ISOCYANATE CURING WITH BOUND WATER

Abstract

A multi-component composition includes an isocyanate-reactive compound, an isocyanate compound, a source of chemically bound water, optionally a catalyst, and optionally a CO.sub.2 scavenger. A process for preparing a polyurea polymer by curing that multi-component composition with the source of chemically bound water. The polyurea polymer obtainable by that process and also the use of a specific source of chemically bound water for curing that multi-component composition.

Claims

1. A multi-component composition comprising the following components: (A) an isocyanate-reactive compound; (B) an isocyanate compound selected from the group consisting of polyisocyanates and NCO-terminated prepolymers; and (C) a source of chemically bound water; and (D) optionally a catalyst; and (E) optionally a CO.sub.2 scavenger.

2. The multi-component composition according to claim 1, wherein the isocyanate-reactive compound (A) is selected polyols.

3. The multi-component composition according to claim 1, wherein the isocyanate-reactive compound (A) is selected from polyfunctional amines.

4. The multi-component composition according to claim 1, wherein the isocyanate compound (B) is selected from the group consisting of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), oligomeric MDI, hexamethylene diisocyanate (HDI), trimeric HDI, isophorone diisocyanate (IPDI), and mixtures of two or more of these polyisocyanates.

5. The multi-component composition according to claim 1, wherein the isocyanate compound (B) is selected from prepolymers of the group consisting of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), oligomeric MDI, hexamethylene diisocyanate (HDI), trimeric HDI, isophorone diisocyanate (IPDI), and mixtures of two or more of these polyisocyanate prepolymers.

6. The multi-component composition according to claim 1, wherein the source of chemically bound water (C) is selected from ettringite, calcium silicate hydrate, aluminum hydroxide, zeolites, and mixtures thereof.

7. The multi-component composition according to claim 1, wherein the catalyst (D) is selected from the group consisting of amine-based catalysts and catalysts based on organic metal compounds.

8. The multi-component composition according to claim 1, wherein the CO.sub.2 scavenger (E) is selected from CaO and Ca(OH).sub.2, and mixtures thereof.

9. The multi-component composition according to claim 1, wherein the components (A) and (C) and optionally (D) and (E) are provided in one component and the isocyanate compound (B) is held available separately in another component.

10. A process for preparing a polyurea polymer by curing a multi-component composition with a source of chemically bound water, comprising mixing (A) an isocyanate-reactive compound, (B) an isocyanate compound selected from the group consisting of polyisocyanates and NCO-terminated prepolymers, and (C) a source of chemically bound water, and (D) optionally a catalyst, and (E) optionally a CO.sub.2 scavenger, and allowing the mixture to cure.

11. A polyurea polymer, obtainable by the process according to claim 10.

12. A method comprising: curing a multi-component composition with a source of chemically bound water selected from ettringite, calcium silicate hydrate, aluminum hydroxide, zeolites, and mixtures thereof, wherein the multi-component composition comprises the following components: (A) an isocyanate-reactive compound; (B) an isocyanate compound selected from the group consisting of polyisocyanates and NCO-terminated prepolymers; and (D) optionally a catalyst; and (E) optionally a CO.sub.2 scavenger.

13. The method according to claim 12, wherein the source of chemically bound water is selected from ettringite, calcium silicate hydrate, aluminum hydroxide, and mixtures thereof.

Description

EXAMPLES

General Procedure

[0065] The materials that have been used are listed in Table 1 hereinbelow. The constituents of the A components were mixed. The viscosities and densities of these A components were measured. Then the isocyanate compounds were added to the A component. This preparation was mixed in a speed mixer (Hauschild DAC 600.1 FVZ) for 1 min. @ 2000 rpm. The resulting freshly prepared reactive mixtures were poured on polypropylene sheets, allowed to dry at 23 C./50% relative humidity for 7 days, peeled off and measured.

[0066] Viscosities were measured with a Modular Compact Rheometer MCR 302 (Anton Paar) according to DIN EN ISO 3219. Densities of the preparations were measured according to DIN EN ISO 2811-1. Shore A/D hardness: DIN 53505. Elongation@Break/Tensile Strength: DIN EN ISO 527-1.

