, the term "arylalkyl" is meant to encompass those groups in which an aryl group is attached to an alkyl group (e.g., benzyl, phenethyl, pyridylmethyl, and the like), including those alkyl groups in which a carbon atom (e.g., methylene) is substituted with, for example, an oxygen atom (e.g., phenoxymethyl, 2-pyridyloxymethyl, 3- (1-naphthyloxy) propyl, and the like).

Each of the above terms (e.g., "alkyl," "heteroalkyl," "aryl," and "heteroaryl") is meant to encompass both substituted and unsubstituted forms of the indicated group. Preferred substituents for each type of group are provided below.

Substituents for alkyl and heteroalkyl (including those groups commonly referred to as alkylene, alkenyl, heteroalkylene, heteroalkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl) are generally referred to as "alkyl substituents" and may be one or more of a variety of groups selected from, but not limited to: substituted OR unsubstituted aryl, substituted OR unsubstituted heteroaryl, substituted OR unsubstituted heterocycloalkyl, -OR ', -O, ═ NR ', -N-OR ', -NR ' R ", -SR ', -halo, -SiR ' R" R ' ", -oc (O) R ', -c (O) R ', -CO₂R'、-CONR'R"、-OC(O)NR'R"、-NR"C(O)R'、-NR'-C(O)NR"R"'、-NR"C(O)₂R'、-NR-C(NR'R"R"')＝NR""、-NR-C(NR'R")＝NR"'、-S(O)R'、-S(O)₂R'、-OS(O)₂R'、-S(O)₂NR 'R ", -NRSO2R', -CN and-NO₂The number is in the range of zero to (2m '+1), where m' is the total number of carbon atoms in such groups. R', R "and R" "each preferably independently represent hydrogen, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl (e.g., aryl substituted with 1-3 halogens), substituted or unsubstituted alkyl, alkoxy or thioalkoxy, or arylalkyl. When a compound of the invention comprises more than one R group, for example when more than one of these groups is present, each of the R groups is independently selected to be each R ', R ", R'" and R "" group. When R' and R "are attached to the same nitrogen atom, they may combine with the nitrogen atom to form a 5-, 6-or 7-membered ring. For example, -NR' R "is meant to include, but is not limited to, 1-pyrrolidinyl and 4-morpholinyl. From the above discussion of substituents, those skilled in the art will understand that the term "alkyl" is meant to encompass a group containing a carbon atom bonded to a group other than a hydrogen groupRadicals, e.g. haloalkyl (e.g., -CF)₃and-CH₂CF₃) And acyl (e.g., -C (O) CH)₃、-C(O)CF₃、-C(O)CH₂OCH₃Etc.).

Similar to the alkyl substituents described, the substituents for aryl and heteroaryl groups are generally referred to as "aryl substituents". The substituents are selected, for example: substituted OR unsubstituted alkyl, substituted OR unsubstituted aryl, substituted OR unsubstituted heteroaryl, substituted OR unsubstituted heterocycloalkyl, -OR ', -O, ═ NR ', -N-OR ', -NR ' R ", -SR ', -halo, -SiR ' R" R ' ", -OC (O) R ', -C (O) R ', -CO2R ', -CONR ' R", -OC (O) NR ' R ", -NR" C (O) R ', -NR ' -C (O) NR "R '", -NR "C (O) ' -C (O) (" R ' ")₂R'、-NR-C(NR'R"R"')＝NR""、-NR-C(NR'R")＝NR"'、-S(O)R'、-S(O)₂R'、-S(O)₂NR'R"、-NRSO₂R', -CN and-NO₂、-R'、-N₃、-CH(Ph)₂Fluorine (C)₁-C₄) Alkoxy and fluorine (C)₁-C₄) Alkyl groups ranging in number from zero to the total number of open valences on the aromatic ring system; and wherein R ', R ", R'" and R "" are preferably independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. When a compound of the invention comprises more than one R group, for example when more than one of these groups is present, each of the R groups is independently selected to be each R ', R ", R'" and R "" group.

As used herein, the terms "about" or "approximately" for any numerical value or range denote suitable dimensional tolerances that allow a portion or the entirety of the component to function together as intended as described herein.

While the present disclosure has been illustrated by a description of several embodiments and while the illustrative embodiments have been described in considerable detail, it is not the intention of the applicants to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications may be apparent to those skilled in the art. Furthermore, features from separate lists may be combined; and features from the examples may be generalized throughout the disclosure.

