Foamable, insulating-layer-forming multi-component composition having improved storage stability and use of the same

Abstract

A foamable, insulating-layer-forming multi-component composition contains alkoxysilane-functional polymer, insulating-layer-forming fire-protection additive, blowing-agent mixture, cross-linking agent, and a flame-protection agent that is miscible in water or another compound that is miscible in water. The individual ingredients of the blowing-agent mixture are separated from one another to ensure inhibition of reaction prior to use of the composition, and the cross-linking agent is separated from the alkoxysilane-functional polymer to ensure inhibition of reaction prior to use of the composition. The foamable, insulating-layer-forming multi-component composition can be used as a foam-in-place foam or for production of molded blocks.

Claims

1. A foamable, insulating-layer-forming multi-component composition, comprising: at least one alkoxysilane-functional polymer, which contains, as terminal groups and/or as side groups along the polymer chain, at least two alkoxy-functional silane groups of formula (I):
—Si(R.sup.1).sub.m(OR.sup.2).sub.3−m  (I), wherein R.sup.1 stands for a linear or branched C.sub.1-C.sub.16 alkyl moiety, R.sup.2 stands for a linear or branched C.sub.1-C.sub.6 alkyl moiety, and m stands for a whole number from 0 to 2, at least one cross-linking agent, which, prior to use of the composition, is separated from the alkoxysilane-functional polymer to ensure inhibition of reaction, a blowing-agent mixture, the individual ingredients of which, prior to use of the composition, are separated from one another to ensure inhibition of reaction, at least one insulating-layer-forming fire-protection additive, and 7 to 20 wt %, relative to the total weight of the composition, of at least one compound selected from the group consisting of liquid flame-protection agents and liquid compounds that are respectively water-soluble or miscible with water, wherein the liquid flame-protection agent is at least one member selected from the group consisting of diethylethane phosphonate, triethylphosphate, dimethylpropyl phosphonate, and dimethylmethane phosphonate, and wherein the liquid compound is at least one member selected from the group consisting of acetone, sulfolane, ethanol, methanol, and mixtures thereof, wherein the polymer has a dynamic viscosity in the range of 5 to 27 Pa.Math.s, measured with a Kinexus Ultra+ from Malvern Instruments Ltd.; at a temperature of 23° C.; with a spindle type: plate with a diameter of 20 mm with a 2 mm slit; at a rotational speed of 100 s.sup.−1, and wherein the polymer comprises a basic backbone, which is at least one member selected from the group consisting of an alkyl chain, a polyether, polyester, polyether ester, polyamide, polyurethane, polyester urethane, polyether urethane, polyether ester urethane, polyamide urethane, polyurea, polyamine, polycarbonate, polyvinyl ester, polyacrylate, polyolefin, polyisobutylene, polysulfide, rubber, neoprene, phenol resin, epoxy resin and melamine, with the proviso that the composition does not contain any organotin catalyst.

2. The composition according to claim 1, comprising the at least one liquid flame-protection agent.

3. The composition according to claim 1, comprising the at least one liquid compound.

4. The composition according to claim 1, wherein the blowing-agent mixture comprises compounds that, after being mixed, react with one another with formation of carbon dioxide (CO.sub.2), of hydrogen (H.sub.2) or of oxygen (O.sub.2).

5. The composition according to claim 4, wherein the blowing-agent mixture comprises an acid and a compound, that is able to react with the acid to form carbon dioxide.

6. The composition according to claim 1, wherein the alkoxysilane-functional polymer is a mixture of two or more alkoxy functional polymers.

7. The composition according to claim 1, wherein the basic backbone is a polyurethane and/or a polyether.

8. The composition according to claim 1, wherein the cross-linking agent is water or a water-containing ingredient.

9. The composition according to claim 1, wherein the insulating-layer-forming fire-protection additive comprises at least one thermally expandable compound and/or a mixture that contains at least one acid former, at least one gas builder and optionally at least one carbon source.

10. The composition according to claim 9, wherein the fire-protection additive further contains an ash-crust stabilizer.

11. The composition according to claim 1, wherein the composition contains a co-cross-linking agent.

12. The composition according to claim 1 further comprising at least one further ingredient which is selected from the group consisting of plasticizers, water scavengers, inorganic fillers and further additives.

13. A molded block, obtained from a composition according to claim 1, wherein the respective components are mixed with one another and the mixture is foamed in a mold.

14. A method comprising: mixing components of the composition according to claim 1 with one another, thereby obtaining a mixture, and foaming the mixture in a mold.

15. A method comprising: applying the composition according to claim 1, as a mixture, to at least one cavity or surface selected from the group consisting of openings; cable or pipe penetrations in walls, floors and/or ceilings; joints between a ceiling and a wall part; joints between a masonry opening and a construction part to be installed; joints between a ceiling and a wall; and joints between an outside wall and a curtain-wall facade of a building, to thereby provide fire protection to the cavity or surface.

16. The composition according to claim 1, containing no metal catalyst.

17. The composition according to claim 1, containing no catalyst.

18. The composition according to claim 1, comprising 9 to 20 wt % relative to the total weight of the composition, of the at least one compound selected from the group consisting of liquid flame-protection agents and liquid compounds that are respectively water-soluble or miscible with water.