Example 1

[0067] Several multi-component compositions comprising a polyether diamine as the isocyanate-reactive compound (i.e. poly(propylene glycol) bis(2-aminopropyl ether)) and an MDI prepolymer were formulated with different sources of water. In two batches, CO.sub.2 scavengers were present. The individual formulations and the results thereof are listed in Table 2 hereinbelow.

[0068] This was a very reactive system. It was not possible to reach sufficient pot life times with 5% of water (although bound to zeolite, i.e. batches #4 and #5), while chemically bound water such as in ettringite, Al(OH).sub.3, and CSH increased pot life times to up to 2 hours. Even Ca(OH).sub.2 could not suppress the foaming of batch #5. Sufficient amounts of ettringite (batch #2) worked better than lime paste in combination with ettringite (batch #1) in suppressing foaming.

Example 2

[0069] Several multi-component compositions comprising a polyester diamine as the isocyanate-reactive compound (i.e. poly(1,4-butanediol) bis(4-aminobenzoate)) and an MDI prepolymer were formulated with different sources of water. In two batches, CO.sub.2 scavengers were present. The individual formulations and the results thereof are listed in Table 3 hereinbelow.

[0070] This was a very reactive system. It was not possible to reach sufficient pot life times with 5% of water (although bound to zeolite, i.e. batches #11 and #12), while chemically bound water such as in ettringite, Al(OH).sub.3, and CSH increased pot life times to 2 hours and more. Ettringite alone (#10) worked better than ettringite in combination with lime paste (#9) in suppressing foaming.

Example 3

[0071] Example 2 was repeated with a carbodiimide-modified MDI as the isocyanate component. The individual formulations and the results thereof are listed in Table 4 hereinbelow.

[0072] The results were essentially the same as in Example 2. Best results were obtained with ettringite as a source of chemically bound water (pot life times of up to 5 h in batch #17 and up to 3 h in batch #18ettringite alone resulted in less foaming than ettringite in combination with lime paste). Zeolite-bound water was also feasible in this experiment.

Example 4

[0073] Example 1 was repeated with polytetramethylene glycol (Poly THF) as the isocyanate-reactive compound and trimeric HDI as the isocyanate component. The individual formulations and the results are listed in Table 5 hereinbelow.

[0074] This was basically a polyurethane system with only a few polyurea functions. All batches (except Al(OH).sub.3 at small A/B mixing ratiosbatch #24) resulted in good pot life times. However, almost all batches resulted in foaming.

TABLE-US-00001 TABLE 1 Component Name Function Chemistry Supplier CAS No. PEthDA Baxxodur EC 303 NCO-Reactive Compound Polyether Diamine BASF SE 9046-10-0 TIBP Triisobutyl Phosphate Diluent Organic Phosphate Ester Lanxess 126-71-6 PEstDA Versalink P-1000 NCO-Reactive Compound Polyester Diamine Evonik 54667-43-5 DisperByk Disperbyk 110 Dispersive Agent Acidic Copolymer Composition Byk/Altana PolyTHF PolyTHF 650 (S) NCO-Reactive Compound Polytetramethylene Glycol BASF SE 25190-06-1 DIBTDL Cosmos 19 Catalyst Dibutyl-Tin Dilaurate Evonik 77-58-7 DIPN Rtasolv DI Diluent Diisopropyl Naphthalene Rain Carbon 38640-62-9 KemFoamEx KemFoamEx 6426 Defoamer Hydrocarbons/Cyclohexanone Kemira Ettringite Casul H1i Chemically Bound Water Synthetic Ettringite Remondis 12004-14-7 Ca(OH).sub.2 Magnesia 7245 CO.sub.2 Scavenger Calcium Hydroxide Magnesia GmbH 1305-62-0 Al(OH).sub.3 Apyral 24 Chemically Bound Water Aluminum Hydroxide Nabaltec 21645-51-2 Zeolite Sylosiv A3 Chemically Bound Water Aluminum Silicate Grace 1318-02-1 CSH # 1 Circosil Chemically Bound Water Tobermorite (88%) Cirkel 1319-31-9 CSH # 2 Circolit Chemically Bound Water Xonotlit Cirkel 1344-95-2 H.sub.2O Water 7732-18-5 Lime Paste Lime Paste CO.sub.2 Scavenger Ca(OH).sub.2 Dispersion .sup.1) MBSD .sup.2) MDI Prepoly. MDI Prepolymer Isocyanate Compound MDI Prepolymer .sup.3) MBSD .sup.2) MMDI Suprasec 2029 Isocyanate Compound Carbodiimide-Modified MDI Huntsman HDI Trimer Desmodur N 3600 Isocyanate Compound HDI Trimer Covestro .sup.1) Consisting of 38.17% DIPN, 0.76% dispersive agent (Trisize 68), and 61.07% Ca(OH).sub.2 .sup.2) Semi fabricate of Master Builders Deutschland GmbH .sup.3) Prepolymer of 50.99% MDI (Lupranat MI, BASF SE), 49% polypropylene glycol (Lupranol 1000, BASF SE) and 0.01% diglycol-bis-chloroformiate

