WO1993011196A1

WO1993011196A1 - Composition with integrated intumescent properties

Info

Publication number: WO1993011196A1
Application number: PCT/EP1991/002247
Authority: WO
Inventors: David Charles Aslin
Original assignee: Chemische Fabrik Budenheim Rudolf A. Oetker
Priority date: 1991-11-27
Filing date: 1991-11-27
Publication date: 1993-06-10

Abstract

A composition with integrated intumescent properties is obtained by blending (a) one or several amino-formaldehyde resins and (b) a mixture of monoesters and diesters of orthophosphoric acid with one or several polyols. The average hydroxyl group content of these polyols amounts to at least 40 % by weight, the molar ratio between monoesters and diesters does not exceed 12:1 and the phosphorus content of the mixture amounts to at least 10 % by weight.

Description

COMPOSITION WITH INTEGRATED INTUMESCENT PROPERTIES

The present invention relates to a composition with integrated intumescent properties, in particular a coating based on partial phosphoric acid ester mixtures, the production thereof and the use thereof for forming intumescent films, coatings, etc.

The compositions according to the invention have possible uses which go beyond the current state of the art.

Intumescent coatings are traditionally applied to the surface of components. With such coatings e.g. Partitions and partitions between individual construction sections are also protected against fire. In this application it is the task of the coating to prevent the flame from spreading from one construction phase to the next. Intumescent coatings are also applied to the surface of flammable substrates in order to reduce their flammability, but also to achieve decorative or protective coatings against other influences.

According to the prior art, intumescent coatings consist of an acidic phosphoric acid compound, a polyhydroxy compound and a blowing agent. These components are bound with a conventional polymeric binder. This binder can be, for example, an acrylic styrene or vinyl toluene copolymer, a styrene or vinyl toluene butadiene copolymer or a styrene or vinyl toluene / acrylonitrile copolymer. Alternatively, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, urea or melamine-formaldehyde resins and vinyl chloride-vinylidene chloride copolymers are also used. Also the use of epoxy resins in combination with various amino functional hardeners is known. All of these formulations contain chlorinated paraffins or optionally chlorinated phosphoric acid esters as plasticizers.

Intumescent flame retardants act through the formation of a bloated, insulating layer of flame-retardant material that forms under the influence of heat, which protects the substrate against the entry of oxygen and / or overheating and thereby prevents or delays the inflammation of combustible substrates or the change in the mechanical and static Properties of load-bearing components prevented or at least delayed by exposure to heat.

The properties of the respective formulations depend very much on their composition, which therefore requires exact coordination. For example, a larger bloating (intumescence) to a thicker protective layer, but at the same time this detaches more easily from the substrate due to a reduced mechanical stability and is therefore less effective. Intumescent systems have long been known and described. GB-A-2151237 describes formulations which contain chlorinated polymers, novolak resins and chlorine- or phosphorus-containing plasticizers. GB-A-2 012 296 describes formulations which contain expandable graphite, aluminum hydroxide and binder systems based on halogenated elastomers and alkylphenol-formaldehyde resin. GB-A-1 604 908 mentions products with vermiculite and inorganic fibers as fillers as well as elastomer binders and clay.

Conventional systems consist of a binder of the type described above, a carbon skeleton, a blowing agent and an acid generator as essential components.

Polyhydroxy compounds such as pentaerythritol, dipentaerythritol, tripentaery hri, starch and sugar are used as carbon skeleton formers. Blowing agents are, for example, nitrogenous ones Compounds such as melamine, urea, dicyandiamide and guanidine. Ammonium phosphates, preferably ammonium polyphosphates, are usually used as acid generators. Other additives are, for example, inorganic fibers, which are intended to increase the mechanical strength of the intumescent layer and / or to prevent its dripping, and metal oxides, which act as smoke suppressants. Typical examples of such formulations can be found in US-A-4,442,157 and 3,562,197, GB-A-755,551 and EP-A-138,546.

The literature also shows that the individual components are not limited in their mode of action to a single function. This is e.g. GB-A-2007 689 shows where a reaction product of an amide with an aldehyde compound acts both as a carbon skeleton and as a blowing agent. An epoxy resin described in EP-A-139 401 functions both as a binder and as a blowing agent. US Pat. No. 3,969,291 describes a water-soluble amidopolyphosphate which acts as an acid generator and blowing agent.

