DE3025217A1 - Flame resistant polyester-melamine sealing cpd. - does not form halogen or phosphorous pyrolysis prods., useful for caulking and shaping into foamed sections - Google Patents

Abstract

Flame-resistant sealing cpd. consists of a combination of melamine and the polyesters of aliphatic carboxylic acids contg. up to 8C atoms, having at least two polyalcohols of two of following gps. of polyols, and with one polyol from the first gp.: (I) Polyols with more than 3 OH gps. and mol.wts. under 200; (II) triols with mol. wts. under 150; (III) Diols with mol.wts. under 80. Pref. the sealing cpd. employs polyesters of adipic acid and pentaerythritol and/or glycerine and/or ethylene glycol. Polyisocyanates may partake in the reaction. More specifically, the sealing cpd. may take the form of a foamed material and shaped objects can be fabricated from it. Flame-resistance cpd. is not combustible and cannot give rise to halogen or phosphorous pyrolysis prods. It offers considerable resistance to flame and can be used as a sealing or caulking cpd. in sanitary installations, air-conditioning plant, joints, window and door construction, etc. It can be continuously or intermittently masticated by machine and applied by hand, by spatula or by means of a putty gun. Pre- fabricated sections can be made from it without difficulty.

Description

Sealants

The present invention relates to flame-retardant sealing compounds, which do not contain halogen, phosphorus, sulfur or silicon.

Fire protection is becoming a sign of increasing safety awareness more and more meaningful. So is the provision of flame retardant Sealing compounds a technical task of increasing problem, in particular in cases where permanently plastic, hardenable or elastic sealing compounds are required, i.e. sealing compounds based on organic binders.

So far one has helped to get through the latter sealants Additions of halogen-containing, sulfur, phosphorus or silicon-containing compounds to be made flame-retardant. Such additives can - if they are not Silicates act - among other things lead to corrosive damage under pyrolysis conditions. Therefore, there is a technical need for flame-retardant plastic or elastic sealants that do not contain these additives.

It has now surprisingly been found that it is actually possible Permanently plastic and, like window putty, workable well supple, if necessary to produce curable sealants that none of the identified as problematic Contains elements (unless as a trace or impurity) and yet in spite of it their organic matter content can be described as flame retardant can.

It has now been found that this effect occurs surprisingly in combinations of melamine and esters of aliphatic polycarboxylic acids containing up to eight carbon atoms with at least two polyalcohols from two different ones of the following three groups of polyols, one polyol from the first group should come from: Group I: Polyols with more than 3 OH functions and molecular weights below 200 Group II: triols with molecular weights below 150 Group III: diols with molecular weights under 80.

The polyesters constructed in this way should be measured at 750C Have viscosity over 1000es.

Preferably those polyesters are used which have acid numbers below 10 to prevent corrosion.

You can use the basic combinations of the special polyesters and melamine of course pigments, Dyes, water, insecticides or bactericides, fungicides or other active ingredients are added, or else Blowing agents such as urea, dicyandiamide, paraformaldehyde or crosslinkers such as methylol compounds of urea, phenol, or melamine or polyisocyanates, optionally in combination with catalysts or their masked forms as hardeners, but especially fillers such as bauxite, aluminum oxide hydrates, dolomite, chalk, kaolin, asbestos, others Mineral fibers, silica, silicates, glass, solid or hollow glass or silicate beads, Graphite, soot, wood flour, starch, cellulose, perlite, vermiculite, solid or foamed Polymers.

Accordingly, the present invention relates to flame retardant optionally containing fillers and optionally curable with isocyanates or foamable sealants that are free from phosphorus and halogen-containing components are characterized by a combination of melamine and esters of aliphatic Polycarboxylic acids containing up to eight carbon atoms with at least two polyalcohols from two different of the three following groups of polyols, one polyol should come from the first group: Group I: Polyols with more than three QH groups and molecular weights below 200 Group II: triols with molecular weights below 150 Group III: Diols with molecular weights below 80.

If appropriate, aluminum oxide hydrates and, if appropriate, are preferred Sealing compounds containing hollow beads as fillers, characterized by a Combination of melamine and polyesters of adipic acid with pentaeythritol and / or Glycerine and / or ethylene glycol, which have viscosities over 1000cP at 750C.

