# US 11,897,995 B2 · Allophanate based dispersing agent

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- Number: US 11,897,995 B2
- Document ID: US11897995B2
- Status: Granted
- Kind: B2
- Application number: 17/626,842
- Filed: 2020-07-17
- Published: 2022-09-01
- Granted: 2024-02-13
- Earliest claimed: 2019-07-18
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Andreas Gernandt; Huiguang Kou; Steffen Onclin; Clemens Auschra; Johannes Hermann Willenbacher
- Web page: https://patentgrep.com/patent/US11897995B2

## CPC

- C08G 18/7837: {containing allophanate groups}
- C08G 18/285: {Nitrogen containing compounds}
- C08G 18/8175: {with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen}
- C08G 18/833: {by nitrogen containing compounds (by azo compounds C08G18/85)}
- C09D 175/04: Polyurethanes
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

The presently claimed invention is directed to a copolymer obtained by reacting at least one isocyanate (A) comprising at least one allophanate group and at least one active double bond with at least one isocyanate reactive component (B) to form an intermediate product (C); and reacting the intermediate product (C) with at least one active double bond reactive component (D) to obtain the copolymer which can be used as dispersant. The at least one isocyanate reactive component (B) is selected from the group consisting of monofunctional polyether amine (B1), monofunctional polyether alcohol (B2), C6-C30 monofunctional alcohol (B3) and monofunctional polyester alcohol (B4).

## Claims

### Claim 1

A copolymer obtained by:
a. reacting at least one isocyanate (A) comprising at least one allophanate group and at least one active double bond with at least one isocyanate reactive component (B) to form an intermediate product (C), wherein the intermediate product (C) has an NCO content <0.2 wt. %, based to the overall weight of the intermediate product (C); and
b. reacting the intermediate product (C) obtained in step a. with at least one active double bond reactive component (D) to obtain the copolymer;
wherein the at least one isocyanate reactive component (B) is selected from the group consisting of monofunctional polyether amine (B1), monofunctional polyether alcohol (B2),—C6-C30 monofunctional alcohol (B3) and monofunctional polyester alcohol (B4);
and wherein the at least one active double bond reactive component (D) is selected from the group consisting of imidazole, 1H-imidazol-1-amine, (1H-imidazol-1-yl)methanamine, (1H-imidazol-1-yl)ethan-1-amine, 3-(1H-imidazol-1-yl)propan-1-amine, 4-(1H-imidazol-1-yl)butan-1-amine, 5-(1H-imidazol-1-yl)pentan-1-amine, N-ethyl-2-(1H-imidazol-1-yl)ethan-1-amine, (1H-imidazol-1-yl)methanethiol, 2-(1H-imidazol-1-yl)ethane-1-thiol, 3-(1H-imidazol-1-yl)propane-1-thiol, 4-(1H-imidazol-1-yl)butane-1-thiol, (1H-1,2,3-triazol-1-yl)methanamine, 1H-1,2,3-triazole, 2-(1H-1,2,3-triazol-1-yl)ethan-1-amine, 3-(1H-1,2,3-triazol-1-yl)propan-1-amine, 4-(1H-1,2,3-triazol-1-yl)butan-1-amine, 5-(1H-1,2,3-triazol-1-yl)pentan-1-amine, (1H-1,2,3-triazol-1-yl)methanethiol, 2-(1H-1,2,3-triazol-1-yl)ethane-1-thiol, 3-(1H-1,2,3-triazol-1-yl)propane-1-thiol, 4-(1H-1,2,3-triazol-1-yl)butane-1-thiol, 5-(1H-1,2,3-triazol-1-yl)pentane-1-thiol, 4H-1,2,4-triazole, (4H-1,2,4-triazol-4-yl)methanamine, 2-(4H-1,2,4-triazol-4-yl)ethan-1-amine, 3-(4H-1,2,4-triazol-4-yl)propan-1-amine, 4-(4H-1,2,4-triazol-4-yl)butan-1-amine, 5-(4H-1,2,4-triazol-4-yl)pentan-1-amine, (4H-1,2,4-triazol-4-yl)methanethiol, 2-(4H-1,2,4-triazol-4-yl)ethane-1-thiol, 3-(4H-1,2,4-triazol-4-yl)propane-1-thiol, 4-(4H-1,2,4-triazol-4-yl)butane-1-thiol, 5-(4H-1,2,4-triazol-4-yl)pentane-1-thiol, (1H-tetrazol-1-yl)methanamine, 2-(1H-tetrazol-1-yl)ethan-1-amine, 3-(1H-tetrazol-1-yl)propan-1-amine, 4-(1H-tetrazol-1-yl)butan-1-amine, N-methyl-4-(1H-tetrazol-1-yl)butan-1-amine, 5-(1H-tetrazol-1-yl)pentan-1-amine, (1H-tetrazol-1-yl)methanethiol, 2-(1H-tetrazol-1-yl)ethane-1-thiol, 3-(1H-tetrazol-1-yl)propane-1-thiol, 4-(1H-tetrazol-1-yl)butane-1-thiol and 5-(1H-tetrazol-1-yl)pentane-1-thiol, N,N-diethyl-1,4-butanediamine, 1-(2-aminoethyl)piperazine, 2-(1-pyrrolidyl)-ethylamine, 4-amino-2-methoxy-pyrimidine, 2-dimethylaminoethanol, 1-(2-hydroxyethyl)piperazine, 4-(2-hydroxyethyl)morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, N,N-dimethyl-1,3-propanediamine, 4-(2-aminoethyl)pyridine, 2-amino-6-methoxy-benzothiazole, 4-aminomethyl-pyridine, N,N-diallylmelamine, 3-amino-1,2,4-triazole, 1-(3-aminopropyl)imidazole, 4-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)imidazole and 3-mercapto-1,2,4-triazole, 1-(2-aminoethyl)imidazolidin-2-one, benzylamine, aniline, branched or linear (C2H5N)1-500 and salts thereof.

