# US 12,180,194 B2 · Multi-aziridine compound > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,180,194 B2 - Document ID: US12180194B2 - Status: Granted - Kind: B2 - Application number: 18/526,220 - Filed: 2023-12-01 - Published: 2024-05-23 - Granted: 2024-12-31 - Earliest claimed: 2018-07-23 - Assignees: Covestro (Netherlands) B.V. - Applicants: Covestro (Netherlands) B.V. - Inventors: Gerardus Cornelis Overbeek; Patrick Johannes Maria Stals; Daan Van Der Zwaag; Alfred Jean Paul Bückmann - Web page: https://patentgrep.com/patent/US12180194B2 ## CPC - C07D 403/14: containing three or more hetero rings - C08G 18/2875: {Monohydroxy compounds containing tertiary amino groups} - C08G 18/227: {of antimony, bismuth or arsenic} - C08G 18/283: {Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds} - C08G 18/758: {containing two or more cycloaliphatic rings} - C08G 18/7628: {containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group} - C08G 18/792: {formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates} - C08K 5/3432: Six-membered rings - C09D 7/40: Additives - C09D 133/08: Homopolymers or copolymers of acrylic acid esters - C09D 133/12: Homopolymers or copolymers of methyl methacrylate - C09D 167/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C09D167/06 takes precedence) - C09D 175/04: Polyurethanes - C08G 18/73: acyclic - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - 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 present invention relates to a multi-aziridine compound having: a) from 2 to 6 of the following structural units (A): whereby R′, R″, R1, R2, R3 and R4 are as defined herein m is an integer from 1 to 6; b) one or more linking chains wherein each one of these linking chains links two of the structural units A; and c) a molecular weight in the range from 600 Daltons to 5000 Daltons. The multi-aziridine compound can be used for example for crosslinking of for example carboxylic acid functional polymers dissolved and/or dispersed in an aqueous medium. ## Claims ### Claim 1 A multi-aziridine compound having: a) from 2 to 6 of the following structural units (A): whereby R1 is H; R2 and R4 are independently chosen from H, a linear group containing from 1 to 8 carbon atoms and optionally containing one or more heteroatoms, a branched or cyclic group containing from 3 to 8 carbon atoms and optionally containing one or more heteroatoms, phenyl, benzyl, or pyridinyl; R3 is linear group containing from 1 to 8 carbon atoms and optionally containing one or more heteroatoms, a branched or cyclic group containing from 3 to 8 carbon atoms and optionally containing one or more heteroatoms, phenyl, benzyl, or pyridinyl; or R2 and R3 (in case R2 is different than H) may be part of the same cyclic group containing from 3 to 8 carbon atoms; R′═H or an aliphatic hydrocarbon group containing from 1 to 12 carbon atoms; R″ is an aliphatic hydrocarbon group containing from 1 to 12 carbon atoms, a cycloaliphatic hydrocarbon group containing from 5 to 12 carbon atoms, an aromatic hydrocarbon group containing from 6 to 12 carbon atoms, CH2—O—(C═O)—R′″, CH2—O—R″″, or CH2—(OCR′″″HCR′″″H)n—OR″″″, whereby R′″ is an aliphatic hydrocarbon group containing from 1 to 12 carbon atoms and R″″ is an aliphatic hydrocarbon group containing from 1 to 12 carbon atoms or an aromatic hydrocarbon group containing from 6 to 12 carbon atoms, n being from 1 to 35, R′″″ independently being H or an aliphatic hydrocarbon group containing from 1 to 12 carbon atoms and R″″″ being an aliphatic hydrocarbon group containing from 1 to 4 carbon atoms; or R′ and R″ may be part of the same saturated cycloaliphatic hydrocarbon group containing from 5 to 8 carbon atoms; m is an integer from 1 to 6; b) one or more linking chains wherein each one of these linking chains links two of the structural units A and wherein the linking chain is a shortest chain of consecutive atoms that links two structural units A; and c) a molecular weight in the range from 600 Daltons to 5000 Daltons. ### Claim 2 (depends on 1) The multi-aziridine compound according to claim 1, wherein R′ is H or an alkyl group containing from 1 to 4 carbon atoms. ### Claim 3 (depends on 1) The multi-aziridine compound according to claim 1, wherein R′ is H or an alkyl group containing from 1 to 2 carbon atoms. ### Claim 4 (depends on 1) The multi-aziridine compound according to claim 1, wherein R2 and R4 are independently chosen from H or an aliphatic hydrocarbon group containing from 1 to 2 carbon atoms, and R3 is an aliphatic hydrocarbon group containing from 1 to 4 carbon atoms. ### Claim 5 (depends on 1) The multi-aziridine compound according to claim 1, wherein R2 is H, R3 is CH3 and R4 is H. ### Claim 6 (depends on 1) The multi-aziridine compound according to claim 1, wherein R2 is H, R3 is CH3 and R4 is CH3. ### Claim 7 (depends on 1) The multi-aziridine compound according to claim 1, wherein m is 1. ### Claim 8 (depends on 1) The multi-aziridine compound according to claim 1, wherein R′═H or an alkyl group containing from 1 to 2 carbon atoms; R″=an aliphatic hydrocarbon group containing from 1 