The effectiveness of such flame retardant systems over a longer period of time is often limited by the fact that components with low molecular weight contained therein are removed from the system by washing, volatilization or other mechanisms. The effectiveness of conventional flame retardant formulations after prolonged storage or weathering is therefore questionable and must be checked in individual cases by fire tests. To overcome this disadvantage, attempts have been made to use higher molecular weight components, e.g. Starch, proteins, polypentaerythritol compounds and epoxy resins as carbon skeletons and aminoplasts and similar compounds as blowing agents.

According to the state of the art, conventional phosphate-catalyzed, intumescent coatings are composed as follows: (i) As an acid source (catalyst), usually ammonium phosphates, usually ammonium polyphosphates, ammonium orthophosphates and melamine phosphates, are used with a share of approx. 25% by weight of the total formulation.

(ii) An organic compound, usually a polyol, acts as a carbon skeleton, which is decomposed to carbon by the released acid (carbonification). Pentaerythritol, dipentaerythritol, tripentaerythritol, starch or starch derivatives are usually used for this.

(iii) A blowing agent leads to the formation of a foamed (intumescent) layer by the release of an inert gas. Common blowing agents are e.g. Melamine, melamine salts, melamine derivatives and / or dicyandiamide.

The mechanism of action of conventional intumescent systems when exposed to heat can be described in a simplified manner as follows:

1. At a temperature above 70 ° C, the binder system softens to a highly viscous melt.

2. Above about 90 ° C., the blowing agent and plasticizer begin to decompose, releasing non-combustible gases which form an inert gas layer over the coating and prevent the combustible organic components of the coating from igniting.

3. The acid generator releases ammonia above approximately 150 ° C., leaving free acid which lowers the viscosity of the melt.

4. The carbon scaffold melts and reacts with the acid released under 3. with elimination of water and carbonification. 5. The blowing agent decomposes with the development of inert gases and expands the melt into a soft foam.

At temperatures around 210 ° C, reactions 3, 4 and 5 run simultaneously.

6. Due to partial decomposition, the soft foam changes into a relatively rigid layer.

7. The free acid still present reacts with the pigment material (metal oxides) present to form phosphate.

8. The carbon-containing protective layer is partially removed by the flame, which reduces the insulating effect. Phosphorus can also escape from the system if no metal oxides are available for a trapping reaction (7th).

9. Depending on the composition of the residue, phase transitions or melting may occur.

The intumescent coatings acting according to this reaction scheme have a serious disadvantage which clearly limits their area of application. This disadvantage consists in the fact that these systems are multi-component systems, the individual components of which have been described above must first undergo decomposition and conversion reactions in order to form the desired intumescent protective layer. In addition, the transport and diffusion processes that lead to the formation of a homogeneous reactive melt are the rate-determining factor for the overall reaction leading to the formation of the protective layer.

The decomposition reactions of the components are each dependent on the temperature. There is a for each of these reactions Minimum temperature above which decomposition begins. Even if the reactions leading to the formation of the intumescent protective layer have a low temperature barrier, this reaction sequence will not proceed until the decomposition reactions of the components have taken place.

In addition, the most widely used acid source, i.e. Ammonium polyphosphate, although sparingly soluble in water, dissolves very well in saline media. For example, a corresponding formulation can be satisfactorily stable in water, while in aqueous solutions containing salt water or sulfur dioxide the above component is increasingly dissolved out of the formulation.

An advantage of the conventional intumescent systems, however, is that the decomposition reactions taking place are endothermic. As a result, the formation of the protective layer is directly proportional to the amount of energy available. The formation of the foam layer is therefore determined by the fire and is not independent of it.

Attempts have been made to overcome the disadvantages of conventional intumescent systems described above by combining acid formers, carbon skeletons and propellants in one compound. In 1967, Sawco and Ricetiello (Journal of Coating Technology 49 (1977), page 624) succeeded. The compositions proposed by these authors respond to high heat flows, but fail at low heat flows, such as occur in real fire situations. Another disadvantage of these systems is that the course of the reaction is partially exothermic. This adds additional energy to the system and makes the process of intumescence independent of the actual fire situation. The salts described by Sawco and Ricetiello must also be fixed with a binder system. However, there is already a system here in which all essential functions of the conventional, phos- phat-catalyzed system are summarized in a polymer molecule. Since there are no unstable groups in this system and all mechanisms of action are combined in one molecule, transport processes are of no importance. For example, in the reaction of conventional systems, the polyol component is dehydrated by the free phosphoric acid formed as an intermediate. Phosphoric acid esters are formed as an intermediate stage, which decompose again immediately because their decomposition points are lower than the reaction temperature. If the phosphate esters were already present in the starting formulation, the intumescence reaction would begin at the lower decomposition temperature of the phosphate esters and not only at the higher decomposition temperature of the ammonium polyphosphate.

