# US 2014/0155525 A1 · Liquid hardening

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- Number: US 2014/0155525 A1
- Document ID: US20140155525A1
- Status: Published application
- Kind: A1
- Application number: 14/176,260
- Filed: 2014-02-10
- Published: 2014-06-05
- Earliest claimed: 2006-07-07
- Assignees: OMG UK Technology Ltd.
- Applicants: OMG UK Technology Ltd.
- Inventors: Ronald HAGE; Philana Veronica WESENHAGEN
- Web page: https://patentgrep.com/patent/US20140155525A1

## CPC

- C08K 5/3467: having more than two nitrogen atoms in the ring
- C09D 11/03: characterised by features other than the chemical nature of the binder
- C09D 167/08: Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
- C09F 9/00: Compounds to be used as driers, i.e. siccatives
- C08K 5/005: {Stabilisers against oxidation, heat, light, ozone}
- C08K 5/0091: {Complexes with metal-heteroatom-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)
- C09F: NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE

## Abstract

Curing agents for air-drying alkyd-based resins, coatings, such as paint, varnish or wood stain, inks and linoleum floor coverings, based on an iron/manganese complex containing tetradentate, pentadentate or hexadentate nitrogen donor ligands are disclosed.

## Claims

### Claim at position 1

1-20. (canceled)

### Claim 21

A curable liquid medium comprising:
from 1 to 90 wt % of an alkyd-based resin; and
from 0.0001 to 0.1 wt % of two or more siccatives wherein the siccative is an iron or manganese complex of a tetradentate, pentadentate or hexadentate nitrogen donor ligand, wherein the ligand is selected from the group consisting of
(a) bispidon ligands of formula I,
(b) N4py ligands of formula II,
(c) TACN-Nx ligands of formula III,
(d) cyclam ligands of formula IV,
(e) cross-bridged ligands of formula V, and
(e) trispicen ligands of formula VI;
and further wherein the ligands are selected from the group consisting of formulae (I) to (VI):
wherein:
each R is independently selected from the group consisting of hydrogen, F, Cl, Br, hydroxyl, C1-4-alkylO', —NH—CO—H, —NH—CO—C1-4alkyl, —NH2, —NH—C1-4alkyl, and C1-4alkyl;
R1 and R2 are independently selected from the group consisting of C1-24alkyl, C6-10aryl, and a group containing one or two heteroatoms (e.g. N, O or S) capable of coordinating to a transition metal;
R3 and R4 are independently selected from the group consisting of hydrogen, C1-8alkyl, C1-8alkyl-O—C1-8alkyl, C1-8alkyl-O—C6-10aryl, C6-10aryl, C1-8hydroxyalkyl and —(CH2)nC(O)OR5 wherein R5 is independently selected from hydrogen and C1-4alkyl,
n is from 0 to 4
X is selected from the group consisting of C═O, —[C(R6)2]y— wherein y is from 0 to 3; and
each R6 is independently selected from the group consisting of hydrogen, hydroxyl, C1-4 alkoxy and C1-4 alkyl.
wherein:
each R1 and R2 independently represents —R4—R5;
R3 represents hydrogen, C1-8-alkyl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-40 arylalkyl, or —R4—R5,
each R4 independently represents a single bond or a linear or branched C1-8-alkyl-substituted-C2-6-alkylene, C2-6-alkenylene, C2-6-oxyalkylene, C2-6-aminoalkylene, C2-6-alkenyl ether, C2-6-carboxylic ester or C2-6-carboxylic amide, and
each R5 independently represents an optionally N-alkyl-substituted aminoalkyl group or an optionally alkyl-substituted heteroaryl: selected from the group consisting of pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl.
wherein:
each R20 is independently selected from: C1-8-alkyl, C3-8-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1,4,7-triazacyclononanyl; 1,4,8,11-tetraazacyclotetradecanyl; 1,4,7,10,13-pentaazacyclopentadecanyl; 1,4-diaza-7-thia-cyclononanyl; 1,4-diaza-7-oxa-cyclononanyl; 1,4,7,10-tetraazacyclododecanyl; 1,4-dioxanyl; 1,4,7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl; heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-40-arylalkyl group optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R21)3,
R21 is selected from hydrogen, C1-8-alkyl, C2-6-alkenyl, C7-40-arylalkyl, arylalkenyl, C1-8-oxyalkyl, C2-6-oxyalkenyl, C1-8-aminoalkyl, C2-6-aminoalkenyl, C1-8-alkyl ether, C2-6-alkenyl ether, and —CY2—R22,
Y is independently selected from H, CH3, C2H5, C3H7 and
R22 is independently selected from C1-8-alkyl-substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and
wherein at least one of R20 is a —CY2—R22.
wherein:
Q is independently selected from
p is 4;
R is independently selected from: hydrogen, C1-6-alkyl, CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or one of R is linked to the N of another Q via an ethylene bridge; and
R1, R2, R3, R4, R5 and R6 are independently selected from: H, C1-4-alkyl, and C1-4-alkylhydroxy.
wherein:
R1 is independently selected from H, C1-20 alkyl, C7-40-alkylaryl, C2-6-alkenyl or C2-6-alkynyl.
R17R17N—X—NR17R17 (VI),
wherein:
X is selected from —CH2CH2—, —CH2CH2CH2—, —CH2C(OH)HCH2—;
each R17 independently represents a group selected from: R17, C1-8-alkyl, C3-8-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1,4,7-triazacyclononanyl; 1,4,8,11-tetraazacyclotetradecanyl; 1,4,7,10,13-pentaazacyclopentadecanyl; 1,4-diaza-7-thia-cyclononanyl; 1,4-diaza-7-oxa-cyclononanyl; 1,4,7,10-tetraazacyclododecanyl; 1,4-dioxanyl; 1,4,7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl; heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, and C7-40 arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R19)3, wherein
R19 is selected from hydrogen, C1-8-alkyl, C2-6-alkenyl, C7-40-arylalkyl, C7-40-arylalkenyl, C1-8oxyalkyl, C2-6-oxyalkenyl, C1-8-aminoalkyl, C2-6-aminoalkenyl, C1-8-alkyl ether, C2-6-alkenyl ether, and —CY2—R18, in which each Y is independently selected from H, CH3, C2H5, C3H7 and R18 is independently selected from an optionally substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and at least two of R17 are —CY2—R18.

