DE3303702A1 - Intumescent compositions - Google Patents

Abstract

The present invention relates to solvent-free intumescent compositions for the production of mouldings having good intumescent properties based on mixtures of 1,2-polyepoxides, preferably mixtures of a 1,2-polyepoxide containing at least one nitrogen atom per molecule, at least one aliphatic or cycloaliphatic polyamine, ethylenediamine phosphate, optionally in combination with cyanuric acid derivatives and additives.

Description

Intumescent materials

The present invention relates to solvent-free intumescent materials for the production of moldings with good intumescent properties on the Based on mixtures of 1,2-polyepoxides, preferably of at least one, at least 1,2-polyepoxide containing one nitrogen atom per molecule, at least one aliphatic or cycloaliphatic polyamine, ethylene diamine phosphate, optionally in combination with cyanuric acid derivatives and additives.

Intumescent compounds are available as putty, mortar or molded parts flame-retardant, foamable masses, which when exposed to a flame or heated above a certain high temperature, around 3000C, expand, doing a flame retardant and insulating Forming foam that protects the rear areas from further flames and closes any cracks or crevices that may appear.

Such intumescent materials are known in principle. They mostly exist from a phosphate or another compound that forms a non-volatile acid, the end a blowing agent such as dicyandiamide, melamine or formaldehyde resins and a carbon source for the resulting carbonization foam, mostly Polyalcohols.

The disadvantage of these constituents of intumescent materials is that they are sensitive to moisture or decompose under hydrolysis conditions, e.g. with elimination of phosphoric acid, such as polyphosphates.

On the other hand, there is considerable interest in intumescent materials for the production of molded parts with good processability and good mechanical properties and less moisture sensitivity than by using the previous one Phosphate mixtures is achievable.

It has now been found that this goal can be achieved if one at least one 1,2-polyepoxide, preferably at least one 1,2-polyepoxide with at least one tertiary nitrogen atom per molecule with at least aliphatic or cycloaliphatic Polyamine, ethylenediamine phosphate and optionally cyanuric acid derivatives such as about melamine and possibly other additives and under shaping for Curing brings.

By using. of ethylenediamine phosphate as an intumescent mediator Fillers for the 1,2-polyepoxide can be added to other, otherwise intumescent mixtures Usual components such as propellants and polyalcohol can be dispensed with.

It is also advantageous that the ethylenediamine phosphate does not is hygroscopic and under hydrolytic conditions conditions neutral remain. Both properties share the same properties as other phosphates used in this field do not have: The usual ammonium or amine phosphates are hygroscopic and the ammonium polyphosphates hydrolyze, releasing excess phosphoric acid.

US Pat. No. 4,198,328 describes paint formulations, which can contain epoxy resins as polymeric binders and for which the possible The use of ethylenediamine phosphate is mentioned, but it does not give any teaching for the use of solvent-free epoxy resins filled with ethylene diamine phosphate for the production of molded parts.

The invention therefore relates to solvent-free intumescent materials for the production of molded parts from mixtures of 1. at least one 1,2-polyepoxide, preferably at least one 1,2-polyepoxide with at least one tertiary nitrogen atom per Molecule, 2. at least one aliphatic or cycloaliphatic polyamine, 3. Ethylenediamine phosphate and optionally 4. at least one cyanuric acid derivative as well as molded parts from it.

The known mixtures are preferred for the mixtures according to the invention halogen-free polyepoxides with more than one 1,2-epoxy group in question (component 1).

These include polyglycidyl ethers of polyhydric phenols, for example from pyrocatechol, resorcinol, hydroquinone, from 4,4'-dihydroxydiphenylmethane 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, from 4,4'-dihydroxydiphenyldimethylmethane (Bisphenol A), from 4,4'-dihydroxydiphenylmethane, from 4,4'-dihydroxydiphenylcyclohexane, from 4,41-dihydroxy-3,3 '-dimethyldiphenylpropane, from 4,4'-dihydroxydiphenyl, from 4,4'-dihydroxydiphenyl sulfone, from tris (4-hydroxyphenyl) methane, from novolaks (i.e. from reaction products of mono- or polyhydric phenols with aldehydes, in particular Formaldehyde, in the presence of acidic catalysts), from diphenols obtained by esterification of 2 moles of the sodium salt of an aromatic oxycarboxylic acid with one mole of one Dihaloalkane or dihalo dialkyl ether were obtained (see. British Patent 1 017 612), from polyphenols, which by condensation of phenols and long-chain, Haloparaffins containing at least 2 halogen atoms were obtained (cf. British Patent Specification 1,024,288).

