Composition that forms an insulating layer and use thereof

Abstract

A composition that forms an insulating layer is described, which contains a thiol-ene-based binder. With the composition according to the invention, the expansion rate of which is relatively high, coatings having the layer thickness necessary for the respective fire resistance time can be applied simply and quickly, the layer thickness being reduced to a minimum and a highly insulating effect still being achieved. The composition according to the invention is particularly suitable for fire protection, in particular as a coating of metallic and/or non-metallic substrates, for example steel components such as pillars, beams or truss members, to increase the fire resistance time.

Claims

1. An insulating layer-forming composition comprising: a component A containing at least one compound having one or multiple reactive carbon multiple bonds per molecule; a component B containing at least one thiol-functionalized compound, the average number of thiol groups per molecule of which is at least 2, and a radical initiator; and a component C including a mixture, the mixture including at least one carbon source, at least one dehydrogenation catalyst and at least one propellant, or including at least expandable graphite.

2. The composition as recited in claim 1 wherein the at least one compound having the reactive carbon multiple bonds contains one or multiple CC double bonds and is selected from among vinylesters, allylesters, vinylethers, allylethers, vinylamines, allylamines, vinylamides, esters and amides of (meth)acrylic acid, esters of fumaric acid, maleinimides.

3. The composition as recited in claim 2 wherein the at least one compound contains one or multiple CC double bonds and is selected from among trimethylolpropane diallylether, pentaerythritol triallylether, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane diallylether, phthalic acid diallylester, succinyl acid diallylester, succinic acid bis[4-(vinyloxy)butyl]ester, adipic acid bis[4-(vinyloxy)butyl]ester, isophthalic acid bis[4-(vinyloxy)butyl]ester, terephthalic acid bis[4-(vinyloxy)butyl]ester, trimellitic acid tris[4-(vinyloxy)butyl]ester, diethyleneglycol divinylether, 1,4-cyclohexanedimethanol divinyl ether, 1,4-butanediol divinylether, pentaerythritol allylether, 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione and triallylamine.

4. The composition as recited in claim 1 wherein the at least one thiol-functionalized compound is a polythiol compound having at least three thiol groups per molecule.

5. The composition as recited in claim 1 wherein the thiol-functionalized compound is selected from the group consisting of glycol-bis(2-mercaptoacetate), glycol-bis(3-mercaptopropionate), 1,2- propylene glycol-bis(2-mercaptoacetate), 1,2-propylene glycol-bis(3-mercaptopropionate), 1,3-propylene glycol-bis(2-mercaptoacetate), 1,3-propylene glycol-bis(3-mercaptopropionate), tris(hydroymethyl)methane-tris(2-mercaptoacetate), tris(hydroxymethyl)methane-tris(3-mercaptopropionate), 1,1,1-tris(hydroxymethyl)ethane-tris(2-mercaptoacetate), 1,1,1-tris(hydroxymethyl)ethane-tris(3-mercaptopropionate), 1,1,1-trimethylolpropane-tris(2-mercaptoacetate), ethoxylated 1,1,1-trimethylolpropane-tris(2-mercaptoacetate), propoxylated 1,1,1-trimethylolpropane-tris(2-mercaptoacetate), 1,1,1-trimethylolpropane-tris(3-mercaptopropionate), ethoxylated 1,1,1-trimethylolpropane-tris(3-mercaptopropionate), propoxylated trimethylolpropane-tris(3-mercaptopropionate), 1,1,1-trimethylolpropane-tris(3-mercaptobutyrate), pentaerythritol-tris(2-mercaptoacetate), pentaerythritol-tetrakis(2-mercaptoacetate), pentaerythritol-tri s(3-mercaptopropionate), pentaerythritol-tetrakis(3-mercaptopropionate), pentaerythritol-tri s(3-mercaptobutyrate), pentaerythritol-tetrakis(3-mercaptobutyrate), Capcure 3-800 (BASF), GPM-800 (Gabriel Performance Products), Capcure LOF (BASF), GPM-800LO (Gabriel Performance Products), KarenzMT PE-1 (Showa Denko), 2-ethylhexylthioglycolate, iso-octylthioglycolate, di(n-butyl)thiodiglycolate, glycol-di-3-mercaptopropionate, 1,6-hexanedithiol, ethyleneglycol-bis(2-mercaptoacetate) and tetra(ethylene glycol)dithiol.

6. The composition as recited in claim 1 wherein the radical initiator is an inorganic or organic peroxide.

7. The composition as recited in claim 1 further comprising a reactive diluent.

8. The composition as recited in claim 1 further comprising an accelerator.

9. The composition as recited in claim 8 wherein the accelerator is a combination of a 1,3-dicarbonyl compound and a metal salt.

10. The composition as recited in claim 1 further comprising an inhibitor.

11. The composition as recited in claim 1 wherein the component C also contains at least one ash crust stabilizer.

12. The composition as recited in claim 1 further comprising organic or inorganic auxiliary agents.

13. A method comprising: applying the composition as recited in claim 1 as a coating.

14. The method as recited in claim 13 wherein the coating coats steel construction elements.

15. The method as recited in claim 13 wherein the coating coats metallic or non-metallic substrates.

16. The method as recited in claim 13 wherein the coating is a fire protection layer.

Description

EXEMPLARY EMBODIMENTS

(1) The following components are used for preparing insulating layer-forming compositions according to the present invention:

(2) In each case, component B together with the ammonium polyphosphate and component A together with the remaining compounds of component C are blended and homogenized with the aid of a dissolver. In this way, components II and I are obtained. For the application, these two mixtures (component I and II) are then mixed together and applied either before spraying or preferably during the spraying.