### Claim 2 (depends on 1)

The copolymer according to claim 1, wherein the at least one isocyanate (A) comprising at least one allophanate group and at least one active double bond contains 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 NCO groups.

### Claim 3 (depends on 1)

The copolymer according to claim 1, wherein the at least one isocyanate (A) comprising at least one allophanate group and at least one active double bond is obtained by reacting at least one polyisocyanate (A1) with at least one compound of formula (A2),
wherein Z is selected from the group consisting of —O—, —NR5— and —S—;
R1 and R2 are independently of each other selected from the group consisting of H or CH3, linear or branched, substituted or unsubstituted C1-C30 alkyl, linear or branched, substituted or unsubstituted C2-C30 alkenyl, and substituted or unsubstituted phenyl;
G is selected from the group consisting of —(CH2)k—OH, —(CH2—CH2—O)mH, —(—CH(R3)—CH(R4)—O—)n—H, —CH2—CH(OH)—CH2—O—C(═O)—C(CH3)═CH2 and —CH2—CH(OH)—CH2—O—C(═O)—CH═CH2;
k, m and n are independently of each other an integer in the range of ≥1 to ≤20;
R3 and R4 are independently of each other selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl; and
R5 is selected from the group consisting of H, linear or branched, substituted or unsubstituted C1s-C30 alkyl, linear or branched, substituted or unsubstituted C2-C30 alkenyl, and substituted or unsubstituted phenyl.

### Claim 4 (depends on 3)

The copolymer according to claim 3, wherein the at least one polyisocyanate (A1) is selected from the group consisting of 4,4′-diphenylmethanediisocyanate, toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3-or 1,4-phenylene-diisocyanate, triphenylmethane-4,4′,4″-triisocyanate, poly phenyl-polymethylene polyisocyanate, hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanate-methylcyclohexane, 2,4- or 2,6-hexahydrotolyene-diisocyanate, hexahydro-1,3- or -1,4-phenyidiisocyanate and perhydro-2,4′- or -4,4′-dicyclohexylmethanediisocyanate.

### Claim 5 (depends on 3)

The copolymer according to claim 3, wherein the at least one compound of formula (A2) is selected from the group consisting of hydroxy acrylate (A2a), and hydroxy acrylamide (A2b).

### Claim 6 (depends on 3)

The copolymer according to claim 3, wherein the at least one compound of formula (A2) is selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyethyl acrylamide, and hydroxyethyl methacrylamide.