TABLE-US-00002 TABLE 2 Component A # 1 # 2 # 3 # 4 # 5 # 6 # 7 PEthDA 22.22 22.50 22.50 37.50 28.50 22.50 22.50 TIBP 22.22 22.50 22.50 37.50 28.50 22.50 22.50 DIPN 8.50 8.50 8.50 8.50 8.50 8.50 KemFoamEx 1.50 1.50 1.50 1.50 1.50 1.50 Ettringite 30.56 45.00 Ca(OH).sub.2 18.00 Al(OH).sub.3 45.00 Zeolite 10.00 10.00 H.sub.2O 5.00 5.00 1.00 CSH # 1 44.00 CSH # 2 45.00 Ca Silicate Lime Paste 25.00 Viscosity @ 23 C. [mPa s] 370 300 110 60 1800 2700 2590 Density @ 20 C. [g/ml] 1.22 1.16 1.32 1.03 1.15 1.30 1.35 Component B MDI Prepolymer .sup.3) Ratio A/B: a) 100/30, b) 100/50, c) 100/100 Pot Life 2 h 2 h 2 h 45 min 30-35 min 2 h 2 h Shore A Hardness @ 7 d Foamed Solid Solid Foamed Foamed a) Foamed Solid a) 79, a) 61, b, c) Solid a) 68, b) 83, b) 83, b) 86, b) 83, c) 86 c) 91 c) 92 Elongation @ Break Foamed a) 80%, a) 77% Foamed Foamed a) Foamed a) 97% b) 109% b) 249% b) 45% b) 152% c) 185% c) 245% c) 47% c) 154% Tensile Strength Foamed a) 2.8 MPa a) 2.3 MPa Foamed Foamed a) Foamed a) 4.0 MPa b) 3.3 MPa b) 7.4 MPa b) 5.5 MPa b) 8.1 MPa c) 5.3 MPa c) 9.1 MPa c) 6.1 MPa c) 9.4 MPa

TABLE-US-00003 TABLE 3 Component A # 8 # 9 # 10 # 11 # 12 # 13 # 14 PEstDA 40.50 58.50 58.50 68.50 46.50 57.50 58.50 DisperByk 0.50 0.50 0.50 0.50 0.50 0.50 0.50 DIPN 10.00 14.50 14.50 14.50 18.50 14.50 14.50 KemFoamEx 1.50 1.50 1.50 1.50 1.50 1.50 1.50 Ettringite 25.00 25.00 Ca(OH).sub.2 18.00 Al(OH).sub.3 25.00 Zeolite 10.00 10.00 Water 5.00 5.00 1.00 CSH # 1 25.00 CSH # 2 25.00 Ca Silicate Lime Paste 22.50 Viscosity @ 23 C. [mPa s] 4600 5330 3180 2600 4700 6780 8600 Density @ 20 C. [g/ml] 1.13 1.18 1.09 1.20 1.18 1.18 Component B MDI Prepolymer .sup.3) Ratio A/B: a) 100/30, b) 100/50, c) 100/100 Pot Life a, b) 2 h a) 2 h, a, b) 2 h a, b) 1 h a, b, c) 15 min a, b) 2 h a) 2 h, c) 5 h b) 3 h c) 5 h c) 1.15 h c) 5 h b) 3 h c) 5 h c) 5 h Shore A Hardness @ 7 d a) 82, a) 70, a) 78, Foamed Foamed Foamed a) 67, b) 76 b) 70 b) 76 b) 74 c) 81 c) 67 c) 79 Foamed c) 74 Elongation @ Break [%] a) Foamed a) 36, a) 170, Foamed Foamed Foamed a) 27, b) 110, b) 42 b) 490 b) 378 c) 450 c) 170 c) 280 c) Foamed Tensile Strength [MPa] a) Foamed a, b) 1.3 a) 2.6, Foamed Foamed Foamed a) 1.7, b) 3.7, c) 6.5 b) 9.6 b) 5.4 c) 2.9 c) 13.1 c) Foamed

