# US 9,751,789 B2 · Fluorescent monomers and tagged treatment polymers containing same for use in industrial water systems

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- Number: US 9,751,789 B2
- Document ID: US9751789B2
- Status: Granted
- Kind: B2
- Application number: 13/730,087
- Filed: 2012-12-28
- Published: 2014-07-03
- Granted: 2017-09-05
- Earliest claimed: 2012-12-28
- Assignees: Ecolab USA Inc.
- Applicants: Jeffery M Atkins; Barbara E. Moriarty; Paul J. Zinn
- Inventors: Jeffery M Atkins; Barbara E. Moriarty; Paul J. Zinn
- Web page: https://patentgrep.com/patent/US9751789B2

## CPC

- C08F 212/32: containing two or more rings
- C02F 5/12: containing nitrogen (C02F5/14 takes precedence)
- C07D 491/06: Peri-condensed systems
- C08F 12/32: containing two or more rings
- C09B 57/08: Naphthalimide dyes; Phthalimide dyes
- C09B 69/109: {containing other specific dyes}
- C09K 11/06: containing organic luminescent materials
- C02F 1/008: {Control or steering systems not provided for elsewhere in subclass C02F}
- C02F 2103/023: {Water in cooling circuits}
- C02F 2103/10: from quarries or from mining activities
- C02F 2103/16: from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
- C02F 2103/28: from the paper or cellulose industry
- C02F 2103/32: from the food or foodstuff industry, e.g. brewery waste waters
- 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)
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

The invention is directed towards methods and compositions for making and using fluorescent monomers which are synthesized by reacting a substituted or non-substituted benzoxanthene anhydride with an amine and with a moiety containing a polymerizable group. Such monomers are useful for the preparation of tagged treatment polymers. Such tagged treatment polymers are useful as scale inhibitors in industrial water systems.

## Claims

### Claim 1

A method of monitoring an industrial water system, comprising:
(a) adding an inert tracer and a tagged treatment polymer to water resulting in a tagged treatment polymer concentration;
(b) detecting fluorescent signals from the inert tracer and the tagged treatment polymer;
(c) adjusting the amount of tagged treatment polymer concentration in the water;
wherein the tagged treatment polymer is selected from GaQjWt, Ga QvWf Sc, or combinations thereof; and wherein
G, Q, W and S are each monomer moieties making up a backbone of a polymer chain, the distribution of G, Q, W and S along the polymer chain are in random order and in relative amounts of a, j, t, v, f, and c;
for polymer Ga Qv Wf Sc, a is from about 0.001 to about 10.00 mole percent; v is from about 0 to about 97.999 mole percent; f is from about 1 to about 97.999 mole percent; c is from about 1 to about 40 mole percent, and the sum of a, v, f, and c is 100;
for polymer GaQjWt, a is from about 0.001 to about 10.0 mole percent; j is from about 0 to about 99.999 mole percent; t is from about 0.001 to about 99.999 mole percent, and the sum of a, j, and t is 100;
G is selected from Formula I or Formula II
in Formula I, each Y is selected from H, F, Cl, Br, NO2, CO2H and its salts, PO3H2 and it salts, SO3H and its salts, SO2NH2 or SO2NR1R2;
Z is one of the following: CH2, C═O, NH, NR1, NH2+, NOH, O, S, SO, or SO2;
R3 is selected from allyl, 2-hydroxy-3-allyloxy-propyl, vinyl benzyl, 3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl or 2-methacryloxyethyl;
A is absent or selected from alkyl, alkyloxyalkyl, alkylamidoalkyl, or aryl, with the proviso that when A is absent, B is nitrogen (N) and B is bonded directly to the imide nitrogen;
B is sulfur or nitrogen with the proviso that when B is sulfur only one of R1 or R2 is present;
X is an anionic counter ion;
in Formula II, each Y is selected from H, F, Cl, Br, NO2, CO2H and its salts, PO3H2 and it salts, SO3H and its salts, SO2NH2 or SO2NR1R2;
Z is selected from CH2, C═O, NH, NR, NR2+, NOH, O, S, SO, or SO2;
A is absent or selected from alkyl, alkyloxyalkyl, alkoxy, alkylamidoalkyl, alkylamino, NH, or aryl;
R4 is selected from allyl, acryl, methacryl, 2-hydroxy-3-allyloxy-propyl, vinyl benzyl, 2-acryloxyethyl or 2-methacryloxyethyl;
R1 and R2 are independently alkyl;
Q is selected from acrylic acid and salts thereof, methacrylic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, acrylamide, crotonic acid, acrylamidomethylpropane sulfonic acid or salts thereof; and Q cannot be the same as W;
W is selected from acrylic acid and salts thereof, methacrylic acid and salts thereof, itaconic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, crotonic acid and salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid, styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl chloride quaternary salts, dimethylaminoethyl acrylate benzyl chloride quaternary salts, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl methacrylamide methyl sulfate quaternary salts, diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylamino ethyl methacrylate acid salts (including, but not limited to, sulfuric acid and hydrochloride acid salts), dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methylene bis acrylamide, diallylamine, acid salts of diallylamine, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonic acid and the sodium salt thereof, vinyl alcohol, vinyl acetate, or N-vinylpyrrolidone; and
S is selected from sulfomethylacrylamide or sulfoethylacrylamide.

### Claim 2 (depends on 1)

The method of claim 1 in which Q is acrylic acid and W is acrylamide.

### Claim 3 (depends on 1)

The method of claim 1 in which Q is acrylamide, W is acrylic acid, and S is N-sulfomethylacrylamide.

### Claim 4 (depends on 1)

The method of claim 1 in which Q is acrylic acid and W is acrylamidomethylpropane sulfonic acid.

### Claim 5 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl quaternary salt, Q is acrylic acid, W is acrylamide and S is N sulfomethylacrylamide.

### Claim 6 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride quaternary salt, Q is acrylic acid, W is acrylamide and S is N sulfomethylacrylamide.

### Claim 7 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt, Q is acrylic acid, W is acrylamide and S is N sulfomethylacrylamide.

### Claim 8 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane sulfonic acid.

### Claim 9 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane sulfonic acid.

### Claim 10 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, vinylbenzyl chloride quaternary salt and Q is acrylic acid.

### Claim 11 (depends on 1)

The method of claim 1 in which the tagged treatment polymer is added in an amount of about 1 ppm to about 30 ppm.

### Claim 12 (depends on 1)

The method of claim 1 wherein G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt, and Q is acrylic acid.

### Claim 13 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl quaternary salt and Q is acrylic acid.

### Claim 14 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt, Q is acrylic acid, and W is acrylamidomethylpropane sulfonic acid.

### Claim 15 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt, Q is acrylic acid, W is acrylamide and S is N-sulfomethylacrylamide.

### Claim 16 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminoethyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt, Q is acrylic acid, W is acrylamide and S is N-sulfomethylacrylamide.

### Claim 17 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane sulfonic acid.

### Claim 18 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminoethyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane sulfonic acid.

### Claim 19 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt and Q is acrylic acid.

### Claim 20 (depends on 1)

The method of claim 1 in which G is sulfonated —N-(3-N′, N′-Dimethylaminoethyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt and Q is acrylic acid.

### Claim 21 (depends on 1)

The method of claim 1, wherein t is from about 0.001 to about 99.998%.