19. The composition according to claim 1, comprising 9 to 15.4 wt %, relative to the total weight of the composition, of the at least one compound selected from the group consisting of liquid flame-protection agents and liquid compounds that are respectively water-soluble or miscible with water, and wherein the at least one compound comprises triethylphosphate, dimethylpropyl phosphonate, acetone, or sulfolane.

20. The composition according to claim 1, wherein the foamable composition gives a stable foam when foamed.

Description

EXEMPLARY EMBODIMENTS

(1) The individual ingredients listed in Tables 2, 3 and 4 are respectively mixed and homogenized. For use, these mixtures are mechanically mixed with one another in a container until homogeneous intermixing has been achieved and until foaming has begun.

(2) TABLE-US-00001 TABLE 1 Substances used Silane-terminated prepolymer I Silane-terminated polyurethane, Desmoseal S XP-2821 of Bayer AG; viscosity at 23° C. ~20000 mPa .Math. s Silane-terminated prepolymer II Silane-terminated polyurethane, Desmoseal S XP-2749 of Bayer AG, viscosity at 23° C. ~4500 mPa .Math. s Silane-terminated prepolymer III Dimethoxy(methyl)silyl methylcarbamate-terminated polyether Geniosil STP-E 10 of Wacker, viscosity, dynamic at 25° C. ~10000 mPa .Math. s (DIN 51562); density at 20° C. 1.0069 g/cm.sup.3 Silane-terminated prepolymer IV KANEKA MS POLYMER SAX015 of Kaneka Beldium NV Triethyl phosphate (TEP) Levagard ® TEP-Z of Lanxess; viscosity at 20° C.: <1.7 mPa .Math. s Dimethylpropane phosphonate (DMPP) Levagard ® DMPP of Lanxess; viscosity 2.16 mPa .Math. s Tri(2-chloroisopropyl) phosphate (TCPP) Levagard ® PP; viscosity 85 mPa .Math. s Acetone Merck Sulfolane of Sigma-Aldrich, product number T22209 Vinyltrimethoxysilane Geniosil ® XL 10 of Wacker, viscosity, dynamic at 25° C. 0.6 mPa .Math. s; density at 25° C. 0.97 g/cm.sup.3 Demineralized water Calcium carbonate OMYABOND 520-OM of Omya Citric acid, anhydrous Citric acid, anhydrous F6000 (CAS no. 77-92-9) of BCD Chemie L-Tartaric acid Natural L(+)-tartaric acid of BCD Chemie; type 2 2-400 mic. 25/SAC Expandable graphite Nord-Min ® 351 of Nordmann-Rassmann, Hamburg, Germany; Ammonium polyphosphate (APP) Exolit ® AP 462 of Clairant; microencapsulated with melamine resin Dipentaerythritol Charmor ® DP 40 of Perstorp . . . ; particle size < 40 μm; moisture content 0.1%; at least 98% Holtac D of Perstorp; particle size < 40 μm; at least 99% Iron oxide (Fe.sub.2O.sub.3) Bayferrox 130 M of Lanxess Xanthan Xanthan of Kremer Pigmente, article number 63450 Fumed silica Cab-O-Sil TS-720 of Cabot Catalyst TIB KAT 223 Dioctyltin acetylacetonate of TIB Chemicals AG

(3) Assessment of the Foam Resistance

(4) The foam resistance or the foam collapse was visually assessed, wherein the assessment was made at the point in time at which the foam had reached its maximum height. It was observed whether the foam had lost its maximum height or had subsided.

(5) Determination of the Tack-Free Time as a Parameter for the Foam Curing Time

(6) After completion of discharge, the tackiness of the foam surface was tested with a wooden spatula at specified time intervals. For this purpose, the wooden spatula was laid lightly on the foam surface and lifted once again. The point in time at which filaments were no longer being drawn or at which it was no longer possible to observe any material detachment at the foam surface defines the tack-free time.

(7) Measurement of the Viscosity

(8) The dynamic viscosity was measured with a Kinexus Ultra+ instrument of Malvern Instruments Ltd. at 23° C., with 2 mm slit and a plate with 20 mm diameter. The value in mPa.Math.s was read at a rotational speed of 100 per second.

(9) TABLE-US-00002 TABLE 2 Foam curing time (tack-free time) and foam stability in dependence on the flame-protection agent used and its quantity (values in wt %) Comparison Comparison Comparison 1 Comparison 2 3 Comparison 4 5 Example 1 Example 2 Example 3 Example 4 Silane-terminated 25.4 22.2 18.6 25.4 25.4 22.2 18.6 22.2 18.6 prepolymer I Silane-terminated 18.1 15.9 13.2 18.1 18.1 15.9 13.4 15.9 13.2 prepolymer IV TEP — — — 3.6 — 9.0 15.2 — — DMPP — — — 3.6 — — 9.0 15.2 TCPP 3.6 9.0 15.2 — — — — — — Vinlytrimethoxysilane 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 Demineralized water 11.1 11.1 11.1 11.1 11.1 11.1 11.1 11.1 11.1 Calcium carbonate 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 Citric acid, anhydrous 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 Expandable graphite 12.1 12.1 12.1 12.1 12.1 12.1 12.1 12.1 12.1 APP 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 Monopentaerythritol 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 Iron oxide (Fe.sub.2O.sub.3) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 L-Tartaric acid 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 Xanthan 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Fumed silica 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Foam curing time [min] 3.33 4 5 4 2 2.33 1.67 1.33 0.55 Foam stability* − − − − − + + + + “−” = foam collapse/“+” = foam remains stable