TABLE-US-00004 TABLE 4 Component A # 15 # 16 # 17 # 18 # 19 # 20 # 21 PEstDA 40.50 58.50 58.50 68.50 46.50 57.50 58.50 DisperByk 0.50 0.50 0.50 0.50 0.50 0.50 0.50 DIPN 10.00 14.50 14.50 14.50 18.50 14.50 14.50 KemFoamEx 1.50 1.50 1.50 1.50 1.50 1.50 1.50 Ettringite 25.00 25.00 Ca(OH).sub.2 18.00 Al(OH).sub.3 25.00 Zeolite 10.00 10.00 Water 5.00 5.00 1.00 CSH # 1 25.00 CSH # 2 25.00 Lime Paste 22.50 Viscosity @ 23 C. [mPa s] 3348 4810 2827 2819 4700 5763 8408 Density @ 20 C. [g/ml] 1.19 1.14 1.18 1.07 1.20 1.19 1.17 Component B MMDI (Carbodiimide-Modified MDI) Ratio A/B: a) 100/30, b) 100/50, c) 100/100 Pot life a) 2 h a) 45 min a) 30 min a) 45 min a) 15 min a) 15 min a) 1 h b) 3 h b) 90 min b) 30 min b) 90 min b) 15 min b) 15 min b) 30 min c) 5 h c) 3 h c) 60 min c) 3 h min c) 30 min c) 45 min c) 2 h Shore D hardness @ 7 d a) 52, a) 52, a) 52, a) 46, Foamed a) 20, a) 51, b) 54 b) 51 b) 56 b) 53 b) 27 b) 49 c) 53 c) 56 c) 58 c) 23 c) 48 c) 61 Elongation @ Break [%] Foamed a) 210 a) 230 a) 270 Foamed Foamed Foamed b) 90 b) 120 b) 150 c) Foamed c) Foamed c) Foamed Tensile Strength [MPa] Foamed a) 10 a) 17.8 a) 19.4 Foamed Foamed Foamed b) 10 b) 15.3 b) 15.8 c) Foamed c) Foamed c) Foamed

TABLE-US-00005 TABLE 5 Component A # 22 # 23 # 24 # 25 # 26 # 27 PolyTHF 40.00 57.95 57.95 82.95 64.95 56.95 DIBTDL 0.05 0.05 0.05 0.05 0.05 0.05 DisperByk 0.50 0.50 0.50 0.50 0.50 0.50 KemFoamEx 1.50 1.50 1.50 1.50 1.50 1.50 Ettringite 40.00 40.00 Ca(OH).sub.2 18.00 Al(OH).sub.3 40.00 Zeolite 10.00 10.00 Water 5.00 5.00 1.00 CSH # 1 40.00 Lime paste 17.95 Viscosity @ 23 C. [mPa s] 5740 3790 985 492 2800 6820 Density @ 20 C. [g/ml] 1.16 1.2 1.31 1.05 1.2 1.3 Component B HDI Trimer Ratio A/B: a) 100/30, b) 100/50, c) 100/100 Pot Life 2 h a) 2 h a) 25 min a) 1 h a) 1.10 h 2 h b) 3 h b) 1 h b) 3 h b) 1.10 h c) 5 h c) 5 h c) 5 h c) 5 h Shore A Hardness @ 7 d a) 65, a) 66, a) 77, Foamed Foamed a) 59, b) 60 b) 76 b) 80 b) 81 c) Foamed c) 70 c) 53 c) (Shore D) 35 Elongation @ Break [%] Foamed Foamed a) 30, Foamed Foamed Foamed b) 20 c) Foamed Tensile Strength [MPa] Foamed Foamed a) 2.0, Foamed Foamed Foamed b) 2.8 c) Foamed