to 4 carbon atoms, CH2—O—(C═O)—R′″, CH2—O—R″″, or CH2—(OCR′″″HCR′″″H)n—OR″″″, whereby R′″ is an alkyl group containing from 1 to 12 carbon atoms and R″″ is an alkyl group containing from 1 to 12 carbon atoms, n being from 1 to 35, R′″″ independently being H or a methyl group and R″″″ being an alkyl group containing from 1 to 4 carbon atoms; or R′ and R″ may be part of the same saturated cycloaliphatic hydrocarbon group containing from 5 to 8 carbon atoms; m is 1. ### Claim 9 (depends on 1) The multi-aziridine compound according to claim 1, wherein R′ is H and R″=an alkyl group containing from 1 to 4 carbon atoms, CH2—O—(C═O)—R′″, CH2—O—R″″, or CH2—(OCH2CH2)n—OCH3, whereby R′″ is an alkyl group containing from 3 to 12 carbon atoms and R″″ is an alkyl group containing from 1 to 12 carbon atoms. ### Claim 10 (depends on 1) The multi-aziridine compound according to claim 1, wherein the multi-aziridine compound contains 2 or 3 structural units (A). ### Claim 11 (depends on 1) The multi-aziridine compound according to claim 1, wherein the linking chains consist of from 6 to 100 atoms and the atoms of the linking chains are C, N and/or O. ### Claim 12 (depends on 1) The multi-aziridine compound according to claim 1, wherein the multi-aziridine compound has a molecular weight of from 840 to 3800 Daltons. ### Claim 13 (depends on 1) The multi-aziridine compound according to claim 1, wherein the multi-aziridine compound comprises one or more connecting groups wherein each one of these connecting groups connects two of the structural units A, whereby a connecting group is defined as an array of consecutive functionalities connecting two structural units A and whereby the connecting groups consist of at least one functionality selected from: aliphatic hydrocarbon functionality, cycloaliphatic hydrocarbon functionality, aromatic hydrocarbon functionality, isocyanurate functionality, iminooxadiazindione functionality, ether functionality, ester functionality, amide functionality, carbonate functionality, urethane functionality, urea functionality, biuret functionality, allophanate functionality, uretdione functionality and any combination thereof. ### Claim 14 (depends on 12) The multi-aziridine compound according to claim 12, wherein the connecting groups of the multi-aziridine compound consist of at least one functionality selected from: aliphatic hydrocarbon functionality, cycloaliphatic hydrocarbon functionality, aromatic hydrocarbon functionality, isocyanurate functionality, iminooxadiazindione functionality, urethane functionality, urea functionality, biuret functionality and any combination thereof. ### Claim 15 (depends on 13) The multi-aziridine compound according to claim 13, wherein the connecting groups consist of at least one aliphatic hydrocarbon functionality and/or at least one cycloaliphatic hydrocarbon functionality and optionally at least one aromatic hydrocarbon functionality and optionally an isocyanurate functionality or an iminooxadiazindione functionality. ### Claim 16 (depends on 13) The multi-aziridine compound according to claim 13, wherein the connecting groups consist of at least one aliphatic hydrocarbon functionality and/or at least one cycloaliphatic hydrocarbon functionality and an isocyanurate functionality or an iminooxadiazindione functionality. ### Claim 17 (depends on 1) The multi-aziridine compound according to claim 1, wherein the multi-aziridine compound is according to the following structural formula: in which Z is a molecular residue obtained by removing isocyanate reactive groups XH of a molecule; q is an integer from 2 to 6; i is an integer from 1 to q; Di independently have the following structural formula in which X is NR11, S or O, whereby R11 is H or an alkyl group with 1 to 4 carbon atoms; Y is an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group or a combination thereof; j is an integer from 1 to p; p is an integer from 0 to 10, m, R′, R″, R1, R2, R3 and R4 are as previously defined. ### Claim 18 (depends on 17) The multi-aziridine compound according to claim 17, wherein the molecule from which isocyanate reactive group are removed to obtain Z is a diol, a triol, a polyether with terminal isocyanate reactive groups, a polyamide with terminal isocyanate reactive groups, a polycarbonate with terminal isocyanate reactive groups, or a polysiloxane with terminal isocyanate reactive groups which groups are linked to the siloxane via at least one carbon atom, p is o and m is 1. ### Claim 19 (depends on 1) The multi-aziridine compound according to claim 1, wherein the multi-aziridine compound contains at least 5 wt. % and less than 20 wt. % of urethane bonds. ### Claim 20 (depends on 1) The multi-aziridine compound according to claim 1, wherein the multi-aziridine compound is obtained by reacting at least a polyisocyanate and a compound B with the following structural formula: whereby the molar ratio of compound B to polyisocyanate is from 2 to 6, more preferably from 2 to 4 and most preferably from 2 to 3, and whereby m, R′, R″, R1, R2, R3 and R4 are as previously defined. ### Claim 21 (depends on 20) The