Multi-component composition for manufacturing polyurethane/urea cementitious hybrid systems
The invention relates to a multi-component composition for the manufacture of polyurethane/urea cementitious hybrid system, comprising at least one isocyanate component selected from the group consisting of monoisocyanate, polyisocyanate and NCO terminated prepolymer, at least one polyol, water, catalyst, at least one acidic additive, and hydraulic binder, wherein the acidic additive is at least one selected from the group consisting of Lewis acids, acid precursors and acidic buffers and is in an amount of 0.01 to 3 wt %, based on the total weight of the composition, to the preparation thereof, and to the use of the composition for the preparation of a flooring, waterproofing, screed, grouting, primer, wall paint, roofing or coating in construction applications.
1. A multi-component composition comprising:
(A) at least one isocyanate component selected from the group consisting of monoisocyanate, polyisocyanate and NCO terminated prepolymer;
(B) at least one organic isocyanate-reactive compound selected from the group consisting of polyol, polyamide, polyamine, and polyesteramide;
(C) water;
(D) catalyst;
(E) at least one acidic additive that is selected from diketones and compounds having the general formula (II):
R 1 —COOCO—R 2 (II)
wherein
R 1 and R 2 are independently from each other selected from the group consisting of C 1 -C 30 -alkyl, C 2 -C 30 -alkenyl, C 3 -C 30 -cyclolalkyl, C 3 -C 30 -heterocyclyl, C 3 -C 30 -heterocyclyl-C 1 -C 30 -alkyl, C 6 -C 30 -aryl, C 6 -C 30 -aryl-C 1 -C 30 -alkyl, C 2 -C 30 -heteroaryl, C 2 -C 30 -heteroaryl-C 1 -C 30 -alkyl, and C 1 -C 30 -alkoxy-C 1 -C 30 -alkyl, each of which radicals is optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, acyl, or C 3 -C 6 -cycloalkyl, with the heteroatom being selected from N, O and S,
or
R 1 and R 2 , together with the carbon and oxygen atoms attached thereto, form a saturated or unsaturated 5- to 10-membered hetero ring, the ring being optionally fused with phenyl, with R 1 and R 2 being optionally replaced by heteroatoms selected from N, O and S, and being optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, acyl, or C 3 -C 6 -cycloalkyl; and
(F) hydraulic binder;
wherein the at least one acidic additive is present in an amount of 0.01 to 3 wt % based on the total weight of the composition.
2. The multi-component composition according to claim 1 , wherein component (A) is selected from the group consisting of n-hexylisocyanate, cyclohexylisocyanate, hexamethylene isocyanate, 2-ethyl hexylisocyanate, n-octyl isocyanate, dodecyl-isocyanate, stearylisocyanate, benzyl isocyanate, diphenylmethane 4,4′-diisocyanate, diphenylmethane 2,4′-diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates with diphenylmethane diisocyanate homologs having a larger number of rings (polymer MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), mixtures of hexamethylene diisocyanates with oligomeric or polymeric homologs of hexamethylene diisocyanate (polynuclear HDI), isophorone diisocyanate (IPDI), tolylene 2,4- or 2,6-diisocyanate (TDI), and mixtures of two or more of these isocyanates.
3. The multi-component composition according to claim 1 , wherein component (B) is selected from the group consisting of polyhydric polyols, aminoalcohols, polyether polyols, polyester polyols, polycarbonate polyols and mixtures thereof.
4. The multi-component composition according to claim 1 , wherein catalyst (D) is selected from the group consisting of amine-based catalysts, catalysts based on organic metal compounds, and combinations thereof.