The following may also be mentioned: glycidyl ethers of polyhydric alcohols, for example from 1,4-butanediol, 1,4-butenediol, glycerol, trimethylolpropane, pentaerythritol and Polyethylene glycols.

Glycidyl esters of polybasic aromatic, aliphatic and cycloaliphatic carboxylic acids, for example phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, tetrahydrophthalic acid, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, which may be optionally substituted by methyl groups and glycidyl esters of reaction products of 1 mol of an aromatic or cycloaliphatic dicarboxylic acid anhydride and 1 /: also come into question 2 mol of a diol or 1 / n mol of a polyol with n hydroxyl groups, such as glycidyl carboxylic acid esters of the general formula wherein A is an at least divalent radical of an aliphatic hydrocarbon optionally interrupted by oxygen and / or cycloaliphatic rings or the divalent radical of a cycloaliphatic hydrocarbon, R is hydrogen or an alkyl radical with 1-3 carbon atoms and n is a number between 2 to 6 mean, or mixtures of glycidyl carboxylic acid esters of the general formula given (cf. British Patent 1,220,702).

The following are particularly preferred: 1,2-polyepoxides with at least one tertiary Nitrogen atom per molecule, e.g. bis- (N-epoxypropyl) -aniline, bis- (N-epoxypropyl) -butylamine, Bis- (N-epoxypropyl) -4-aminophenylglycidyl ether, triglycidyl isocyanurate, N, N'-diepoxypropyloxamide, Triglycidyl-1,2,4-triazolidine-3,5-diones according to DE-OS 2 935 354, glycidyl 1,2,4-triazolindine-3,5-diones with 2 to 10 glycidyl groups according to DE-OS 3 027 623, N, N'-diglycidyl-bis-hydantoinyl compounds according to DE-AS 1 670 490, N, N'-diglycidyl compounds of cyclic ureides according to British patent specification 1 148 570, DE-PS 2 263 492 and DE-AS 1 954 503, polyurethane diglycidyl ether according to US Pat. No. 2,830,038, DE-AS 1 947 001 and DE-AS 1 966 182, containing imide groups Diglycidyl ester according to DE-AS 2 306 403.

The above 1,2-polyepoxides having at least one tertiary nitrogen atom per molecule can with nitrogen-free 1,2-polyepoxides, especially with polyglycidyl ethers polyhydric phenols, e.g. bisphenol A, can be mixed. Preferred solvent-free As component 1, intumescent compositions contain 10-100% by weight of a 1,2-polyepoxide with at least one tertiary nitrogen atom per molecule and 0-90% by weight of one nitrogen-free 1,2-polyepoxide.

The 1,2-polyepoxides, especially solid 1,2-polyepoxides, can be used for Viscosity reduction also with liquid monoepoxides such as phenyl glycidyl ether, tert-butylphenyl glycidyl ether, allyl glycidyl ether and others.

As component 2, customary aliphatic and / or cycloaliphatic Polyamines are used, for example triethylenetetramine, pentaethylenehexamine, the hydrogenation products of addition products from 1 mole of a glycol (such as 1,4-butylene glycol) and 2 moles of acrylonitrile, 4,4'-diamino-3,3'-dimethyl-dicyclohexylmethane, Mixtures of the aforementioned polyamines or alkoxylation products of the aforementioned Polyamines. Preferably 0.8 to 1.2 NH equivalents of the are used per epoxide equivalent Polyamine used.

Component 3 of the intumescent compositions according to the invention is ethylene diamine phosphate, including preferably the neutralization product of ethylenediamine and orthophosphoric acid is understood. In principle, salts of ethylenediamine with other phosphoric acids, e.g. pyro- or metaphosphoric acid or phosphoric acids with a lower degree of oxidation can be used.

It is also possible to use ethylenediamine in a mixture with if less than the stoichiometric amount of phosphoric acid directly as hardener or hardener component to use for the 1,2-polyepoxide.