Examples of the invention

Sulfonation of SMP resins

Supermacroporous resin (SMP, 25g) was dispersed in 125g glacial acetic acid. Sulfuric acid (500g concentration) was added and mixed well and sonicated in a water bath at room temperature for 60 minutes. The reaction mixture was poured into about 1000g of ice. Once the reaction reached room temperature, the reaction mixture was filtered and the resin was washed with deionized water until the washings showed a pH near neutral. The resin was isolated for further functionalization.

₂Example a: 3 layers of MeNH

A reaction column of 9 × 250mm (diameter × length) was packed with a surface sulfonation 25m with a diameter of 4.0 μm²SMP resin particles of/g wide pore resin (DVB/EVB). Applying a base condensation layer to the packed column by: polyethylene glycol diglycidyl ether-methylamine solution mixture (26% (wt/wt%)) was mixed at 69 ℃ with respect to polyethylene glycol diglycidyl ether: 4% (wt/wt%) relative to methylamine) was flowed through the column at 0.5 mL/min for 60 minutes to form the base polycondensate. Unless otherwise stated, reagent solutions were prepared in deionized water. Next, the following reagents were flowed through the column at a rate of 0.5 mL/min at 69 ℃.

a) Deionized water (5 minutes)

b) 26% (wt/wt%) polyethylene glycol diglycidyl ether solution, (30 minutes)

c) Deionized water (5 minutes)

d) 4% (wt/wt%) methylamine solution, (30 minutes)

e) Deionized water (5 minutes)

f) 26% (wt/wt%) polyethylene glycol diglycidyl ether (30 minutes)

g) Deionized water (5 minutes)

h) 4% (wt/wt%) methylamine solution, (30 minutes)

i) Deionized water (5 minutes)

j) 26% (wt/wt%) polyethylene glycol diglycidyl ether solution, (30 minutes)

k) Deionized water (5 minutes)

l) 4% (wt/wt%) methylamine solution, (30 minutes)

m) deionized water (25 min).

The anion exchange resin was transferred from the reaction column into a vessel and dispersed with physical force. 200 grams of 0.05M NaOH was mixed with 20 grams of anion exchange resin (resin to 0.05M NaOH ratio 1:10, wt/wt%) in a vessel. The mixture was then sonicated to disperse the resin particles for 2 minutes at room temperature, and then sieved and filtered. Next, the filter cake was washed with deionized water. The resulting filter cake formed a clean resin packed into a 2X 250mm chromatographic column.

Example B: 2-layer MDEA

A reaction column of 9 × 250mm (diameter × length) was packed with a surface sulfonation 25m with a diameter of 4.0 μm²SMP resin particles of/g wide pore resin (DVB/EVB). Applying a base condensation layer to the packed column by: polyethylene glycol diglycidyl ether-methylamine solution mixture (26% (wt/wt%)) was mixed at 69 ℃ with respect to polyethylene glycol diglycidyl ether: 4% (wt/wt%) (relative to methylamine) was flowed through the column at 0.5 mL/min for 60 minutes to form the base polycondensate. Unless otherwise stated, reagent solutions were prepared in deionized water. Next, the following reagents were flowed through the column at a rate of 0.5 mL/min at 69 ℃.

a) Deionized water (5 minutes)

b) 26% (wt/wt%) polyethylene glycol diglycidyl ether solution, (30 minutes)

c) Deionized water (5 minutes)

d) 4% (wt/wt%) methylamine solution, (30 minutes)

e) Deionized water (5 minutes)

f) 26% (wt/wt%) polyethylene glycol diglycidyl ether (30 minutes)

g) Deionized water (5 minutes)

h) 10% (wt/wt%) methyldiethanolamine, (40 minutes)

i) Deionized water (25 minutes).

The anion exchange resin was transferred from the reaction column into a vessel and dispersed with physical force. 200 grams of 0.05M NaOH was mixed with 20 grams of anion exchange resin (resin to 0.05M NaOH ratio 1:10, wt/wt%) in a vessel. The mixture was then sonicated to disperse the resin particles for 2 minutes at room temperature, and then sieved and filtered. Next, the filter cake was washed with deionized water. The resulting filter cake formed a clean resin packed into a 2X 250mm chromatographic column.