(3) The curing behavior was observed in each case, the intumescence factor and the relative ash crust stability being subsequently determined. For this purpose, the mixtures were each placed in a round Teflon mold having a depth of approximately 2 mm and a diameter of 48 mm.

(4) The time of curing in this case corresponds to the time after which the samples were fully hardened and could be removed from the Teflon mold.

(5) To determine the intumescence factor and the relative ash crust stability, a muffle kiln was preheated to 600 C. A multiple measurement of the sample thickness was carried out with the caliper and the mean value h.sub.M was calculated. Each of the samples was then introduced into a cylindrical steel mold and heated in the muffle kiln for 30 min. After cooling to room temperature, the foam height h.sub.E1 was first non-destructively determined (mean value of a multiple measurement). The intumescence factor I is calculated as follows:
Intumescence factor I: I=h.sub.E1:h.sub.M

(6) Subsequently, a defined weight (m=105 g) was dropped from a defined height (h=100 mm) onto the foam in the cylindrical steel mold and the residual foam height h.sub.E2 after this partially destructive impact was determined. The relative ash crust stability was calculated as follows: relative ash crust stability (AKS): AKS=h.sub.E2:h.sub.E1

(7) In addition, the shrinkage during drying, i.e., the reaction of the two components, was measured.

(8) For this purpose, a mold having a thickness of 10 mm was filled with each mixture. After curing, the molded bodies formed were removed from the mold and the thickness measured. The shrinkage is the product of the difference.

Example I

(9) Component A

(10) TABLE-US-00001 Component Amount [g] 1,4-butanediol divinyl ether 42.4 Acetylacetone 0.6 Octa-Soligen Mangan 10.sup.1 0.6 TEMPOL.sup.2 0.0288 .sup.1Mn(ll)-octoate .sup.24-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl
Component B

(11) TABLE-US-00002 Component Amount [g] Thiocure PETMP.sup.3 72.8 Trigonox C.sup.4 3.6 .sup.3Pentaerythritol-tetra(3-mercaptopropionate) .sup.4tert-butylperbenzoate, 55-% aqueous solution
Component C

(12) TABLE-US-00003 Component Amount [g] Pentaerythrite 98% 37.5 Melamine 37.5 Exolit AP 422.sup.5 71.1 Titanium dioxide 34.0 .sup.5Ammonium polyphosphate

(13) After mixing of the three components, the mixture cured after 11 minutes to form a white polymeric solid.

Example 2

(14) Component A

(15) TABLE-US-00004 Component Amount [g] 1,4-Cyclohexanedimethanol divinylether 63.9 Tempol 0.0216 Acetylacetone 0.5 Octa-Soligen Mangan 10 0.5
Component B

(16) TABLE-US-00005 Component Amount [g] Thiocure TMPMP.sup.6 86.5 Trigonox C 4.8 .sup.6Trimethylolpropanetri(3-mercaptopropionate)
Component C

(17) TABLE-US-00006 Component Amount [g] Pentaerythrite 98% 49.9 Melamine 49.9 Exolit AP 422 94.8 Titanium dioxide 45.4

(18) After mixing of the three components, the mixture cured after 10 minutes to form a white polymeric solid.

Example 3

(19) Component A

(20) TABLE-US-00007 Component Amount [g] BVBI.sup.7 38.3 Tempol 0.0288 Acetylacetone 0.6 Octa-Soligen Mangan 10 0.6 .sup.7Bis[4-(vinyloxy)butyl]isophthalate
Component B

(21) TABLE-US-00008 Component Amount [g] Thiocure PETMP 60.5 Trigonox C 94.8
Component C

(22) TABLE-US-00009 Component Amount [g] Pentaerythrite 98% 49.9 Melamine 49.9 Exolit AP 422.sup.4 94.8 Titanium dioxide 54.4

(23) After mixing of the three components, the mixture cured in 4 minutes to form a white polymeric solid.

(24) The shrinkage in the case of all three compositions was less than 5.0%

Comparison Example 1

(25) A commercial fire protection product (Hilti CFP S-WB) based on aqueous dispersion technology was used as a comparison.

Comparison Example 2

(26) As an additional comparison, a standard epoxy amine system was used (Jeffamin T-403, liquid, solvent-free and crystallization-resistant epoxy resin, made up of low molecular bisphenol A and bisphenol F-based epoxy resins (Epilox AF 18-30, Leuna-Harze GmbH) and 1,6 hexanediol diglycidylether) which was tested, filled to 60% with an intumescent mixture similar to the examples above.

Comparison Example 3

(27) As an additional comparison, a standard epoxy amine system was used (isophorone diamine, trimethylol propane triacrylate and liquid, solvent-free and crystallization-resistant epoxy resin, made up of low molecular bisphenol A and bisphenol F-based epoxy resin (Epilox AF 18-30, Leuna-Harze GmbH)), which was tested, filled to 60% with an intumescent mixture similar to the examples above.

(28) TABLE-US-00010 TABLE 1 Measurement results of the intumescence factor, the ash crust stability and the curing time Intu- mescence Relative ash Sample factor crust stability thickness h.sub.M Example I (multiple) AKS (multiple) (mm) Curing time 1 28.7 0.94 1.8 11 minutes 2 20.6 0.78 1.6 10 minutes 3 24.1 0.60 1.4 4 minutes Comparison 36 0.62 1.8 10 days example 1 Comparison 22 0.04 1.6 12 hours example 2 Comparison 1.7 0.60 1.2 1 day example 3