DE2112838A1 - Flame-proofing of materials - using inorganic based adhesive coatings - Google Patents

Abstract

Flame proofing compsns. for e.g. treatment of tars, asphalts, resins, plastics, cellulose and foams are made by adding oxide, hydroxide, carbonate or acetate of Ca, Sr or Ba to aluminium sulphate soln., thus pptg. complex insol. Al/alkaline earth sulphates of pH 4-6.5 (4.3-5.7). Aluminium sulphate can be wholly or partly replaced by FeSO4, MnSO4 or TiSO4 for specific applications. A solid compsn. for inclusion in resins etc. at the manufacturing stage is prepd. by adding a source of phosphate or borate ions before pptn., pref. phosphoric or boric acid.

Description

Flame retardant, inorganic adhesives.

In the patent applications P 10 94 334.3 from 20.6. 1967 and in P 19 09 644.7 from 02.26. In 1969 there were already methods of flame retardancy using water-containing crystals Aluminum sulphates have been described and their related production of insulating refractories, particularly with regard to flame retardancy are the aforementioned processes with the disadvantage of water solubility of the normal Aluminum sulfate afflicted. According to the present invention, these disadvantages become fixed by the water-soluble sulfates in practically insoluble or very little soluble aluminum sulfates are transformed without losing their chemically bound Water on which the flame retardancy is based is reduced.

As a rule, these are the new insoluble aluminum sulfates to those that contain no more than two ## half moles of SO2 for one mole of Al2O3 and Often referred to as "basic sulfates", although their pH levels are in the area of 3. @ up to 5.5 tend to be, preferably at A - 4.7, as far as the connections according to the present invention relates to their pH measurement in adaptation to practice the adhesive application is measured in such a way that it first dries out and then only for measurement, rewetting.

Suitable for the said conversion into water-insoluble aluminum sulphates calcium compounds with particularly good alkaline reaction, such as calcium oxide, calcium hydroxide, Calcium sulfide, calcium carbonate and also calcium compounds of volatile organic acids mainly acetic acid, whereby partial Neutralization or deacidification evidently not only mixtures with hydrated ones Calcium sulphates form in the precipitation, but also complex compounds when hydrated Sulfates.

This is particularly evident when replacing the calcium compounds mentioned by the corresponding barium compounds, which because of their increased water insolubility are of significant practical interest even with only partial application, but also with other alkaline earth compounds of the type mentioned for calcium.

Modifications of the procedure do not relate only to said one Replacement of calcium compounds but also replacement of aluminum sulfate by sulfates of other, preferably trivalent metals, such as iron, manganese and also Titanium, the value of which can be found in the @ eye of the process conversion @@.

Influences of phosphoric acid and / or boric acid play a special role or of compounds after the addition of phosphoric acid ions and / or boric acid ions can form, which are to be excluded from the partial neutralization in these - The adhesives produced tend to have a tendency after the materials have cooled down in to pass the crystalline state, usually in a foamed form, the The water content of the crystalline compounds dissolves corresponds to those who have adhesive consistency and moves in the area of before All. In this way, the crushed crystalline products can be used in more beneficial They serve as fillers for the flame retardancy of polyesters, including liquid ones Monomers can be added without affecting the filler's mechanical strength values adversely affects the polymers.

The @einfluence occurs more in a positive, useful sense.

Extrudable plastics can also use said fillers Can be made flame retardant by adding the filler to the granules prior to extrusion clogs.

The nature of the new process for producing said flame retardants All materials containing aluminum sulphates of an insoluble nature and the nature of the Modifications allow numerous useful combinations of all kinds of them The details of the application of the said new products are given by the the following meiopiele illustrated.

Embodiments.

1. In a mixer equipped with a steam jacket, 1200kg of aluminum sulphate are converted melted down together with 300-400 kg of water and then under constant Stirring and heating, starting at 60 ° and gradually increasing at almost the boiling point, 250 - 300 kg hydrated lime are gradually becoming necessary for partial neutralization (deacidification) entered, as the foam head of the liquid allowed by the The exact setting of the partial Neutralization takes place on the basis of the pH value, which should be 4.5-4.7 and so on what is measured is that the measurement sample is dried out and re-moistened for the measurement so that which occurs when the adhesive is used in the drying phase To take changes into account.

Already shortly before reaching PH4.5, the addition of the @@ lkhydrate least. interrupted for 20-30 minutes with constant further heating and mixing then the final setting is made to HH 4.5 - 4.7 in the same as described, namely with drying of the sample and rewetting.