If a conventional intumescent system is examined by means of thermogravimetric methods, it is found that weight losses occur both after the coating has been applied and during the flame treatment, as is shown in Table 1 below using an example.

TABLE 1

Total 100 70 41.5 26.5 From Table 1 it can be seen that at the end of the flaming only 26.5% of the protective coating originally applied contribute to the insulating effect.

It is therefore an object of the present invention to provide a composition with integrated intumescent properties which avoids or at least mitigates the disadvantages of conventional intumescent systems described above.

It has been found according to the invention that certain orthophosphoric acid esters of carbonifying polyols which are crosslinked with certain reactive polymers are polymers with integrated intumescent properties. A process has also been developed with which these orthophosphoric acid esters can be produced without the usual synthetic route via phosphorus trichloride or phosphorus oxychloride having to be labeled as a phosphorus source and in which chemically and technically complex cleaning steps are avoided.

The phosphoric acid esters used according to the invention essentially correspond to those which occur as an intermediate in the course of the reaction to form an intumescent layer and whose decomposition leads to intumescence.

Intumescent coatings on the basis of the composition according to the invention show below those in the table above

1 underlying conditions the in the following table

2 reproduced properties.

Total 100 100 89 77.5

From Table 2 it can be seen that at the end of the flame treatment of a coating obtainable according to the invention, 77.5% of the starting material is still present. The protective effect is about three times as good as that of a conventional system.

One object of the present invention is therefore a composition with integrated intumescent properties, which can be obtained by combining

(a) one or more amino formaldehyde resins and

(b) a mixture of mono- and diesters of orthophosphoric acid, optionally modified with carboxylic anhydride, with one or more polyols, the average hydroxyl group content of these polyols being at least 40

% By weight, the molar ratio of monoester / diester does not exceed 12: 1 and the phosphorus content of the mixture is at least 10% by weight.

The above component (b) and its production from polyphosphoric acid and the corresponding polyols at elevated temperature and reduced pressure is also an object of the invention, as is the use of the above composition for coatings, ins! ^' Especially of objects made of wood, plastics, cellulose cerialien, rubber and metal, as well as for the impregnation of textiles.

In the drawings shows - Figure 1 shows the dependence of the acid value obtained in practice on the degree of condensation of phosphoric acid in the esterification of polyphosphoric acid (2 mol equivalents H.-P0.) With a mole of glycerol and a mole of pentaerythritol (reaction temperature 115 ° C; pressure 160 mm Hg or Vacuum 600 mm Hg); and

2 shows the dependence of the acid value obtained in practice on the pressure in the esterification on which FIG. 1 is based (reaction temperature 115 ° C.).

It is preferred according to the invention if the molar ratio of monoester / diester in component (b) above does not exceed 6: 1 and in particular 3: 1. A particularly preferred molar ratio of monoester / diester is in the range from 2: 1 to 1: 1.

It is further preferred that the component

(a) an optionally modified melamine-formaldehyde resin and / or an optionally modified urea-formaldehyde resin. is. The modification can consist of a conventional modification (e.g. methylation). However, the urea and melamine-formaldehyde resins are preferably modified with aromatic glycidyl ethers and / or cycloaliphatic epoxides. Specific examples of such modifiers are 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and bisphenol A diglycidyl ether. This modification increases the strength of the hardened composition and leads to better adhesion of the intumescent layer in the event of a fire. The above-mentioned modifiers are preferably used in an amount such that they make up 1 to 15% by weight of component (a).

The quantitative ratio of component (a) to component (b) depends essentially on the desired phosphorus content of the dried and cured composition. This phosphorus content is preferably at least 8 and in particular at least 10% by weight, while a phosphorus content of 16% by weight is generally not exceeded mentioned, the minimum phosphorus content in component (b) is 10% by weight, while a preferred maximum is 25% by weight. A particularly preferred range is 15 or 22% by weight phosphorus for component (b).

It is further preferred that about 1 mole of methylol function is available in component (a) per mole of acid function in component (b).