5. The multi-component composition according to claim 1 , wherein the acidic additive is selected from compounds having the general formula (II):
R 1 —COOCO—R 2 (II)
wherein
R 1 and R 2 are independently from each other selected from the group consisting of C 1 -C 30 -alkyl, C 2 -C 30 -alkenyl, C 3 -C 30 -cyclolalkyl, C 3 -C 30 -heterocyclyl, C 3 -C 30 -heterocyclyl-C 1 -C 30 -alkyl, C 6 -C 30 -aryl, C 6 -C 30 -aryl-C 1 -C 30 -alkyl, C 2 -C 30 -heteroaryl, C 2 -C 30 -heteroaryl-C 1 -C 30 -alkyl, and C 1 -C 30 -alkoxy-C 1 -C 30 -alkyl, each of which radicals is optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, acyl, or C 3 -C 6 -cycloalkyl, with the heteroatom being selected from N, O and S,
or
R 1 and R 2 , together with the carbon and oxygen atoms attached thereto, form a saturated or unsaturated 5- to 10-membered hetero ring, the ring being optionally fused with phenyl, with R 1 and R 2 being optionally replaced by heteroatoms selected from N, O and S, and being optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, acyl, or C 3 -C 6 -cycloalkyl.
6. The multi-component composition according to claim 5 , wherein the acidic additive is selected from compounds having the general formula (II):
R 1 —COOCO—R 2 (II)
wherein
R 1 and R 2 are independently from each other selected from the group consisting of C 1 -C 15 -alkyl, C 2 -C 15 -alkenyl, C 3 -C 15 -cyclolalkyl, C 3 -C 15 -heterocyclyl, C 3 -C 15 -heterocyclyl-C 1 -C 15 -alkyl, C 6 -C 15 -aryl, C 6 -C 15 -aryl-C 1 -C 15 -alkyl, C 2 -C 15 -heteroaryl, C 2 -C 15 -heteroaryl-C 1 -C 15 -alkyl, and C 1 -C 15 -alkoxy-C 1 -C 15 -alkyl, each of which radicals is optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, acyl, or C 3 -C 6 -cycloalkyl, with the heteroatom being selected from N, O and S,
or
R 1 and R 2 , together with the carbon and oxygen atoms attached thereto, form a saturated or unsaturated 5- to 10-membered hetero ring, the ring being optionally fused with phenyl, with R 1 and R 2 being optionally replaced by heteroatoms selected from N, O and S, and being optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, acyl, or C 3 -C 6 -cycloalkyl.
7. The multi-component composition according to claim 6 , wherein the acidic additive is selected from compounds having the general formula (II):
R 1 —COOCO—R 2 (II)
wherein
R 1 and R 2 are independently from each other selected from the group consisting of C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 3 -C 10 -cyclolalkyl, C 3 -C 10 -heterocyclyl, C 3 -C 10 -heterocyclyl-C 1 -C 10 -alkyl, C 6 -C 10 -aryl, C 6 -C 10 -aryl-C 1 -C 10 -alkyl, C 2 -C 10 -heteroaryl, C 2 -C 10 -heteroaryl-C 1 -C 10 -alkyl, and C 1 -C 10 -alkoxy-C 1 -C 10 -alkyl, each of which radicals is optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, acyl, or C 3 -C 6 -cycloalkyl, with the heteroatom being selected from N, O and S,
or
R 1 and R 2 , together with the carbon and oxygen atoms attached thereto, form a saturated or unsaturated 5- to 10-membered hetero ring, the ring being optionally fused with phenyl, with R 1 and R 2 being optionally replaced by heteroatoms selected from N, O and S, and being optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, acyl, or C 3 -C 6 -cycloalkyl.
8. The multi-component composition according to claim 7 , wherein R 1 and R 2 are independently from each other and are selected from the group consisting of C 3 -C 6 -alkyl, C 3 -C 6 -alkenyl, and C 3 -C 6 -cyclolalkyl, each of which radicals is optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, or acetyl.
9. The multi-component composition according to claim 5 , wherein R 1 and R 2 , together with the carbon and oxygen atoms attached thereto, form a saturated or unsaturated 5- to 10-membered hetero ring, the ring being optionally fused by phenyl, with R 1 and R 2 being optionally replaced by N, and being optionally substituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, oxo, or acetyl.
10. The multi-component composition according to claim 1 , wherein the acidic additive is selected from the group consisting of butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, ε-caprolactone, methacrylic anhydride, isatoic anhydride, 2-acetyl butyrolactone, methyl 2-oxo cyclopentanecarboxylate, and combinations thereof.