Based on 1,2-polyepoxide, the ethylene diamine phosphate is in amounts by weight from 1: 0.1 to 1: 2.5, preferably 1: 0.3 to 1: 1.5 in the mixture of the intumescent material available.

As component 4, which may be present in the intumescent materials Cyanuric acid derivatives can be used. Including will be in this Registration understood: Cyanuric acid, cyanamide, dicyanamide, dicyandiamide, Guanidine and its salts, urea, hydrazodicarbonamide, biguanide, biuret, allophanate, Urazole, urazole cyanurate, melamine cyanurate, melamine phosphate, cyanuric acid salts and cyanuric acid esters and amides and especially melamine.

The melamine base is preferably 2,4,6-triamino-s-triazine Understood.

The term cyanuric acid derivatives also includes aldehyde condensation products, preferably formaldehyde condensation products of the aforementioned compounds, which, in the case of the methylol compounds, is also etherified with lower alcohols (C1-C4) could be.

With respect to the 1,2-polyepoxide, the cyanuric acid derivative, e.g. the melamine, in amounts by weight of 1: 0.01 to 1: 2.0, preferably 1: 0.2 to 1: 1.2 must be present in the intumescence mass.

As additives in the intumescent compositions according to the invention also fillers of spherical or almost spherical shape, in particular fillers Hollow pearls may be present.

Although inorganic spherical fillers because of their lack If flammability is preferred, spherical or hollow spherical fillers are also used made of organic material, e.g. made of crosslinked or uncrosslinked polystyrene or polyethylene, phenolic resin or polyvinyl chloride. The material that makes the spherical Particles should be insoluble in water.

Quartz or silica balls, glass balls, fly ash balls and especially spheres made of aluminosilicates deserve special mention. Spheres and hollow spheres of this type are easily accessible. The particle size can be up to 800 microns and more be; particle sizes between 5 and 500 microns are preferably used.

The spherical filler particles can be used in conjunction with non-spherical Fillers or in connection with organic or inorganic fibers Find.

However, they are preferably used as the sole filler.

The spherical or nearly spherical fillers can be used in quantities from 1-80, preferably 20-70,% by weight, based on the molding composition according to the invention, be used.

Although the use of other fillers such as glass, carbon or mineral fibers, chalk, rock flour, talc, perlite, vermiculite, asbestos, kaolin, Silicic acid, clay, carbon, magnesium oxide, aluminum oxides, iron oxides for reduction of foaming leads, their use should be taken into account, especially where less foaming can be accepted.

The intumescent materials according to the invention are produced by Mixing the components 1, -2 and 3 and optionally 4 and additives in common mixing unit gate at room temperatures. The mixes can for example as putty, plaster or mortar or after shaping for production are used by molded parts.

Depending on the type of 1,2-polyepoxide and the amount of ethylenediamine phosphate and optionally cyanuric acid derivative and additive can be storage-stable mixtures can be obtained. The intumescent mixture can be used to produce molded parts Shaping hardened at room temperatures or elevated temperatures up to 1500C will. The intumescent effect on these molded parts can be increased by heating Show temperatures of approx. 2000C and higher.

The subject matter of the invention is explained below by way of example. The parts and percentages given relate to weight, unless otherwise noted.

Characterization of the starting materials used in the examples: Component 1: a. 1,2-polyepoxide A: diglycidyl hexahydrophthalate, viscosity at 200C 600 mPas, epoxy equivalent 176 b. 1,2-polyepoxide B: mixture of 70% bisphenol A-diglycidyl ether epoxy equivalent 190 30% bis (N-epoxypropyl) aniline epoxy equivalent 120 The mixture has a viscosity of 1950 mPas (at 200C) and an epoxy equivalent of 162 component 2: pentaethylene hexamine, NH equivalent : 35 Component 3: Phosphate P: Dried and ground neutralization product sieved from ethylenediamine and o-phosphoric acid, proportions over 0.2 mm.

Component 4: The malamine used is a dried, powdery commercial product.

Example 1 In 100 parts of 1,2-polyepoxide A, 20 parts of pentaethylene hexamine, 100 parts of a mixture of equal parts melamine and phosphate P mixed in. You get a paste that is pressed into a plate shape (plate dimensions: 20x10x1 cm).