Component (b) above is preferably derived from at least 2 and in particular from 2 to 4 polyols. The average hydroxyl group content of these polyols (calculated as the molecular weight of the hydroxyl groups divided by the total molecular weight of the polyols times 100%) is at least 40% by weight and preferably at least 45, in particular at least 47% by weight. However, it is not necessary that each individual polyol. The polyol mixture has a hydroxyl group content of at least 40% by weight. Rather, one or more polyols with a hydroxyl group content of less than 40% by weight can be used in polyol mixtures, preferably not more than 15% % of all polyol hydroxyl groups present originate from such polyols. Of course, an excessively low hydroxyl group content (<40% by weight) of an existing polyol must be compensated for by the presence of polyols with a correspondingly higher hydroxyl group content.

Preferred examples of polyols with a hydroxyl group content of less than 40% by weight are e.g. aromatic polyols such as bisphenol-A and hydroxyl-containing polymers, in particular styrene-allyl alcohol copolymers.

Even in the presence of higher molecular weight polyols, however, it should be ensured that the polyol mixture is liquid in the temperature range from 100 to 150 ° C. (the preferred temperature range for the production of component (b)), although this is not absolutely necessary. Polyols which are particularly preferably used according to the invention are those having 2 to 12, in particular 2 to 6, carbon atoms. Specific examples of this are glycerol, trimethylolpropane, pentaerythritol, inositol, ethanediol and propanediol. Suitable compounds are also sugars, especially mono- and disaccharides.

The above phosphoric acid partial ester mixtures can advantageously be modified with aromatic and / or aliphatic carboxylic acid anhydrides. This modification leads to an improved water resistance of the coating and to the formation of a more stable intumescent layer when exposed to flame. Particularly suitable carboxylic anhydrides are those which contain carbon _{six-membered fragments of} the formula C _g R. or C _fi R ₁₀ , in which the radicals R can be the same or different and represent hydrogen, halogen (in particular fluorine and chlorine) or methyl. Specific examples of such carboxylic anhydrides are phthalic anhydride and cyclohexane-1,2-dicarboxylic anhydride, as well as the partially or completely fluorinated / chlorinated derivatives thereof. In the above modification, the carboxylic anhydride is preferably used in an amount such that it constitutes 10 to 20% by weight of the component (b). A proportion of about 15% by weight is particularly preferred in the case of phthalic anhydride.

With regard to the production of component (b) according to the invention described below, the ester mixtures according to the invention preferably also contain hydroxyl-containing polysiloxanes and / or surface-active compounds (surfactants) or wetting agents, preferably fluorosurfactants, in customary amounts. Polysiloxane and surfactant can also be combined in a single compound. These components facilitate the removal of the condensation water formed in the esterification reaction described below by forming a hydrophobic environment and reducing the surface tension and In the case of polysiloxanes, the hardened end product also leads to a more stable intumescent coating that adheres better to the substrate.

Any polysiloxane containing hydroxyl groups, which is soluble or dispersible in the esterification reaction medium described in more detail below and whose hydroxyl groups can react with phosphoric acid, can be used. However, the total content of SiO 2 in the cured composition resulting from such polysiloxanes should preferably be 2

Do not exceed wt .-%, otherwise the intumescent coating will be relatively rigid. Specific examples of preferred polysiloxanes are dihydroxy-functional methylsiloxanes, e.g. Type LA 157 (Th. Goldschmidt). Solid types of siloxane (e.g. Type Z 8018 from Dow Corning) can also be used if very compact coating films with low intumescence are desired.

In principle, it is also possible to use all surfactants or surface-active substances or wetting agents which are sufficiently stable in the respective reaction mixture and which reduce the surface tension. This is particularly true of fluorinated phosphate esters, e.g. Type Fluowet PP (Hoechst) too. These products are advantageously added to the polyphosphoric acid used to prepare the phosphate ester mixture before being combined with the polyol. Non-reactive fluorotides such as Fluorad 431 (3M) can also be used.

Although the compositions according to the invention as such lead to intumescence, it can be advantageous in certain circumstances to add additional blowing agent to the composition, for example in order to increase the rate of climb of the intumescent layer and to lower its density. Particularly suitable blowing agents, which are generally used in an amount of up to 20% by weight, based on the ester mixture, are nitrogen-containing blowing agents, in particular urea, melamine and derivatives thereof. Conventional fillers and / or pigments can also be added to the compositions according to the invention, the total amount of which generally makes up 5 to 50%, in particular 10 to 40%, of the total weight of the cured composition.