2. In the mode of operation according to embodiment 1, instead of.

of the said hydrated lime 50-60kg barium sulfide used, only for that first phase of PE adjustment to 4.5-4.7. for the second phase of adjustment instead of barium sulfide, barium acetate is used for a pH of 5-6 the working procedure is based on example 1, including the method of pH measurement Drying and rewetting of the samples.

3. The working methods according to example 1 and 2 are combined in this way combined that 250kg hydrated lime is used for the first phase of pH adjustment and barium acetate for the final setting, so that pH 5-6 is reached, otherwise the procedure is based on Example 1, including the Methede pH measurement, namely prior drying of the sample with subsequent rewetting.

Example 4. For the flame-retardant coating of spruce wood 1.7kg of the adhesive @ according to example @ applied in warm condition per square meter the adhesive is still warm in some cases as a cladding of the adhesive with this An absorbent paper wallpaper is also glued onto the @@ layer. Main use in construction.

Example @. Flameproof packing paper is made by lamination with Kraft paper or wrapping paper of close to 150g per square meter with suctionrah @ -gem little linen Paper of 30-40g / m² produced using glue according to the example @ or example @ in quantities of 0.4 - 0.6 kg / m² for @ ashing. Main use for packaging purposes, including the manufacture of corrugated cardboard.

Example 6.

Flame retardation of polyurethane foam panels.-These panels are made Laminated with aluminum foil using 0.8-1.5kg adhesive according to the example 1 or 3 for the lamination 7. In the flame retardancy according to example parts of polyurethane foam sheets Polystyrene foam sheets are used and instead of aluminum foil, absorbent, poorly gelled paper of 50-70 g / m². Adhesive for the lamination according to Example 6. Laminating the foams on both sides with paper wallpaper is used to create panels for partition walls and others Purposes in the construction sector. Mineral fiber boards can also be used instead of foams.

Example 8. In the manufacture of flame-retardant chipboard panels For 80 kg of adhesive according to Example 3, 20 kg of olzsüähne consumed. The chips can can be replaced by @ sawdust from softwood or @artwood.

9, For flame-retardant fittings of all kinds instead of plates the same proportions are observed as in Example 8 10.For The manufacture of insulation panels from mineral fibers are used to bond the Fassern adhesives according to Example 3 diluted with water to a sprayable consistency and used in the same way as that. in a manner known per se with formaldehyde-phenolic resins happens, only in the drying phase the temperatures are kept lower, preferably below 110 ° C. In contrast to the known way of working with phenol-formaldehyde resin the waste vapors from the drying phase to avoid air pollution Require gas cleaning for the use of adhesives according to the example 1 uno 3 not required, 11. flame retardancy of polyesters, mainly glass fiber reinforced Polyester plates in the production according to Example 1 are before the entry of said Kaklhydrates per 25kg phosphoric acid of 85% and of crystallized boric acid added If the foamed charge cools, it will spontaneously transform into the crystalline Leave the modification, which is then ground 100kg polyester for flame retardancy 150kg of said ground material as filler used before polymerization.

12. Manufacture of foamed refractory panels.-Mixing the Starting materials is composed of @ 00kg aluminum sulfate 9 kg sulfuric acid, 25 kg mineral fiber, 600 kg plastic clay, 600 kg zirconium silicate sand and 40 kg sodium resinate together @@@ 300 - 400 kg of water for a consistency that is easy to process in the kneader.

After homogenization in the kneader, 10-15 kg of ammonium bicarbonate are deposited there added with constant operation of the kneader and the foamed mixture in the Forms introduced for the plates.

After complete cooling and pre-drying at 50-60 ° it is complete Thorough drying and subsequent calcination at 80-1000 ° in one for the production of refractory material known per se.

For the above mixture you can also use zirconium silicate Chromite can also be used or other non-plastic ceramic raw materials @. Furthermore, 50-70kg starch, molasses or coal dust can be used as a reducing agent can be added to accelerate the thermal diasociation of the aluminum sulfate and let it run at a lower temperature, since this way the Calcination from the sulphates form sulphites, which decompose by splitting off SO2 will.

In general terms, the above examples are primarily intended to cover the area of application of the invention in the main outlines. But you can because the wide range of possible variations in production and the special diverse possible uses of the invention are far from complete be. above all, aluminum sulphates containing iron sulphate cannot be found in many laliols obtained only from clay but also from bauxites by adding sulfuric acid The sulfuric acid is often advantageously replaced by setroleum sulfuric acid are to be replaced whose content of organizing, reducing substance in particular in the context of example 12 may be useful.