₂Example C: 2 layers of MeNH

A reaction column of 9 × 250mm (diameter × length) was packed with a surface sulfonation 25m with a diameter of 4.0 μm²SMP resin particles of/g wide pore resin (DVB/EVB). Applying a base condensation layer to the packed column by: polyethylene glycol diglycidyl ether-methylamine solution mixture (26% (wt/wt%)) was mixed at 69 ℃ with respect to polyethylene glycol diglycidyl ether: 4% (wt/wt%) (relative to methylamine) was flowed through the column at 0.5 mL/min for 60 minutes to form the base polycondensate. Unless otherwise stated, reagent solutions were prepared in deionized water. Next, the following reagents were flowed through the column at a rate of 0.5 mL/min at 69 ℃.

a) Deionized water (5 minutes)

b) 26% (wt/wt%) polyethylene glycol diglycidyl ether solution, (30 minutes)

c) Deionized water (5 minutes)

d) 4% (wt/wt%) methylamine solution, (30 minutes)

e) Deionized water (5 minutes)

f) 26% (wt/wt%) polyethylene glycol diglycidyl ether (30 minutes)

g) Deionized water (5 minutes)

h) 4% (wt/wt%) methylamine solution, (30 minutes)

i) Deionized water (25 minutes).

The anion exchange resin was transferred from the reaction column into a vessel and dispersed with physical force. 200 grams of 0.05M NaOH was mixed with 20 grams of anion exchange resin (resin to 0.05M NaOH ratio 1:10, wt/wt%) in a vessel. The mixture was then sonicated to disperse the resin particles for 2 minutes at room temperature, and then sieved and filtered. Next, the filter cake was washed with deionized water. The resulting filter cake formed a clean resin packed into a 2X 250mm chromatographic column.

Chromatographic conditions

Mounting the column to Thermo Scientific Dionex ICS-5000⁺Ion chromatography systems (available from Thermo Fisher Scientific, Sunnyvale, California) available from seemer feishel technologies, Sunnyvale, California. Deionized water was pumped into a seemex @ EGC 500KOH cartridge (seemex feishel technologies, son neville, ca) using a pump to generate a predetermined concentration of KOH eluent. The temperature regulator was used to maintain a column temperature of 30 ℃. A Dionex AERS 500 suppressor (Sammer Feichel technologies, Senneville, Calif.) and a Thermo Scientific conductivity detector were used. The Dionex AERS 500 suppressor typically uses a constant current to electrolyze water for regeneration of the suppressor. Details of each analysis are given below.

And (3) chromatography: anion(s)

Chromatography was performed by injecting a standard solution containing the anions listed below into a chromatography column containing the resin of one of examples A, B and C.

Anion standard solution

Chromatographic conditions

The resulting chromatogram is shown in FIG. 10.

And (3) chromatography: polythionates

Chromatography was performed by injecting standard solutions containing one of dithionate, tetrathionate, and tetrathionate at the concentrations listed below into a chromatography column containing the resin of one of examples A, B and C.

Polythionate standard solution

Chromatographic conditions for example A

Chromatographic conditions for example B

Chromatographic conditions for example C

The resulting chromatograms are shown in figures 11, 12 and 13, where dithionate is the top chromatogram, trithionate is the middle chromatogram and tetrathionate is the bottom chromatogram. Example C of figure 13 shows the dithionate distortion peak due to too low capacity of the ion exchange resin. The chromatogram of fig. 11 using the ion exchange resin of example a requires a higher eluent concentration than the chromatogram of fig. 12 using the ion exchange resin of example B, thereby providing a simpler and more economical separation. Additionally, the ion exchange resin of example a requires additional reaction cycles compared to the ion exchange resin of example B, making example B easier to manufacture.

And (3) chromatography: polarizable anions

Chromatography was performed by injecting a standard solution containing one of the polarizable anions listed below into a chromatography column containing the resin of one of examples a and B.

Anion standard solution

Chromatographic conditions for example A

Chromatographic conditions for example B

The resulting chromatograms are shown in fig. 14 and 15, in which polarizable anions elute in the order shown in the above table. In fig. 14, it should be noted that FDC yellow #5 and #6 each exhibited an additional peak eluting before peak 1, and FDC red #40 exhibited an additional peak overlapping peak 2. In fig. 15, it should be noted that FDC yellow #6 and FDC red #40 each exhibit additional peaks that elute before peak 1 and between peaks 2 and 3. The chromatogram of fig. 14 using the ion exchange resin of example a requires a higher eluent concentration than the chromatogram of fig. 15 using the ion exchange resin of example B, thereby providing a simpler and more economical separation. Additionally, the ion exchange resin of example a requires additional reaction cycles compared to the ion exchange resin of example B, making example B easier to manufacture.

And (3) chromatography: perchlorate detection

Chromatography was performed on example B using extracts of soil samples containing chlorine and sulphate. Perchlorate was detected only in sample 1. The chlorine to perchlorate ratio was estimated to be about 4000:1 and the sulfate to perchlorate ratio was estimated to be about 2000: 1.

Chromatographic conditions for example B

Because perchlorate elutes before sulfate, this column is suitable for mass spectrometric quantification of perchlorate at ppb levels.