The plate is then allowed to harden at 1250C for 5 hours. You get one white, mechanically very stable plate, which can be easily processed by cutting. It is used to manufacture strips with an intumescent effect.

Example 2 In 125 parts of 1,2-polyepoxide B, 25 parts of pentaethylene hexamine, 170 Tle Phosphate P mixed in. A flowable paste is obtained. This is in a tube made of polyethylene cast in (0 6 cm, wall thickness 1.5 cm, Height 12 cm) and hardened at room temperature for 2 days. An opaque piece of pipe is obtained with considerable mechanical strength: 2 ball indentation hardness (DIN 53 456) 180 N / mm2, impact strength (DIN 53 453) 8 kJ / m2, compressive strength (DIN 53 455) 120 MPa.

Such pipe sections are used as cable entry elements with an intumescent effect Suitable for wall breakthroughs, in the event of fire they lead to the closure of the cable duct.

Example 3 In 125 parts of 1,2-polyepoxide B, 25 parts of pentaethylene hexamine, 125 parts of a mixture of 70% phosphate P and 30% melamine incorporated. The putty-like material obtained is placed on a heatable platen press between two pieces of glass fabric cured at 500C for 10 minutes, so that a 1.5 cm thick sandwich panel arises. Such panels serve as flame-retardant protective cladding for those at risk Areas in plant engineering.

Example 4 The mass obtained according to Example 3 is treated with 50 parts of triglycidyl isocyanurate and 5 parts iron oxide red pigment mixed. The flowable mass thus obtained is into a mold made of polypropylene, heated to 800C, for round plates (5 cm, thickness 0.5 cm) and hardened in it. Stable plate elements are obtained to protect junction boxes.

Example 5 In 100 parts of 1,2-polyepoxide B, 25 parts of pentaethylene hexamine, 40 parts of phosphate P and 40 parts of melamine, and 20 parts of dicyandiamide incorporated. then 40 parts of hollow silicate beads (0 less than 0.3 mm) are added and the resulting material is processed Paste according to Example 2 for a pipe socket.

This is cut parallel to the axis, so that two pipe half-shells which are also created as construction elements with an intumescent effect in cable and pipe penetrations through walls are suitable.

To assess the intumescent effect, according to the example 1 - 5 available intumescent materials cuboids with 1 cm edge length produced.

These cuboids are stored at 50 "C and 100% relative humidity. They show a weight gain of less than 3% after 3 months of storage and have become not noticeably changed.

After drying, these cubes are preheated to 3000C in a Brought a convection cabinet. After 60 minutes, the volume expansion is estimated and the Determined weight loss.

Example Expansion Weight Loss No. Volume% Weight% 1 approx. 300 approx. 28 2 approx. 500 approx. 30 3 approx. 550 approx. 24 4 approx. 400 approx. 31 5 approx. 250 approx. 18 The findings confirm the good intumescence behavior of the intumescent compositions according to the invention.

Place the test specimen on a wire mesh and apply a flame to it If the flame of a natural gas Bunsen burner is lit from above for 3 minutes, then a strong expansion (intumescence) achieved in the flame area in all cases, at short-term and after various times repeated removal of the flame no afterburning observed that lasts longer than approx. 3 seconds. This behavior will also observed when the test specimen was previously tempered for 1 hour at 2000C, which indicates the good properties of the materials in the event of a smoldering fire.

Claims (4)

Claims Solvent-free intumescent compounds for the production of molded parts from mixtures of 1. at least one 1,2-polyepoxide, 2. at least one aliphatic or cycloaliphatic polyamine, 3. ethylenediamine phosphate and optionally 4. at least one cyanuric acid derivative. 2. Solvent-free intumescent compositions according to claim 1, characterized characterized in that 10 to 100% by weight of component 1 consists of at least one 1,2-polyepoxide with at least one tertiary nitrogen atom per molecule and 0 to 90% by weight of the Component 1 consists of at least one nitrogen-free 1,2-polyepoxide. 3. Solvent-free intumescent compositions according to claim 1, characterized q indicates that the cyanuric acid derivative is melamine and / or dicyandiamide. 4. Moldings made from the - Mixtures according to the claims 1 to 3 by curing at room temperature and / or elevated temperatures up to 1500C.