Reaction product of a cyclic urea and a multifunctional aldehyde

Patent metadata

Field	Value
Publication number	US-10155836-B2
Application number	US-201113823782-A
Country	US
Kind code	B2
Filing date	Sep 23, 2011
Priority date	Sep 30, 2010
Publication date	Dec 18, 2018
Grant date	Dec 18, 2018

Abstract

The invention relates to a reaction product UA of at least one cyclic urea U and at least one multifunctional aldehyde A which reaction product has as substituents on the carbonyl carbon atoms of the aldehyde A at least one kind of functional groups selected from the group consisting of hydroxyl groups —OH and alkoxy groups —OR characterised in that the groups —OR comprise at least two kinds of alkoxy groups —OR 1 and —OR 2 , where R 1 and R 2 are both selected from the group consisting of linear, branched or cyclic alkyl groups having from one to twelve carbon atoms, where R 1 and R 2 may be the same or may be different from each other, to a process of making these, and to a method of use as crosslinker in coating compositions.

First claim

What is claimed is:

1. A reaction product UA of at least one cyclic urea U and at least one multifunctional aldehyde A which reaction product has as substituents on the carbonyl carbon atoms of the aldehyde A at least one kind of functional groups selected from the group consisting of hydroxyl groups —OH and alkoxy groups —OR characterized in that the groups —OR comprise alkoxy groups —OR1 and —OR2, where R1 and R2 are both selected from the group consisting of linear, branched or cyclic alkyl groups having from one to twelve carbon atoms, which may be interrupted by one or more of —O—, —NR″—, —S—, where R″ stands for H, or an alkyl group having from one to six carbon atoms, with the proviso that not two —O—or not two —S—atoms may be immediately adjacent, wherein
R1 and R2 are different from each other, and R2 has at least one carbon atom more than R1, the reaction product UA being made by a process comprising the steps of
a) mixing a multifunctional aldehyde A with a cyclic urea U to effect an addition reaction, optionally, in the presence of a co-solvent which does not react with any of the multifunctional aldehyde A, the cyclic urea U, and the reaction product UA,
b) adding an aliphatic alcohol R1 —OH, and etherifying under acid conditions
c) further etherifying under acid conditions with an added aliphatic alcohol R2 —OH which has at least one carbon atom in its molecule more that there is in R1 —OH,
wherein the etherification is conducted in a sequential manner involving at least 2 subsequent steps b) and c), and
wherein the reaction product UA has a degree of etherification, measured as the ratio n(RO—) / n(U) of the amount of substance n(RO—) of alkoxy groups to the amount of substance n(U) of cyclic urea U chemically bound in the reaction products, of at least 1.1 mol/mol.

2. The reaction product UA of claim 1 wherein R 1 and R 2 are different from each other, and R 2 has at least one carbon atom more than R 1 , and the ratio of the number of —OR groups to the sum of the number of —OH groups and the number of —OR groups which are substituents on the carbonyl carbon atoms of the aldehyde A in the reaction product UA is at least 50%, the number of —OR groups being the sum of the number of —OR 1 groups and the number of —OR 2 groups.

3. The reaction product UA of claim 1 , wherein the ratio of the amount of substance of residual >NH groups to the amount of substance of moieties derived from the cyclic urea U is not more than 0.2 mol/mol.

4. The reaction product UA of claim 1 characterised in that the aldehyde A is glyoxal or a mixture comprising glyoxal.

5. The reaction product UA of claim 1 characterised in that the cyclic urea U is selected from the group consisting of ethylene urea, 1,3-propylene urea, 1,2-propylene urea, 1,4-butylene urea, glycoluril, or a mixture comprising at least two of these.

6. The reaction product UA of claim 5 characterised in that the cyclic urea U is purified before reaction with the multifunctional aldehyde A by one or more processes selected from the group consisting of recrystallisation, extraction, complexation, adsorption and ion exchange reactions, distillation, sublimation, and melt crystallisation.

