Composition crosslinkable by Real Michael Addition (RMA) reaction

1. A kit of parts for manufacturing a crosslinkable composition crosslinkable by Real Michael Addition (RMA) reaction, wherein the crosslinkable composition comprises:

a) Component(s) A having at least 2 acidic C—H donor groups in activated methylene or methine and having a pKa(A) between 10.5 and 14,

b) Component(s) B having at least 2 activated unsaturated acceptor groups, wherein a molar ratio R of acceptor groups to donor groups is between 3:1 to 1:6 and which component(s) B react with component(s) A by Real Michael Addition (RMA) to form a crosslinked network,

c) basic component(s) C being a salt of a basic anion X— from an acidic X—H group containing compound wherein X is N, P, O, S or C,

i) in an amount xc between 0.001 and 1 meq/(gr of components A, B, C),

ii) anion X— being a Michael Addition donor reactable with component B and

iii) anion X— is characterized by a pKa(C) of the corresponding acid X—H of more than two units lower than the pKa(A) of the majority component A and being lower than 10.5, wherein the majority component A is the component A providing at least 50 mole % of the C—H acidic RMA donor groups,

wherein the kit comprises 1) a part I.1, comprising component C and a part II.1 not comprising component C and comprising components A, B or alternatively 2) a kit of parts comprising a part I.2 comprising component C, component A, but not comprising component B and part II.2 comprising component B or alternatively 3) a kit of parts comprising part I.3 comprising components A, B and instead of component C the corresponding acidic compound X—H and a part II.3 comprising a strong base for mixing with part I.3.

2. The kit of claim 1 , wherein the crosslinkable composition comprises:

component(s) D comprising one or more acidic X′—H groups wherein X′ is N, P, O, S or C,

i) X′ being a same or different group as group X in component C,

ii) the X′— anion being a Michael Addition donor reactable with component B,

iii) the pKa(D) of the X′—H group in component D being more than two units lower than pKa(A) of the majority component A and being lower than 10.5,

iv) the equivalent ratio Rd/c of acidic X′—H groups in component D over basic anion X— in component C is between 1 and 5000%,

wherein the kit comprises:

a part I.1, comprising component C and at least part of component D and a part II.1 not comprising component C and comprising components A, B and D or alternatively 2) a kit of parts comprising a part I.2 comprising component C, component A, and at least a part of component D but not comprising component B and part II.2 comprising component B and components D or alternatively 3) a kit of parts comprising part I.3 comprising components A, B, D and instead of component C the corresponding acidic compound X—H and a part II.3 comprising a strong base for mixing with part I.3.

3. The kit of claim 2 , wherein the composition and the kit do not comprise an ethylmalonate modified polyester based on neopentyl glycol and hexahydrophthalic anhydride, di-trimethylolpropane-tetraacrylate and tetrabutylammonium succinimide and ethylacetoacetate.

4. The kit of claim 2 , wherein pKa(D) is equal to or higher than pKa(C).

5. The kit of claim 1 , wherein the crosslinkable composition further comprises component(s) F comprising an acidic X″—H group wherein X″ is N, P, O, S or C

i) different from components A,

ii) F being a Michael addition donor reactable with component B,

wherein the kit comprises:

1) a part I.1, comprising component C and a part II.1 not comprising component C and comprising components A, B and F or alternatively 2) a kit of parts comprising a part I.2 comprising component C, component A, optional solvents but not comprising component B and part II.2 comprising component B and component F or alternatively 3) a kit of parts comprising part I.3 comprising components A, B and F and instead of component C the corresponding acidic compound X—H and a part II.3 comprising a strong base for mixing with part I.3.

6. The kit of claim 1 , wherein the composition comprises less than 50 mole % and relative to basic components C of other basic compound other than C that can initiate or catalyse the RMA crosslinking reaction.

7. The kit of claim 1 , wherein the crosslinkable composition comprises:

component(s) D and F, wherein the component D comprises one or more acidic X′—H groups wherein X′ is N, P, O, S or C,

i) X′ being a same or different group as group X in component C,

ii) the X′— anion being a Michael Addition donor reactable with component B,

iii) the pKa(D) of the X′—H group in component D being more than two units lower than pKa(A) of the majority component A and being lower than 10.5,

iv) the equivalent ratio Rd/c of acidic X′—H groups in component D over basic anion X— in component C is between 1 and 5000%, and

wherein the component F comprises an acidic X″—H group wherein X″ is N, P, O, S or C

i) different from components A and D,

ii) F being a Michael addition donor reactable with component B,

wherein the kit comprises:

1) a part I.1, comprising component C and a part II.1 not comprising component C and comprising components A, B, D and F or alternatively 2) a kit of parts comprising a part I.2 comprising component C, component A, and at least a part of component D but not comprising component B and part II.2 comprising component B and other components D and F or alternatively 3) a kit of parts comprising part I.3 comprising components A, B, D and F and instead of component C the corresponding acidic compound X—H and a part II.3 comprising a strong base for mixing with part I.3.