Suitable fillers and pigments are all substances used in conventional intumescent compositions, which are preferably mineral (inorganic) in nature. Examples include pigments such as titanium dioxide and carbon black, silicates such as aluminum silicate, and mineral fibers such as asbestos. The fillers / pigments can be added to component (a) and / or component (b) before the combination of these components or after, but the addition is preferably carried out before the combination. " ^~

The compositions according to the invention are preferably in a form suitable for coating or impregnation purposes, i.e. e.g. in aqueous or water-containing solution or dispersion. The water content of the composition depends on the amount and nature of the components used, but is preferably not higher than 60% by weight of the total composition, including water. The water content of component (a) before the combination with component (b) is, depending on the application, preferably in the range from 20 to 40% by weight, while the water content of component (b) is preferably in the range from 25 to 90% by weight. -% lies.

The compositions according to the invention are preferably used for coating objects made of wood, plastics (including plastic composites and plastic foams), cellulose materials, rubber and metal and for impregnating textiles. The composition can be applied in any conventional manner, for example by spraying, dipping, pulling and brushing. If necessary, the coating process can be repeated several times. Thieves- Layer thicknesses can be varied within a wide range, depending on the viscosity of the composition and the substrate to be coated. Usual layer thicknesses are in the range from 10 μm to 3 mm.

The composition (of the coating) is preferably cured at room temperature, although depending on the nature of the components used, curing at elevated temperatures (preferably up to about 60 ° C.) can also take place.

The ester mixture used as component (b) for the preparation of the composition according to the invention can be prepared according to the invention by a process which starts from polyphosphoric acids (optionally in a mixture with Pa-O-), which is carried out at elevated temperature and reduced pressure with effective removal of the water formed during the esterification (preferably with vigorous stirring) with the polyol (s) in a molar ratio suitable for achieving the required monoester / diester ratio.

A preferred process for the preparation of the partial phosphoric acid ester mixture (b) can be summarized as follows:

1. A polyol mixture which is liquid in the temperature range from 100 to 150 ° C. and has an average hydroxyl group content of at least 40% by weight is placed in a vacuum-tight mixing vessel made of inert materials and equipped with a controllable heating device.

2. Polyphosphoric acid is added to this polyol mixture under reduced pressure (preferably at most 160 mm Hg), vigorous stirring and temperature control so slowly that a local excess of acid is avoided and the proportion of free, non-esterified acid remains relatively low in the batch.

3. After all of the polyphosphoric acid has been added, stirring is continued under a constant vacuum and at a constant temperature until the acid number of the batch assumes a constant value.

The reaction product thus obtained is a viscous, more or less colored mass. This so-called prepolymer can be used in this form or, if necessary or desired, e.g. can be further cleaned by treatment in a thin film evaporator, further esterification taking place through the escape of water.

Another cleaning method is azeotropic drainage. The prepolymer is dissolved in a solvent suitable for the formation of an azeotrope with water, preferably methyl isobutylke on. The solution is boiled under reflux and the redistillate is returned to the distillation flask using a suitable drying agent.

The most important factor for the successful implementation of the above reaction is the early and effective removal of the water formed in the esterification reaction, since otherwise orthophosphoric acid is preferably formed from the polyphosphoric acid under hydrolysis, which is difficult to esterify under the reaction conditions described and which Decomposition (hydrolysis) catalyzed esters already formed.

The preferred reaction temperature for the above reaction is in the range of 115 to 130 ° C, while the reduced pressure is preferably 70 mbar or less. As already mentioned above, the reaction is preferably carried out in the presence of polysiloxanes and / or surfactants, which remove the water of condensation formed from the reactor. tion mixture by forming a hydrophobic environment and lowering the surface tension.

The polyphosphoric acids 5 which can be used in the above reaction can have any degree of condensation, provided they are in liquid or finely divided form which is readily dispersible under the reaction conditions described. For the calculation of the batch amount it must be assumed that pyrophosphoric acid corresponds to 105% orthophosphoric acid and tetraphos-10 phosphoric acid corresponds to 117.5% orthophosphoric acid. Phosphorus pentoxide corresponds to 138% orthophosphoric acid.

The achievable acid number depends on the degree of condensation of the polyphosphoric acid used. For the implementation of two

15 molar equivalents of acid orthophosphoric acid in the form of Polyphosphor¬, one molar equivalent of pentaerythritol, and a molar Äqui¬ valent glycerol is given the achievable acid number in dependi ^g vit the degree of condensation of Polyphosphorsäui used in FIG. 1

20th

According to the invention, it was also found that only a maximum of 50% of the phosphoric acid required may originate from phosphorus pentoxide, since otherwise decomposition reactions occur. It is known that triester of orthophosphoric acid is converted directly by

When phosphorus pentoxide is obtained with mono- and difunctional alcohols, with carbonifying polyols which are characterized by their hydroxyl group content as described above, the reaction continues with dehydration until carbon formation.

