# US 11,897,984 B2 · Tagging agents, anti-scalant polymer compositions, and methods

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- Number: US 11,897,984 B2
- Document ID: US11897984B2
- Status: Granted
- Kind: B2
- Application number: 17/755,564
- Filed: 2020-12-04
- Published: 2023-04-13
- Granted: 2024-02-13
- Earliest claimed: 2019-12-05
- Assignees: Kemira Oyj
- Applicants: Kemira Oyj
- Inventors: Vesa Nuutinen; Erkki Johannes Metsälä; Reijo Aksela; Vesa Vuori; Mehrdad Hesampour
- Web page: https://patentgrep.com/patent/US11897984B2

## CPC

- C08F 224/00: Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen (cyclic esters of polyfunctional acids C08F218/00; cyclic anhydrides of unsaturated acids C08F220/00, C08F222/00)
- C02F 5/10: using organic substances
- C07D 311/82: Xanthenes
- C07D 319/24: [b,e]-condensed with two six-membered rings
- C07D 493/10: Spiro-condensed systems
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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)
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

Tagging agents, including fluorescent monomers, which may be polymerized. Anti-scalant polymer compositions that include a copolymer of a tagging agent and an anti-scalant monomer. Methods for synthesizing tagging agents, anti-scalant polymer compositions, and detecting an anti-scalant polymer composition.

## Claims

### Claim 1

A polymer composition comprising:
a copolymer comprising—
(i) a first monomer selected from the group consisting of (a) a compound of Formula (I), (b) a compound of Formula (II), (c) a compound or isomer of Formula (III), and (d) a compound or isomer of Formula (IV), wherein the first monomer is a tagging monomer, and
(ii) at least one second monomer comprising at least one polymerizable double bond or at least one polymerizable triple bond, wherein the at least one second monomer is a scale-inhibiting monomer;
wherein R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, and R44 are independently selected from the group consisting of hydrogen, hydroxyl, C1-C6 alkoxy, C2-C6 alkenoxy, C2-C6 alkynoxy, —N(R′)(R″), C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and C4-C14 aryl,
wherein R′ and R″ are independently selected from the group consisting of hydrogen and C1-C6 alkyl,
wherein R9, R10, R31 and R32 are independently selected from the group consisting of hydrogen, hydroxyl, C1-C6 alkyl, and C1-C6 alkenyl,
wherein y is a single bond or a double bond, and
wherein z is a single bond or a double bond;
wherein the isomers of Formula (III) comprise a compound of Formula (Illi), a compound of Formula (IIIii), a compound of Formula (IIIiii), or a combination thereof —
and
wherein the isomers of Formula (IV) comprise a compound of Formula (IVi), a compound of Formula (IVii), a compound of Formula (IViii), or a combination thereof—

### Claim 2 (depends on 1)

The polymer composition of claim 1, wherein the first monomer is present in the copolymer at an amount of about 0.01% to about 5%, by weight, based on the weight of the copolymer.

### Claim 3 (depends on 1)

The polymer composition of claim 1, wherein (a) the first monomer comprises the compound of Formula (I), wherein:
(i) R1, R2, R4, R5, R7, R8, R10 are hydrogen, R3 and R6 are hydroxyl, R9 is an unsubstituted C1 alkyl, y is a double bond, and the first monomer is 3′,6′-dihydroxy-3-methyl-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof —
or
(ii) R1, R2, R4, R5, R7, R8, R9, and R10 are hydrogen, R3 and R6 are hydroxyl, y is a double bond, and the first monomer is 3′,6′-dihydroxy-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—
or
(b) the first monomer is the compound of Formula (II), the compound or isomer of Formula (III), or the compound or isomer of Formula (IV), wherein:
(i) R11, R12, R14, R15, R17, and R18 are hydrogen, R13 and R16 are hydroxyl, and the first monomer is 9-methylene-9H-xanthene-3,6-diol, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof —
or
(ii) R19, R20, R21, R23, R24, R25, R26, R28, R29, and R30 are hydrogen, R22 and R27 are hydroxyl, R31 is an unsubstituted C1 alkyl, z is a double bond, R32 is hydrogen, and the first monomer is 3,11-dihydroxy-3′-methyl-5′H-spiro[dibenzo[c,h]xanthene-7,2′-furan]-5′-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—
or
(iii) R33, R34, R35, R37, R38, R39, R40, R42, R43, and R44, are hydrogen, R36 and R41 are hydroxyl, and the compound is 7-methylene-7H-dibenzo[c,h]xanthene-3,11-diol, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof —

### Claim 4 (depends on 1)

The polymer composition of claim 1, wherein the first monomer is the compound of Formula (I) or the compound of Formula (II), wherein:
(i) R1, R2, R4, R5, R7, R8, R10 are hydrogen, R3 and R6 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, R9 is an unsubstituted C1 alkyl, y is a double bond, and the first monomer is 3′,6′-bis(diethylamino)-3-methyl-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—
or
(ii) R11, R12, R14, R15, and R18 are hydrogen, R13 and R16 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, and the first monomer is N3, N3, N6, N6-tetraethyl-9-methylene-9H-xanthene-3,6-diamine, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof:
or
(iii) R1, R2, R4, R5, R7, R8, R9, and R10 are hydrogen, R3 and R6 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, y is a double bond, and the first monomer is 3′,6′-bis(diethylamino)-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—
or
(iv) R1, R2, R4, R5, R7, R8 are hydrogen, R9 and R10 are unsubstituted C1 alkyl, R3 and R6 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, y is a double bond, and the first monomer is 3′,6′-bis(diethylamino)-3,4-dimethyl-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—
or
(v) R1, R2, R4, R5, R7, R8, and R10 are hydrogen, R9 is an unsubstituted C1 alkenyl, R3 and R6 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, y is a single bond, and the first monomer is 3′,6′-bis(diethylamino)-3-methylene-3,4-dihydro-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—

### Claim 5 (depends on 1)

The polymer composition of claim 1, wherein the at least one second monomer comprises (i) sodium allyl sulfonate and at least one of maleic acid, maleic anhydride, or acrylic acid, or (ii) a compound of Formula (V):
wherein R45 and R46 are independently selected from the group consisting of hydrogen and C1-C6 alkyl.

### Claim 6 (depends on 1)

A method for preventing or reducing scale formation, the method comprising:
providing a system comprising a fluid in circulation, wherein the fluid comprises a polymer composition of claim 1;
measuring with an analytical technique an amount of the first monomer in the system or the fluid to determine an amount of the polymer composition in the system or the fluid, wherein the measuring is performed periodically or continuously; and
optionally (i) adding an additional amount of the polymer composition to the system or the fluid if the amount of the polymer composition in the system or the fluid is less than a predetermined value, or (ii) removing a portion of the polymer composition from the system or the fluid if the amount of the polymer composition in the system or the fluid is greater than the predetermined value.

### Claim 7

A compound or isomer of Formula (I), Formula (II), Formula (III), or Formula (IV):
wherein R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, and R44 independently selected from the group consisting of hydrogen, hydroxyl, C1-C6 alkoxy, C2-C6 alkenoxy, C2-C6 alkynoxy, —N(R′)(R″), C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and C4-C14 aryl;
wherein R′ and R″ are independently selected from the group consisting of hydrogen and C1-C6 alkyl;
wherein R9, R10, R31 and R32 are independently selected from the group consisting of hydrogen, hydroxyl, C1-C6 alkyl, and C1-C6 alkenyl;
wherein y is a single bond or a double bond;
wherein z is a single bond or a double bond;
wherein the following compounds are excluded—
(i) 3′,6′-dihydroxy-5H-spiro[furan-2,9′-xanthen]-5-one —
and
(ii) 9-methylene-9H-xanthene-3,6-diol—
wherein the isomers of Formula (III) comprise a compound of Formula (IIIi), a compound of Formula (IIIii), a compound of Formula (IIIiii), or a combination thereof —
and
wherein the isomers of Formula (IV) comprise a compound of Formula (IVi), a compound of Formula (IVii), a compound of Formula (IViii), or a combination thereof—

### Claim 8 (depends on 7)

The compound of claim 7, wherein R1, R2, R4, R5, R7, R8, and R10 are hydrogen, R3 and R6 re hydroxyl, R9 is an unsubstituted C1 alkyl, y is a double bond, and the compound is 3′,6′-dihydroxy-3-methyl-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—