The fillers used alone or in combination are, in particular, aluminum oxide hydrates, Chalk, kaolin, glass and solid or hollow beads made of silicate material in Consideration, e.g. so-called microballoons, aluminum oxide hydrates are due to their dehydration ability preferred next to hollow beads.

As the aliphatic polycarboxylic acids, there are preferably those with two up to six carbon atoms understood, because of the good accessibility adipic acid is preferred, but there are also to be considered, for example: citric acid, oxalic acid, maleic and fumaric acid, succinic acid.

Among the group I polyols, pentaerythritol is preferred, they are but e.g. also to consider mannitol, sorbitol, xylitol, formitol, i.e. sugar polyols.

Among the group II polyols, glycerol is preferred However, trimethylolpropane or triethanolamine, for example, are also to be taken.

From group III, preference should be given to ethylene glycol.

The polyesters should have viscosities over 1000cP at 750C, to have sufficient binding properties; viscosities of 1200 are preferred up to 5000cP at 750C. The acid numbers should be below 10, preferably between 0 and 5.

The use of other polyesters with a different composition is fundamental possible, but their proportion should not exceed 20% by weight of the total amount of polyester.

The main body 2,4,6-triamino-s-triazine is preferably used as the melamine understood, but there are also e.g.

this by thermal treatment or reaction with formaldehyde available condensation products into consideration.

Based on the polyester used, the combination should be 30 to 400 Contain wt .-% melamine, preferably 40 to 300 wt .-%. The additional amount of, if applicable The fillers to be used depend on the desired consistency of the Sealing compound, which ranges from viscous to putty-like to thermoplastic, i.e. Difficult to deform at room temperature, can be enough.

The amount of melamine can also be reduced to values below 30% by weight, if in the sealant at least 100 wt .-% aluminum oxide hydrate, based on Polyester content.

Leave by adding polyisocyanates and, if necessary, water The masses to tough to elastic in the presence of moisture if necessary Transfer porous, no longer flowing materials or foams.

In addition to aliphatic or cycloaliphatic polyisocyanates or aromatic single-core polyisocyanates and their derivatives, especially aromatic ones Multinuclear polyisocyanates can be considered, such as those technically based on (methyl) Aniline-formaldehyde condensates are accessible.

Such polyisocyanates are used in amounts from 0 to 150, preferably 20 - 80% by weight, based on polyester, used, depending on the desired degree of hardening.

Those reacted with isocyanates to be used as sealing materials Materials can have the character of hard or soft, solid or foamed Have crowds. They are expediently by mixing the components or their premixes are made directly on site and added to the before reacting filling cavities or introduced into molds. Also the manufacture of semi-finished products, by subsequent deformation or cutting to size of plates, foils, flexible Sheets, half-shells, granulates or profiles can be processed is possible to pull.

The polyesters are conventionally known to those skilled in the art Process made.

A common method is to combine the reaction components, i. Carboxylic acids and alcohols, in a pre-condensation phase over approx. 20 h at 2000C to heat, then a condensation phase of about the same length in a vacuum at approx. 80 Connect millibars until the desired acid number is reached.

The sealing compounds according to the invention are advantageously by simple kneading of the components in kneading machines continuously or discontinuously manufactured. You can fill in by hand, by troweling, painting or can also be used with a putty gun. From such types that at room temperature difficult to deform or no longer deformable due to crosslinking reactions carried out are, semi-finished products and preforms can be produced, which are then at the desired Place of use. Thermoplastic processing of the sealing compounds is also possible is to be considered.

The sealing compounds are preferably used where required consists of non-flammable and long-lasting resistance to the fire, normally to use plastic sealing materials and the occurrence of Pyrolysis products, which could be halogen or phosphorus compounds, are avoided shall be. The sanitary and installation areas, air conditioning systems, Grouting, window construction, door construction, sealing off electrical equipment, computer construction use.

The following examples are intended to illustrate the invention by way of example, the parts given are parts by weight, unless otherwise noted.