### Claim 22 (depends on 21)

The curable liquid medium of claim 21 wherein
the iron ion in the iron complex is selected from the group consisting of Fe(II) and Fe(III); and
the manganese ion in the manganese complex is selected from the group consisting of Mn(II), Mn(III) and Mn(IV).

### Claim 23 (depends on 22)

The curable liquid medium of claim 22 wherein
the ligand is pyridin-2-yl.

### Claim 24 (depends on 22)

The curable liquid medium according to claim 22, wherein
X is C═O or C(OH)2.

### Claim 25 (depends on 24)

The curable liquid medium according to claim 24, wherein in formula (I):
R3═R4 and is selected from —C(O)—O—CH3, —C(O)—O—CH2CH3, —C(O)—O—CH2C6H5 and CH2OH.

### Claim 26 (depends on 22)

The curable liquid medium according to claim 22, wherein in formula (I)
at least one of R1 or R2 is pyridin-2-ylmethyl and
the other is selected from —CH3, —C2H5, —C3H7, —C4H9, —C6H13, —C8H17, —C12H25, and —C18H37.

### Claim 27 (depends on 22)

The liquid curable medium of claim 22 wherein in formula (II):
the ligand is selected from the group consisting of N,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine and N,N-bis(pyridin-2-yl-methyl-1,1-bis(pyridin-2-yl)-1-aminoethane.

### Claim 28 (depends on 1, 22)

The liquid curable medium of claim 22, wherein in formula (Ill):
the curable liquid medium according to claim 1, wherein R1 is selected from the group consisting of a C1-C8 alkyl and a C1-C8 aryl.

### Claim 29 (depends on 28)

The curable liquid medium of claim 28, wherein in formula (III)
the ligand is 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane.

### Claim 30 (depends on 22)

The curable liquid medium of claim 22, wherein in formula (IV)
the ligand is selected from the group consisting of 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, 1,4,7,10-tetraazacyclododecane, 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane, and 1,4,7,10-tetrakis(pyridine-2-ylmethyl)-1,4,7,10-tetraazacyclododecane.

### Claim 31 (depends on 30)

The curable liquid medium according to claim 30 wherein in formula (IV)
the ligand is 1,4,7,10-tetrakis(pyridine-2-ylmethyl)-1,4,7,10-tetraazacyclododecane.

### Claim 32 (depends on 22)

The curable liquid medium according to claim 22 wherein in formula (V)
the ligand is 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane.

### Claim 33 (depends on 22)

The curable liquid medium according to claim 22 wherein in formula (VI)
the ligand is selected from the group consisting of N-methyl-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octyl-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octadecyl-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N′,N′-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-ethyl-N,N′,N′-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N′,N′-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-ethyl-N,N′,N′-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-benzyl-N,N′,N′-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-benzyl-N,N′,N′-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-butyl-N,N′,N′-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octyl-N,N′,N′-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-dodecyl-N,N′,N′-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octadecyl-N,N′,N′-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N′,N′-tris(imidazol-2-ylmethyl)ethylenediamine; N-ethyl-N,N′,N′-tris(imidazol-2-ylmethyl)ethylenediamine; N,N′-dimethyl-N,N′-bis(imidazol-2-ylmethyl)ethylenediamine; N-(1-propan-2-ol)-N,N′,N′-tris(imidazol-2-ylmethyl)ethylenediamine; N-(1-propan-2-ol)-N,N′,N′-tris(1-methyl-imidazol-2-ylmethyl)ethylenediamine; N,N-diethyl-N′,N″,N″-tris(5-methyl-imidazol-4-ylmethyl)-diethylenetriamine; N-(3-propan-1-ol)-N,N′,N′-tris(1-methyl-imidazol-2-ylmethyl)ethyle-nediamine; N-hexyl-N,N′,N′-tris(imidazol-2ylmethyl)-ethylenediamine; N-methyl-N,N′,N′-tris(benzimidazol-2ylmethyl)ethylenediamine; and N-(3-propan-1-ol)methyl-N,N′,N′-tris(benzimidazol-2ylmethyl)ethylenediamine.

### Claim 34 (depends on 22)

The curable liquid medium of claim 22 which further comprises:
at least one antioxidant in an amount between 0.001 and 0.1 wt %,

### Claim 35 (depends on 34)

The curable liquid medium of claim 34 wherein
the at least one antioxidant is selected from the group consisting of di-tert-butyl hydroxy toluene, ethoxyquine, a-tocopherol, and 6-hydroxy-2,5,7,8-tetra-methylchroman-2-carboxylic acid.

### Claim 36 (depends on 35)

The curable liquid medium of claim 35 wherein
the at least one antioxidant is present in an amount between 0.002 and 0.05 wt %.

### Claim 37 (depends on 36)

The curable liquid medium of claim 36
when cured.