(10) TABLE-US-00003 TABLE 3 Foam curing time and foam stability in dependence on the solvent used and its quantity (values in wt %) Comparison 6 Example 5 Example 6 Comparison 7 Example 8 Example 9 Silane-terminated prepolymer I 25.7 22.5 18.9 25.7 22.5 18.9 Silane-terminated prepolymer IV 18.4 16.1 13.4 18.7 16.1 13.5 Acetone 3.7 9.1 15.4 — — — Sulfolane — — — 3.7 9.1 15.4 Vinlytrimethoxysilane 2.2 2.1 2.1 2.1 2.1 2.1 Demineralized water 11.1 11.1 11.1 11.1 11.1 11.1 Calcium carbonate 6.3 6.2 6.2 6.2 6.2 6.2 Citric acid, anhydrous 5.4 5.4 5.4 5.4 5.4 5.4 Expandable graphite 12.7 12.1 12.1 12.1 12.1 12.1 APP 6.1 5.8 5.8 5.8 5.8 5.8 Dipentaerythritol 2.9 2.9 2.9 2.9 2.9 2.9 L-Tartaric acid 5.4 5.4 5.4 5.4 5.4 5.4 Xanthan 0.2 0.2 0.2 0.2 0.2 0.2 Foam curing time [min] 2.6 2.4 1.7 2.5 2.0 1.9 Foam resistance − + + − + +

(11) TABLE-US-00004 TABLE 4 Influence of the catalyst on the storage stability (shelf life) of the polymer component, determined on the basis of the viscosity of the composition Example 10 Comparison 8 Example 11 Comparison 9 Example 12 Comparison 10 Example 13 Comparison 11 Silane-terminated 52.5 52.5 26.25 26.25 prepolymer I Silane-terminated 52.5 52.5 prepolymer II Silane-terminated 52.5 52.5 prepolymer III Silane-terminated 26.25 26.25 prepolymer IV TEP 12 12 12 12 12 12 12 12 Vinlytrimethoxysilane 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 Calcium carbonate 8.25 8.25 8.25 8.25 8.25 8.25 8.25 8.25 Expandable graphite 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 APP 8.33 8.33 8.33 8.33 8.33 8.33 8.33 8.33 Catalyst additionally additionally additionally additionally 0.7% 0.7% 0.7% 0.7% Shear viscosity at 23° C. 2.825 5.376 5.692 7.472 1.686 1.786 4.461 6.972 100 rev. per sec. [Pa .Math. s], freshly prepared Shear viscosity at 23° C., 3.567 100 8.114 13.23 2.194 4.767 5.008 84.07 100 rev. per sec. [Pa .Math. s], storage: 1 week at 40° C. Shear viscosity at 23° C., 4.842 not 9.771 49 2.439 50.49 7.683 not 100 rev. per sec. [Pa .Math. s], measurable measurable storage: 4 weeks at 40° C.

(12) The results of Comparison Examples 1 to 3 (Table 2) show that a composition that contains a non-water-soluble flame-protection agent in the form of TCPP indeed foams up, but the foam collapses before it cures.

(13) The results of Comparison Examples 4 to 7 (Tables 2 and 3) show that a composition that contains a water-soluble flame-protection agent in the form of TEP or DMPP and that contains a water-soluble liquid in the form of acetone or sulfolane in a concentration of 3.6 wt % foams up, but the foam collapses before it cures.

(14) When the concentration of liquid flame-protection agent (TEP, DMPP) or of liquid compounds (acetone, sulfolane) that are water-soluble is increased, the curing time of the foams becomes shorter and the foam remains preserved. This is shown by Examples 1 to 9.

(15) The formulations produced according to Table 4, which in a two-component system correspond to the polymer component, were stored at 40° C. The viscosity both of the freshly prepared formulations and also of the respective formulation after a storage time of one week or four weeks were measured according to the foregoing method.

(16) From Table 4 it is evident that, in the formulations that contain a catalyst (Comparison Examples 8 to 11), a distinct increase of the viscosity can already be recognized after one week of storage, or at least after four weeks of storage. As a result, the component that contains the prepolymer in formulations using cartridges, for example, such as two-component cartridges, becomes highly viscous, which leads to very high squeezing forces, to mixing disorders and consequently to inadequate foaming.

(17) Compared with the catalyst-containing formulations, the catalyst-free formulations (Examples 10 to 13) exhibit hardly any increase in viscosity.

(18) From this, it can be concluded that the catalyst-free formulations have a distinctly increased and thus improved storage stability.