The following polyesters were used by way of example: Polyester A: esterification product from 6 mol adipic acid OHN: 276 1 mol pentaerythritol AN: 4.7 1 mol glycerine visc. 750C: 1078 @@ m Pas 5 mol ethylene glycol polyester B: esterification product from 6 mol Adipic acid OHN: 207 1 mol pentaerythritol AN: 4.7 0.5 mol glycerine mPas visc. 750C: 1950 P 5.5 moles of ethylene glycol polyester C: Esterification product from 6 moles of adipic acid OHN: 192 1 mol pentaerythritol AN: 2.2 6 mol ethylene glycol visc. 750C: 1997 #P mPas Polyester D: esterification product from 1 mol of phthalic acid OHN: 292 1.7 mol of ethylene glycol SZ: 0.6 visc. 250C: 3500 eP mPa s Polyester E: Esterification product from 6 mol of adipic acid ÖHZ: 200 1 mol pentaerythritol SZ: 2.5 0.25 mol glycerine visc. 750X: 2880 ePmPos 5.25 mol Ethylene glycol Example 1: 10 parts of polyester A are mixed with 35 parts. Melamine kneaded into a mass with a putty-like consistency.

A 2 gram sample is made with a Bunsen burner flame out 20 seconds applied, then the flame removed, the afterburn assessed and after 5 sec. The next exposure to the flame is carried out. This test cycle is 5 times repeated. No afterburning is found in any case. It is also stated that that no shrinkage of the test body has occurred. It is also noted that no afterglow of the applied putty sample takes place.

Another cement sample is tempered for 1 H at 2600C.

The material has only darkened and hardened. In the flame test described above, the same results are then again applied Assessments achieved. There was no shrinkage.

Example 2: A mixture of 17.5 tonnes. Chalk powder and 17.5 tsp.

Melamine is ground in the ball mill and then with 10 parts polyester kneaded to a putty-like consistency.

In the tests described under Example 1, the same thing occurs in each case received positive result.

Example 3: A mixture of 17.5 parts of melamine and 17.5 parts of aluminum oxide hydrate is ground in a ball mill and kneaded with 11 parts of polyester B to form a putty.

In the tests carried out according to Example 1, the tests of the same type are again used positive results found.

Example 4: A mixture of 17.4 parts of melamine and 17.5 parts of Sili-µm cathode beads (particle size 5 - 300 G micron, spec.

Weight 0.4) is kneaded with 10 parts polyester B to form a putty.

In addition, a similar putty is made by in place So-called glass microballoons are used for the silicate hollow beads.

Both types of putty are subjected to the tests according to Example 1. It will the same positive results are registered, only in the last flame exposure cycle a slight afterburn of less than 3 seconds was observed.

Example 5: 10 parts of melamine and 25 parts of aluminum oxide hydrate are used ground in a ball mill and kneaded with 10 parts polyester C to form a putty.

This putty passes the tests according to Example 1 with an equally positive result Result.

Example 6: 17.5 parts of corn starch powder and 17.5 parts of melamine kneaded with 10 parts polyester B to form a putty. This runs through the tests Example 1. The equally good results are registered, although the proportion of organic matter is 100%.

Example 7: This is a comparative example in which another to the skilled person possibly as also for the production of difficult Flammable putty suitable appearing polyester is used, namely a ethylene glycol aromatic polyester.

17.5 parts of melamine and 17.5 parts of aluminum oxide hydrate are used in the Ground ball mill and kneaded with 10 parts polyester D to form a putty. This is subjected to the tests according to Example 1. It turns out that in the flame test after the second flame application cycle there is a noticeable afterburn with flame standing times over 5 sec.

is observed. In addition, the putty tends to run, which is the case is not observed in the previous examples. This polyester can be used to manufacture putty are not recommended in the sense of the invention.

The following examples are intended to provide a means of networking the Explain combination according to the invention or their reaction with isocyanates: Example 8: 100 parts of polyester B are mixed well with 40 parts of melamine. To 40 parts of this Premix 0.2 Tle.

Water and 10 parts of one by phosgenation of aniline-formaldehyde condensates commercially available multicore polyisocyanate (Desmodur 44 V 10 from BAYER AG).

After a few minutes, solidification begins with slight foaming. After standing overnight, a tough, elastic foam with a volume weight is obtained around 500 kg / m3, which is easily deformable and can be cut into flexible sheets can.

Example 9: In 100 parts of polyester C there are 35 parts of melamine and 0.7 Teaspoon of water stirred in.

In 40 parts of this premix A, 20 parts are made by stirring of the polyisocyanate used in Example 8 with the same amount by weight of melamine prepared premix B stirred into it. After a few minutes, it starts to foam the hardening. A viscoplastic foam with the density is obtained of approx. 500 kg / m3.