### Claim 9 (depends on 7)

The compound of claim 7, wherein:
(i) R1, R2, R4, R5, R7, R8, and R10 are hydrogen, R3 and R6 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, R9 is an unsubstituted C1 alkyl, y is a double bond, and the first monomer is 3′,6′-bis(diethylamino)-3-methyl-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—
or
(ii) R11, R12, R14, R15, R17, and R18 are hydrogen, R13 and R16 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, and the first monomer is N3, N3, N6, N6-tetraethyl-9-methylene-9H-xanthene-3,6-diamine, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof —
or
(iii) R1, R2, R4, R5, R7, R8, R9, and R10 are hydrogen, R3 and R6 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, y is a double bond, and the first monomer is 3′,6′-bis(diethylamino)-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—
or (v) R1, R2, R4, R5, R7, R8 are hydrogen, R9 and R10 are unsubstituted C1 alkyl, R3 and R6 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, y is a double bond, and the first monomer is 3′,6′-bis(diethylamino)-3,4-dimethyl-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—
or
(vi) R1, R2, R4, R5, R7, R8, and R10 are hydrogen, R9 is an unsubstituted C1 alkenyl, R3 and R6 are —N(R′)(R″), R′ and R″ are unsubstituted C2 alkyl, y is a single bond, and the first monomer is 3′,6′-bis(diethylamino)-3-methylene-3,4-dihydro-5H-spiro[furan-2,9′-xanthen]-5-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—

### Claim 10 (depends on 7)

The compound of claim 7, wherein:
(i) R33, R34, R35, R37, R38, R39, R40, R42, R43, and R44 are hydrogen, R36 and R41 are hydroxyl, and the compound is 7-methylene-7H-dibenzo[c,h]xanthene-3,1 1-diol, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof —
or
(ii) R19, R20, R21, R23, R24, R25, R26, R28, R29, and R30 are hydrogen, R22 and R27 are hydroxyl, R31 is an unsubstituted C1 alkyl, z is a double bond, R32 is hydrogen, and the compound is 3,11-dihydroxy-3′-methyl-5′H-spiro[dibenzo[c, h[xanthene-7,2′-furan[-5′-one, a salt, a hydrate, a salt hydrate, a stereoisomer, a dehydrate, a tautomer, or a derivative thereof—

### Claim 11 (depends on 7)

A method for forming a condensation product comprising a compound of claim 7, the method comprising:
contacting an aryl alcohol, a condensation catalyst, and a compound according to formula (A) to form the condensation product;
wherein R50 and R51 are independently selected from the group consisting of hydrogen, hydroxyl, C1-C6 alkyl, and C1-C6 alkenyl, and
x is a single bond or double bond.

### Claim 12 (depends on 11)

The method of claim 11, wherein the contacting of the aryl alcohol, the condensation catalyst, and the compound occurs at a temperature of about 50° C. to about 150° C.

### Claim 13 (depends on 11)

The method of claim 11, further comprising:
contacting the condensation product with at least one second monomer to form a copolymer;
wherein the at least one second monomer comprises a polymerizable double bond or a polymerizable triple bond, and
wherein the at least one condensation product is present in the copolymer at an amount of about 0.01% to about 5%, by weight, based on the weight of the copolymer.

### Claim 14 (depends on 13)

The method of claim 13, wherein the at least one second monomer comprises:
(i) sodium allyl sulfonate and at least one of maleic acid, maleic anhydride, or acrylic acid, or
(ii) a compound of Formula (V)—
wherein R45 and R46 are independently selected from the group consisting of hydrogen and C1-C6 alkyl.

### Claim 15 (depends on 11)

The method of claim 11, wherein:
(i) R50 is an unsubstituted C1 alkyl, x is a double bond, R51 is hydrogen, and the compound of Formula (A) is 3-methylfuran-2,5-dione—
or
(ii) R50 and R51 are hydrogen, x is a double bond, and the compound of Formula (A) is furan-2,5-dione—
or
(iii) R50 is hydrogen, x is a single bond, R51 is an unsubstituted C1-alkenyl, and the compound of Formula (A) is 3-methylenedihydrofuran-2,5-dione—
or
(iv) R50 and R51 are an unsubstituted C1 alkyl, x is a double bond, and the compound of Formula (A) is 3,4-dimethylfuran-2,5-dione—
or
(v) R50 is hydrogen, x is a single bond, R51 is an unsubstituted C3-alk-1-enyl, and the compound of Formula (A) is 3-allyldihydrofuran-2,5-dione—