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US 2024/0368378 A1Published application
Process for improving resin performance
AssigneeBorchers GmbH
InventorsNeil John Simpson, Sabrina Nehache, Claudia Menzel
Life of this patent
Estimating the term…
Abstract
The invention pertains generally to a process and resulting product of following the steps of the process involving adding an Iron- or Manganese- or Vanadium- or Copper- in combination with a multidentate ligand to form a metal-ligand complex with a thiol or polythiol to an alkyd resin, said steps performed in any order or the synthesis performed in-situ.
Claims11
A process for improving the hardness of an alkyd resin comprising the following steps, without regard to order, of:
- adding at least one metal ligand complex wherein the metal is selected from the group consisting of Fe, V, Cu and Mn;
- and
- adding at least one ligand selected from the group consisting of Bispidon, N4py-type, TACN-type, Cyclam and cross-bridged ligands, and Trispicen-type ligands in either a preformed metal ligand complex of the metal and the ligand or formed in-situ as the metal ligand complex;
- and
- adding at least one thiol or polythiol, said thiol or polythiol comprising up to 10% by weight on resin solids;
- and
- at least 25% thiol group content by weight of thiol, wherein
- the Bispidon ligand is a ligand of Formula (I)
- wherein:
- each R is independently selected from the group consisting of hydrogen, F, Cl, Br, hydroxyl, C1-4-alkylO—, —NH—CO—H, —NH—CO—C1-4-alkyl, —NH2, —NH—C1-4-alkyl, and C1-4-alkyl;
- R1 and R2 are independently selected from the group consisting of C1-24-alkyl, C6-10-aryl, 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, C1-8-alkyl, C1-8-alkyl-O—C1-8-alkyl, C1-8-alkyl-O—C6-10-aryl, C6-10-aryl, C1-8-hydroxyalkyl and —(CH2)nC(O)OR5 wherein R5 is independently selected from hydrogen and C1-4-alkyl,
- 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
- the N4py-type ligand is a ligand of Formula (II)
- 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
- the TACN-type ligand is a ligand of Formula (III)
- 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-cyclo-nonanyl;
- 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
- the Cyclam or cross-bridged ligand is a ligand of Formula (IV)
- 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 the Trispicen-type ligand is a ligand of formula (VI):
- R
-
- 17
-
- R
-
- 17
-
- N
- -
- X
- -
- NR
-
- 17
-
- R
-
- 17
- ,
- (
- 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-triaza-cyclononanyl;
- 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-tetraaza cyclododecanyl;
- 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, C1-8-oxyalkyl, 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.
204 more elements
A coating composition which comprises:
- at least one metal wherein the metal is selected from the group consisting of Fe, V, Cu and Mn;
- and
- at least one ligand selected from the group consisting of Bispidon, N4py type, TACN-type, Cyclam and cross-bridged ligands, and Trispicen-type ligands, said ligands added as an in-situ complex or as a pre-made complex with the at least one metal;
- and
- at least one thiol or polythiol, said thiol or polythiol comprising
- at least 15% thiol group content by weight of the thiol
- preferably wherein the at least one thiol or polythiol has at least 25% thiol group content by weight of the thiol, wherein:
- (A) the Bispidon ligand is a ligand of Formula (I)
- wherein:
- each R is independently selected from the group consisting of hydrogen, F, Cl, Br, hydroxyl, C1-4-alkylO—, —NH—CO—H, —NH—CO—C1-4-alkyl, —NH2, —NH—C1-4-alkyl, and C1-4-alkyl;
- R1 and R2 are independently selected from the group consisting of C1-24-alkyl, C6-10-aryl, 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, C1-8-alkyl, C1-8-alkyl-O—C1-8-alkyl, C1-8-alkyl-O—C6-10-aryl,
- C6-10-aryl, C1-8-hydroxyalkyl and —(CH2)nC(O)OR5 wherein R5 is independently selected from hydrogen and C1-4-alkyl,
- 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
- (B) the N4py-type ligand is a ligand of Formula (II)
- 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
- (C) the TACN-type ligand is a ligand of Formula (III)
- 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-tetraaza-cyclododecanyl;
- 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
- (D) the cyclam or cross-bridged ligand is a ligand of Formula (IV)
- 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, and
- (E) the cross-bridged ligand is a ligand of the formula (V):
- wherein
- R1 is independently selected from H, C1-20-alkyl, C7-40-alkylaryl, C2-6-alkenyl or C2-6-alkynyl
- (I) the Trispicen-type ligand is a ligand of formula (VI):
- wherein:
- R
-
- 17
-
- R
-
- 17
-
- N
- -
- X
- -
- NR
-
- 17
-
- R
-
- 17
- ,
- (
- VI
- )
- 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-tetraaza-cyclotetradecanyl;
- 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, C1-8-oxyalkyl, 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.
207 more elements
Dependencies are inferred from the claim text.