Example 10: The procedure is as in Example 9, except that the Premix A replaced the melamine with aluminum oxide hydrate. A tough, elastic one is obtained Foam with a density of approx. 500 kg / m3.

Example 11: The procedure is as in Example 9. However, you bet twice the amount by weight of premix B. A hard foam is created with a density of approx. 430 kg / m3.

The foams obtained in Examples 8-11 are the in Example 1 subjected to the tests described.

It turns out that the positive results are also obtained here: There is no shrinkage or flow of the material under the test conditions. After the second flame treatment cycle, however, the sample from Example 8 shows afterburning, which can exceed 5 seconds, but goes out by itself and does not shrink the trial leads. The foams obtained according to the other Examples 9-11 show an afterburning after the 3rd flame treatment cycle, but not for more than 5 sec.

lasts. There is no shrinkage of the sample.

This behavior enables the use of such types of sealing material for sealing breakthroughs, as the sealing material burns through suitable layer thicknesses are not to be feared.

Example 12: In a 1 cm thick steel plate a slot of 10 milled cm length and 1 cm width. This slot is now made with the putty according to the example 3 closed flush with the plate surface. Then the plate becomes horizontal and flamed the putty joint from below with a Bunsen burner. Even after 1-2 h exposure to a flame with the unlit flame (temperature around 9000C) became the The slit is still sealed by the putty. The putty was slightly swollen, hadn't burned and hadn't drained or drained at any point.

Example 13: The joint described in Example 12 is this time with the mixture of premixes A and B prepared according to Example 9 is poured out. Any excess material is cut off. Then the flame is applied: Even after one hour of exposure to fire, the joint is still tightly sealed, fire gases do not penetrate and nothing has drained, shrunk or expired.

Example 14: The sample joint described in Example 12 is made with a Poured the reaction mixture prepared according to Example 9, but without the addition of water. After approx. 15 minutes the mass has hardened essentially without bubbles.

In the case of flame exposure according to Example 12, similar service lives are i.e. 1 hour of sealing the joint achieved without difficulty.

Example 15: A premix A is prepared according to Example 9, which, however, instead of 0.7 now contains 2.8 parts of water. This premix A is now mixed with the premix B according to Example 9 in the mixing ratio used there of premixes A and B. This mixture is pressed through a 0.8 mm in diameter having circular nozzle opening on a smooth surface. Here it foams Mixture and hardens to form a semicircular profile strand.

Another portion of the mixture is left in a cylindrical mold foam and harden.

In both cases, molded parts are obtained with which one, since they Made of tough, elastic foamed material with a density of approx. 200 kg / m3 exist and are therefore compressible, very convenient slots, joints and openings can seal tightly and protect against flame penetration.

This is how the joint described in Example 13 is made with the profile strand obtained sealed sealed.

In the case of flame exposure with the burner, as described in Example 13 the joint is kept sealed for 30 minutes to prevent the passage of flames.

Example 16: The procedure is analogous to Example 9, with the following Changes are made: The polyester E is used instead of Melamine is a mixture of 90 parts of aluminum oxide hydrate and 10 parts of melamine a tough foam with a density of approx. 600 kg / m3.

A strip of this foam is sealed in the pattern joint pressed in according to example 12 and flame-treated analogously. After 1 hour of exposure to flame is the joint still sealed. The putty did not run off at any point or drained. No afterburn was observed when the flame was removed became.

Claims (5)

Claims: 1. Permanently plastic, flame-retardant if necessary Sealing compounds containing fillers that are free from halogen and phosphorus Components characterized by a combination of melamine and polyesters of aliphatic polycarboxylic acids containing up to eight carbon atoms, with at least two polyalcohols from two different of the following three groups of polyols, one polyol coming from the first group: Group I: Polyols with more than three OH groups and molecular weights below 200; Group II: triols with molecular weights below 150; Group III: diols with molecular weights below 80. 2. Sealing compounds according to claim 1 using polyesters from adipic acid and pentaerythritol and / or glycerine and / or ethylene glycol. 3. Sealing compounds according to Claim 1 and 2, containing polyisocyanates are implemented. 4. Sealing compounds according to claim 1 to 3, present in foamed Shape. 5. Moldings made from the sealing compounds according to claim 1 to 4.