multi-aziridine compound according to claim 20, wherein the polyisocyanate is a polyisocyanate with aliphatic reactivity. ### Claim 22 (depends on 20) The multi-aziridine compound according to claim 20, wherein compound B is obtained by reacting at least a non-OH functional monoepoxide compound with an aziridine with the following structural formula: whereby R1, R2, R3 and R4 are as previously defined. ### Claim 23 (depends on 22) The multi-aziridine compound according to claim 22, wherein the non-OH functional monoepoxide compound is selected from the group consisting of propylene oxide, 2-ethyl oxirane, n-butylglycidylether, 2-ethylhexylglycidylether, glycidyl neodecanoate and any mixture thereof. ### Claim 24 (depends on 1) The multi-aziridine compound according to claim 1, wherein the multi-aziridine compound contains polyoxyethylene (—O—CH2-CH2-)x groups or polyoxypropylene (—O—CHCH3-CH2-)x groups or polytetrahydrofurane (—O—CH2-CH2-CH2-CH2)x groups in an amount of at least 0.1 wt. % and in an amount of less than 45 wt. %, relative to the multi-aziridine compound. ### Claim 25 (depends on 1) A crosslinker composition comprising at least one multi-aziridine compound according to claim 1 and further comprising at least one additional component. ### Claim 26 (depends on 25) The crosslinker composition according to claim 25, wherein the molecular weight of the multi-aziridine compounds present in the crosslinker composition is in the range from 600 Daltons to 5000 Daltons. ### Claim 27 (depends on 25) The crosslinker composition according to claim 25, wherein the amount of aziridine functional molecules having a molecular weight lower than 580 Daltons is lower than 5 wt. %, relative to the total weight of the crosslinker composition, whereby the molecular weight is determined using LC-MS as described in the description. ### Claim 28 (depends on 25) The crosslinker composition according to claim 25, wherein the crosslinker composition contains less than 5 wt. % of water. ### Claim 29 (depends on 1) A method for crosslinking a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium comprising providing the multi-aziridine compound according to claim 1. ### Claim 30 (depends on 1) A two-component system comprising a first component and a second component each of which is separate and distinct from each other and wherein the first component comprises a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium and the second component comprises a multi-aziridine compound according to claim 1. ### Claim 31 (depends on 30) A substrate having a coating obtained by (i) applying a coating composition obtained by mixing the first and second component of the two-component system according to claim 30 to a substrate and (ii) drying the coating composition by evaporation of volatiles. ### Claim 32 (depends on 25) A method for crosslinking a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium comprising providing the crosslinker composition according to claim 25. ### Claim 33 (depends on 2) The multi-aziridine compound according to claim 2, wherein m is 1. ### Claim 34 (depends on 3) The multi-aziridine compound according to claim 3, wherein m is 1. ### Claim 35 (depends on 4) The multi-aziridine compound according to claim 4, wherein m is 1. ### Claim 36 (depends on 5) The multi-aziridine compound according to claim 5, wherein m is 1. ### Claim 37 (depends on 6) The multi-aziridine compound according to claim 6, wherein m is 1. ### Claim 38 (depends on 9) The multi-aziridine compound according to claim 9, wherein m is 1. ### Claim 39 (depends on 10) The multi-aziridine compound according to claim 10, wherein m is 1. ### Claim 40 (depends on 11) The multi-aziridine compound according to claim 11, wherein m is 1. ### Claim 41 (depends on 12) The multi-aziridine compound according to claim 12, wherein m is 1. ### Claim 42 (depends on 13) The multi-aziridine compound according to claim 13, wherein m is 1. ### Claim 43 (depends on 7) The multi-aziridine compound according to claim 7, wherein R′ is H and R″=an alkyl group containing from 1 to 4 carbon atoms, CH2—O—(C═O)—R′″, CH2—O—R″″, or CH2—(OCH2CH2)n—OCH3, whereby R′″ is an alkyl group containing from 3 to 12 carbon atoms and R″″ is an alkyl group containing from 1 to 12 carbon atoms, wherein the multi-aziridine compound contains 2 or 3 structural units (A), wherein the multi-aziridine compound has a molecular weight of from 840 to 3800 Daltons. ### Claim 44 (depends on 17) The multi-aziridine compound according to claim 17, wherein m is 1. ### Claim 45 (depends on 19) The multi-aziridine compound according to claim 19, wherein m is 1. ### Claim 46 (depends on 20) The multi-aziridine compound according to claim 20, wherein m is 1. ### Claim 47 (depends on 21) The multi-aziridine compound according to claim 21, wherein m is 1. ### Claim 48 (depends on 22) The multi-aziridine compound according to claim 22, wherein m is 1. ### Claim 49 (depends on 23) The multi-aziridine compound according to claim 23, wherein m is 1. ### Claim 50 (depends on 24) The multi-aziridine compound according to claim 24, wherein m is 1.