11. The multi-component composition according to claim 1 , wherein the acidic additive is selected from diketones.
12. The multi-component composition according to claim 11 , wherein the acidic additive is selected from compounds having the general formula (V):
R 5 —C(O)—CHR 4 —C(O)—R 6 (V)
wherein
R 4 is selected from H and C 1 -C 8 -alkyl,
R 5 and R 6 are independently from each other selected from C 1 -C 8 -alkyl and C 1 -C 8 -alkoxy,
or
R 5 and R 4 , or R 5 and R 6 , together with the carbon atoms attached, form a 5- to 8-membered ring or hetero ring, with the ring member optionally replaced by N or O, and the ring member optionally substituted by C 1 -C 6 -alkyl, cyano, amino, hydroxyl, or oxo group.
13. The multi-component composition according to claim 1 , wherein the acidic additive is selected from 2-acetyl cyclopentanone and/or 1,3-dimethylbarbituric acid.
14. The multi-component composition according to claim 1 , wherein the hydraulic binder comprises cement and/or lime.
15. The multi-component composition according to claim 14 , wherein the hydraulic binder further comprises aggregates, fillers and/or admixtures.
16. The multi-component composition according to claim 15 , wherein the admixtures comprise accelerators, retarders, air entraining agents, defoamers, plasticizers, corrosion inhibitors, bonding agents, or mixtures thereof.
17. The multi-component composition according to claim 1 , wherein the amount of the acidic additive is present in the range of 0.01 to 1.5 wt % based on the total weight of the composition.
18. The multi-component composition according to claim 1 , comprising
(A) 5-35 wt % of at least one isocyanate component selected from the group consisting of monoisocyanate, polyisocyanate and NCO terminated prepolymer;
(B) 2-20 wt % of at least one polyol;
(C) 2-10 wt % of water;
(D) 0.001-3 wt % of catalyst;
(E) 0.02-1.5 wt % of at least one acidic additive; and
(F) 15-50 wt % of hydraulic binder, based on the total weight of the composition,
wherein the at least one acidic additive is selected from the group consisting of butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, ε-caprolactone, methacrylic anhydride, isatoic anhydride, 1,3-dimethylbarbituric acid, 2-acetylcyclopentanone, methyl 2-oxo cyclopentanecarboxylate, 2-acetylbutyrolactone, and combinations thereof.
19. The multi-component composition according to claim 18 , wherein the amount of acidic additive is 0.2-1.5 wt %, and is selected from the group consisting of butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, ε-caprolactone, methacrylic anhydride, isatoic anhydride, 1,3-dimethylbarbituric acid, 2-acetylcyclopentanone, methyl 2-oxo cyclopentanecarboxylate, 2-acetylbutyrolactone, and combinations thereof.
20. A polyurethane/urea cementitious hybrid system comprising the multi-component composition according to claim 1 .
21. A process for preparing a flooring, waterproofing, screed, grouting, primer, wall paint, roofing or coating, comprising the steps of
mixing the components (A)-(F) according to claim 1 to form a mixture;
applying the mixture onto a substrate; and
curing the applied mixture to form a flooring, waterproofing, screed, grouting, primer, wall paint, roofing or coating on the substrate.
22. The process according to claim 21 , wherein step (1) further comprises the sub-steps of: mixing the components (A)-(E) together, and then adding component (F) to form a mixture.
23. The process according to claim 21 , wherein step (1) further comprises the sub-steps of:
(a) mixing the components (D), (E) and optionally part of (C) to form a mixture;
(b) mixing the components (A), (B), (C) or residual of (C) with mixture obtained in sub-step (a) to form a mixture;
(c) adding component (F) to mixture obtained in sub-step (b) to form a mixture.
24. A method for preparing a flooring, waterproofing, screed, grouting, primer, wall paint, roofing or coating, the method comprises applying the multi-component composition of claim 1 onto a substrate; and curing the applied composition.
25. Flooring, waterproofing, screed, grouting, primer, wall paint, roofing or coating obtained by the process of claim 21 .
26. A method for preparing a flooring, waterproofing, screed, grouting, primer, wall paint, roofing or coating, the method comprises applying the polyurethane/urea cementitious hybrid system of claim 20 onto a substrate; and curing the applied composition.