### Claim 7 (depends on 1)

The copolymer according to claim 1, wherein the at least one isocyanate (A) has active double bonds in the range from ≥1 to ≤10.

### Claim 8 (depends on 1)

The copolymer according to claim 1, wherein the at least one active double bond is a double bond which is conjugated with at least one carbonyl group.

### Claim 9 (depends on 1)

The copolymer according to claim 1, wherein the monofunctional polyether amine (B1) is of formula (B1),
wherein Y is selected from the group consisting of H, linear or branched, substituted or unsubstituted C1-C30 alkyl, and G—(O(CH2)sCH2)o—(CH2—CH(Q))p—;
o and p are independently of each other an integer in the range of ≥0 to ≤2000;
s is an integer in the range of ≥1 to ≤10;
wherein o+p is an integer in the range of ≥1 to ≤4000; and
Q and G are independently of each other selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl.

### Claim 10 (depends on 9)

The copolymer according to claim 9, wherein the monofunctional polyether amine (B 1) has a weight average molecular weight in the range of ≥120 to ≤10000 g/mol, as determined according to GPC.

### Claim 11 (depends on 1)

The copolymer according to claim 1, wherein the copolymer has weight average molecular weight Mw in the range of ≥1000 g/mol to ≤100000 g/mol, as determined according to GPC.

### Claim 12 (depends on 1)

A method for preparing a copolymer according to claim 1, wherein the process comprises the steps of:
i) mixing at least one isocyanate (A) comprising at least one allophanate group and at least one active double bond, with at least one isocyanate reactive component (B) to obtain a mixture;
ii) heating the mixture obtained m step a. to a desired temperature to obtain an intermediate product (C);
iii) mixing the intermediate product (C) obtained in step b. with at least one active double bond reactive component (D) to obtain a mixture; and
iv) heating the mixture obtained in step c. to a desired temperature to obtain the copolymer;
wherein the at least one isocyanate reactive component (B) is selected from the group consisting of monofunctional polyether amine (B1), monofunctional polyether alcohol (B2), C6-C30 monofunctional alcohol (B3) and monofunctional polyester alcohol (B4).

### Claim 13 (depends on 12)

The method according to claim 12, wherein the step ii) is conducted at a temperature in the range of ≥20 to ≤150° C.

### Claim 14 (depends on 12)

The method according to claim 12, wherein the steps i) to iv) are conducted in the presence or in the absence of at least one solvent.

### Claim 15 (depends on 14)

The method according to claim 14, wherein the at least one solvent is selected from the group consisting of ketones, esters, aromatic solvents, aliphatic solvents, cyclic ethers, ethers and mixtures thereof.

### Claim 16 (depends on 12)

The method according to claim 12, wherein the step iv) is conducted at a temperature in the range of ≥20 to ≤150° C.

### Claim 17 (depends on 1)

A liquid composition in the form of a dispersion comprising the copolymer according to claim 1 and a particulate solid material selected from the group consisting of pigments and fillers and a liquid diluent, wherein the particulate solid material is dispersed in the liquid diluent selected from organic solvent or water or mixture from both.

### Claim 18 (depends on 17)

The liquid composition according to claim 17, wherein the weight ratio of the particulate solid material to the copolymer is in the range from ≥100:1 to ≤1:50.

### Claim 19 (depends on 17)

The liquid composition according to claim 17, comprising
a) ≥1 to ≤70% by weight, based on the total weight of the liquid composition, of at least one particulate solid material, selected from the group consisting of pigments and fillers;
b) ≥0.5 to ≤50% by weight, based on the total weight of the liquid composition of the copolymer, and
c) ≥10 to ≤98.5% by weight, based on the total weight of the liquid composition, of at least one liquid diluent.

### Claim 20 (depends on 19)

The liquid composition according to claim 19, wherein the composition is a millbase, a coating composition or an ink.

### Claim 21 (depends on 1)

A method comprising utilizing the copolymer according to claim 1 and salts thereof as a dispersant for particulate solid material selected from the group consisting of pigments and fillers.

### Claim 22 (depends on 1)

The copolymer according to claim 1, wherein the at least one active double bond reactive component (D) is a primary amine or a secondary amine, and wherein the copolymer has a Millbase viscosity after a two-week storage period of from 63 to 1520 mPa*s.