To replace aluminum sulfate, iron sulfate-containing compounds can also be used in some cases Waste solutions are used, not only in fort of heating waste liquors but for example also those from the Titanweiss fabrication or solutions in general that result from digestion from low-percentage @lmenit can be obtained by means of sulfuric acid Halle it is advantageous to check the OK content of the alkalis before the said partial neutralization by reduction with iron filings into the trivalent state (titanosulphate) to ver @@@@@@ n with subsequent ventilation for re-oxidation of the partial neutralization Titano compounds in titani compounds and oxidation of ferrous compounds in the Fe3O4 level. After applying the adhesive, this Fe3O4 level goes within the porosity of the bonded material in the Fe2O3 stage over under increase the volume and therefore with an increase in the adhesive strength.

One of the numerous other illustrations of the multiple application possibilities invention relates to the paper industry, because the said adhesive can except Gluing iur finished paper can also be used in the manufacture of the paper itself However, the replacement of conventional gluing with aluminum resinate will be used not be complete, only partial.

To the special products of the paper industry, which deviate from the known which can be advantageously produced according to the invention also include flame-resistant, stiff paper laminates, of which sufficient water resistance is also required for the packaging industry, including bags, said laminations or lamination can be carried out analogously to Example 5, but using 10-15 pieces of wood sawdust for 100 pieces of adhesive according to example 2 or 3 are to be used for the above purpose.

Another useful combination concerns flame retardant coverings Correspondingly long hollow boards with aluminum foil can often be used for this purpose 0.5mm thick laminated or laminated are made using adhesives according to example 2 or 3. The aluminum foil used is Serten which previously in per se known to previously with paper or other per se Flammable foils are laminated. The width of the aluminum foil will be like this chosen that it conveniently rides the board width significantly over @@, so that the butt joints between two roofing boards are sealed by overlapping As an adhesive for the seal, at least some of those according to Example 2 or 3 are used, but preferably, per se known, flammable, elastic, organic Adhesives including tar, acid or asphalt, which are made flame resistant in this way can, as described in Example 11 for polyester, namely with the fillers to be used crystalline modifications of the adhesives according to the invention @ ei @ e flame-retardant tar, acid tar or asphalt can also be used in general especially in the roofing sector and other branches of the construction sector.

Claims (8)

Patent claims: 1. Flame retardant materials, which are hydrated aluminum sulfates according to patent application P 16 94 354.3 of June 20, 1967 and P 19 09 644.7 of February 26, 1969 contain, characterized in that they are practically insoluble or only There is very little soluble aluminum sulfate, which is usually no more than two and a half Moles SO3 for one mole Al2O3 contain, these sulfates in the form of complex compounds and / or mixtures together with insoluble alkaline earth metal sulfates of soluble aluminum sulfates be precipitated by means of oxides, hydroxides, carbonates, sulfides or Acetic acid compounds of calcium, strontium or barium, so that in the at The material PH values of 4-6.5 achieved during the filling are maintained, preferably 4.5-5.7, measured after the measurement samples have dried and rewetted. 2. Flame-proofing materials according to claim 1, characterized in that the said calcium, strontium or barium compounds of acetic acid by corresponding Compounds of other volatile organic acids are replaced by the Said drying can also be split off and volatilized. 3. Flame-proofing materials according to claim 1 and 2, characterized marked that the aluminum sulfates at least in part by corresponding iron sulfates, manganese sulfates or titanium sulfates can be replaced. 4. Flame-proofing materials according to claims 1-3 by the addition of substances to be made by the said precipitation, the phosphate ions or generate borate ions, preferably by adding phosphoric acid or boric acid. 5. Flame-proofing materials according to claims 1-4, characterized by any combination of said generation methods. 6. Application of the flame-retardant materials according to claims 1-3 and 5, characterized in that they are used as adhesives, preferably there @@ at least one flammable material is involved in the bond and / or for flame-retardant coatings and / or flame-retardant impregnations, where the said flammable substances of natural or synthetic origin around wood, wood components, organic fibers including cellulose and Plastics of all kinds, including foams, are non-flammable Material mainly around mineral barrels. 7. Application of the flame-retardant materials according to claim 4 through this characterized that after cooling to normal temperature and their transition to crystalline structure as flaa £ sst. Making fillers are used in relation to natural flammable substances especially for tar and asphalt 'in relation to polyester manomers of their polymerisation, in Relation to extrudable plastics from extrusion. 8. Application of the materials according to claim 1 for the production of foamed, insulating refractory materials, characterized by the use of plastic aluminum silicates, Chromites, zirconium oxide, zirconium silicate in any combination, through use of ammonium carbonate or bicarbonate instead of the said alkaline earth compounds , preferably with the use of reducing agents such as starch or molasses for the acceleration of the thermal decomposition of sulphates in the generation phase the known calcination phase for the decomposition of aluminum sulfate.