8. The kit of claim 7 , comprising:

a) Component(s) A in an amount xa between 5 and 95 wt %,

b) Component(s) B in an amount xb between 5 and 95 wt %, wherein xa plus xb is at least 40 wt %,

c) basic component(s) C in an amount xc between 0.001 and 1 meq/(gr total resin),

d) component(s) D in an amount xd such that the equivalent ratio Rd/c of acidic X′—H groups in component D over basic anion groups X− in component C is between 0% and 5000%,

e) component(s) F in an amount xf between 0 and 30 wt %,

wherein wt % is relative to total resin forming components A, B, C, D and F.

9. The kit of claim 1 , wherein at least 50 mole % of the RMA donor groups in component(s) A are from malonate or acetoacetate groups.

10. The kit of claim 1 , wherein components B are acryloyl or maleate groups or mixtures thereof.

11. The kit of claim 2 , wherein anions X− and X′− in components C and D have a lower Michael Addition reactivity towards component B than an anion of the majority component A by a factor of at least 3, but no more than 10,000.

12. The kit of claim 2 , wherein

a) more than 50 mole % of RMA donor groups in components A are from malonate groups,

b) more than 50 mole % of the RMA acceptor groups in component B are from acryloyl groups,

c) component C is a benzotriazolide salt, a salt of 1,2,4-triazole or a salt of 1,3-cyclohexanedione, and

d) component D is benzotriazole or a triazole, a 1,3-diketone, or an imid.

13. The kit of claim 2 , wherein the anion X− in component C, and/or the X′ group in component D is an aza-acidic compound (X=N) comprising a molecule containing the N—H as part of a group Ar—NH—(C═O), —(C═O)—NH—(C═O)—, or a —NH—(O═S═O)— group, or a heterocycle in which the nitrogen of the N—H group is contained in a heterocyclic ring, or a cyclic imide, or substituted succinimide or a triazole component.

14. The kit of claim 2 , wherein the anion X− from component C, and/or the X′ group in component D is a carbon-acidic compound (X=C).

15. The kit of claim 2 , wherein the anion X− in component C, and/or the X′ group in component D are derived from an aromatic sulfonamide.

16. The kit of claim 2 , wherein component C is a triazole and component D an imid or a 1,3 diketone.

17. A coating composition comprising paint additives, and a crosslinkable composition comprising:

a) Component(s) A having at least 2 acidic C—H donor groups in activated methylene or methine and having a pKa(A) between 10.5 and 14,

b) Component(s) B having at least 2 activated unsaturated acceptor groups, wherein a molar ratio R of acceptor groups to donor groups is between 3:1 to 1:6 and which component(s) B react with component(s) A by Real Michael Addition (RMA) to form a crosslinked network,

c) basic component(s) C being a salt of a basic anion X— from an acidic X—H group containing compound wherein X is N, P, O, S or C,

i) in an amount xc between 0.001 and 1 meq/(gr of components A, B, C),

ii) anion X— being a Michael Addition donor reactable with component B and

iii) anion X— is characterized by a pKa(C) of the corresponding acid X—H of more than two units lower than the pKa(A) of the majority component A and being lower than 10.5.

18. A composite article comprising a filler material and as a binder material a crosslinked composition comprising:

a) component(s) A having at least 2 acidic C—H donor groups in activated methylene or methine and having a pKa(A) between 10.5 and 14,

b) component(s) B having at least 2 activated unsaturated acceptor groups, wherein a molar ratio R of acceptor groups to donor groups is between 3:1 to 1:6 and which component(s) B react with component(s) A by Real Michael Addition (RMA) to form a crosslinked network,

c) basic component(s) C being a salt of a basic anion X− from an acidic X—H group containing compound wherein X is N, P, O, S or C,

i) in an amount xc between 0.001 and 1 meq/(gr of components A, B, C),

ii) anion X— being a Michael Addition donor reactable with component B, and

iii) anion X— is characterized by a pKa(C) of the corresponding acid X—H of more than two units lower than the pKa(A) of the majority component A and being lower than 10.5.