7. A process to make a reaction product UA, comprising
a) mixing a multifunctional aldehyde A with a cyclic urea U to effect an addition reaction, optionally, in the presence of a co-solvent which does not react with any of the multifunctional aldehyde A, the cyclic urea U, and the reaction product UA, and further optionally, removing water,
b) after step a, adding an aliphatic alcohol R1 —OH, and etherifying under acid conditions, and
c) after step b, adding a further aliphatic alcohol R2—OH which has at least one carbon atom in its molecule more that there is in R1 —OH, and etherifying under acid conditions to obtain the reaction product UA,
wherein either or both of steps b) and c) may be repeated one or more times,
wherein R1 and R2 are different from each other,
wherein R2 has at least one carbon atom more than R1, and
wherein the reaction product UA has as substituents on the carbonyl carbon atoms of the aldehyde A at least one kind of functional groups selected from the group consisting of hydroxyl groups —OH and alkoxy groups —OR,
wherein the alkoxy groups —OR comprise alkoxy groups —OR1 and —OR2,
wherein R1 and R2 are both selected from the group consisting of linear, branched or cyclic alkyl groups having from one to twelve carbon atoms, which are optionally interrupted by one or more of —O—, —NR″—, —S—with the proviso that not two —O—or not two —S—atoms may be immediately adjacent,
wherein R″ stands for H, or an alkyl group having from one to six carbon atoms.

8. The process of claim 7 wherein the ratio of the amount of substance n (—O—R 2 ) of alkoxy groups —O—R 2 to the amount of substance n (—O—R 1 ) of alkoxy groups —O—R 1 in the etherified product of the process of claim 7 is between 0.11 mol/mol and 20 mol/mol.

9. The process of claim 7 to make the reaction product UA,
where step c) is done at least twice.

10. The process of claim 7 characterised in that in step a), the amount of multifunctional aldehyde A added is between 20% and 80% of the stoichiometric amount needed, and that after step a), a further quantity of multifunctional aldehyde A is added and reacted with the reaction mixture formed in step a) wherein the total amount of multifunctional aldehyde A added is chosen such that the ratio of the amount of substance of aldehyde groups n(—CHO) in the multifunctional aldehyde A and the amount of substance of amide groups n(—CO—NH—) in the cyclic urea U is from 0.8 mol/mol to 1.4 mol/mol.

11. The process of claim 7 characterised in that the mixture of cyclic urea U, multifunctional aldehyde, and optionally, water or solvent, is concentrated before or during the reaction by removing volatile constituents by distillation, or distillation under reduced pressure.

12. The process of claim 7 characterised in that during or after step a) and/or during or after step b), at least a part of the unreacted alcohol R 1 OH and/or water is removed by distillation.

13. A method of use of the reaction product UA of claim 1 as crosslinker, comprising admixing the said reaction product UA to a binder resin having at least one of hydroxyl groups, acid groups, preferably carboxyl groups, carbamate groups, amide groups, imide groups, amino groups, imino groups, mercaptan groups, or phosphine groups, homogenising, and applying the homogenised mixture to a substrate by spraying, brushing, wire coating, curtain coating, blade coating, roll coating, dipping, electrophoretic deposition, powder spraying, or electrostatic spraying.

14. The method of claim 13 , characterised in that at least one of water, an organic solvent, a catalyst, a pigment, a filler, a light stabiliser, a coalescing agent, a defoamer, a wetting agent, a levelling agent, a wetting agent, a thickening agent, an antisettling agent, an antiskinning agent, and a preservative, is added to the mixture of the reaction product UA and the binder resin.

15. The method of use of claim 13 , characterised in that the substrate is selected from the group consisting of plastics including thermoplastics and thermosets, wood, ceramics and glass, fabricated wood, leather, textiles, tyre cord, rubber objects, paper, cardboard, plaster, concrete, and metal, metallised circuit boards, semiconductor surfaces, displays, and packagings for electronic circuitry.

16. A method of use of the reaction product UA of claim 1 as crosslinker for substrates selected from the group consisting of paper, tex

Assignees

• Gupta Ram B
• Flood Lawrence A
• Treasurer Urvee Y
• Lawless Barry A
• Brogan Colin
• Allnex Netherlands Bv

Inventors

• Gupta Ram B
• Flood Lawrence A
• Treasurer Urvee Y
• Lawless Barry A
• Brogan Colin

Classifications

• C08G12/36 Primary

  Ureas; Thioureas · CPC title

• C09D161/26

  of aldehydes with heterocyclic compounds · CPC title

• C09D161/24

  with urea or thiourea · CPC title

• C08L61/30

  of aldehydes with heterocyclic and acyclic or carbocyclic compounds · CPC title

• B32B21/02 Primary

  the layer being formed} of fibres, chips, or particles {, e.g. MDF, HDF, OSB, chipboard, particle board, hardboard · CPC title