30

The final value of the acid number under the given conditions also depends on the level of the vacuum, as shown in FIG. 2. It is important that all of the reaction mixture be exposed to vacuum. Effective stirring 35 and thorough mixing are advantageous so that the reaction mixture with a large and constantly renewing surface is exposed to the vacuum. The batches described in the examples given below can be heated beyond the end point of the reaction, although the proportion of the decomposition products increases. -----

The course of the reaction can be followed using the acid number. Since each polyphosphoric acid used is hydrolyzed to orthophosphoric acid, the course of the reaction can be monitored by determining the acid number and the number of esterified acid functions of the orthophosphoric acid.

The acid number can be determined by titration against potassium hydroxide. The first acid function reacts to the ester in all cases. The degree of esterification of phosphoric acid can be defined via the ratio of the first to the second acid function. If orthophosphoric acid is titrated against strong bases such as potassium hydroxide solution, one turning point in the titration curve is obtained for each neutralized acid function at three discrete pH values. These values are at pH 4.5, 9.0 and 13.0.

If acid functions are esterified, the acidic character of the remaining acid residues increases. Thus a monoester shows equivalence point values at pH 4.5 or 9.0, while a diester has an end point at pH 4.5.

If a mixture of mono- and diesters of orthophosphoric acid is titrated, the ratio of monoesters / diesters can be determined from the position of the equivalence point at pH 9.0. A monoester contributes 50% to both equivalence points (pH 4.5 and 9.0). The amount of equivalence up to the first transition point will therefore make up half of the total consumption up to the second transition point. According to the invention, those phosphoric acid partial ester mixtures can be used in which more than 52% of the total consumption up to the first transition point

(up to the second transhipment point) (i.e. that

Molar ratio monoester / diester does not exceed 12: 1). at lower values, the resulting coatings are hygroscopic and sticky, but water-soluble.

The acid number and the ratio of monoester / diester thus serve to determine the course of the reaction and the efficiency of the production process with regard to the desired end products. A particularly preferred molar ratio of monoester / diester is 1: 1, which means that 67% of the total consumption in the titration is attributable to the first end point of the titration.

The decomposition, which is accompanied by changes in the color of the product, is characterized by a drop in the ratio of the first to the second acid function from a maximum for the given synthesis system to 50%.

Since the maximum value of the diester / monoester ratio that can be achieved is 2: 1, further cleaning methods are available to achieve this maximum value, e.g. circulating thin film evaporation in vacuum. This process can be carried out until the physical properties, in particular the viscosity, of the prepolymer preclude further thin-film evaporation.

Forms at the reaction temperature with the selected polyols, e.g. Styrene-allyl alcohol copolymers, not a liquid reaction mixture, the above prepolymers can be prepared by azeotropic dewatering. As already o; εn mentioned, this method is also suitable for lowering the acid number of other prepolymers.

The following examples illustrate the present invention without, however, restricting its scope.

EXAMPLE 1

This example illustrates a simple preparation of a composition with integrated intumescent properties. In a 1 liter round bottom flask equipped with an anchor stirrer, a vacuum line (achievable reduced pressure 160 mm Hg or below), a heating jacket with temperature control, a dropping funnel and a powder funnel, 184 g glycerin are filled in via the powder funnel. The heating is set to 140 ° C. 272 g of pentaerythritol are added to the hot, slowly stirred glycerol. At approx. 145 ° C and under vacuum, the water contained in the polyol mixture is removed for approx. 0.5 hours. After cooling to 115 ° C. and setting the target temperature to this value, 338 g of commercially available tetraphosphoric acid are added at a high stirring speed (approx. 1000 rpm) and at such a speed that the temperature in the reactor does not exceed 115 ° C. After all of the tetraphosphoric acid has been added, the reaction mixture is kept at 115 ° C. and under vacuum for a further 4 hours. The course of the reaction is followed by determining the acid number, which has dropped to a constant value of about 440 mg KOH / g at the end of the reaction.

The flask is emptied and the contents are allowed to cool to about 100 ° C.

Production of intuition coatings

The product obtained above is formulated with water to a 50% solution. 32.5 g of urea-formaldehyde resin solution (type BT 970, manufactured by British Industrial Plastics) are added to 100 g of this solution. The resulting mixture is applied to wood and, after curing at room temperature, gives a clear coat with good adhesion for about 24 hours. Curing can also take place at a maximum temperature of 60 ° C. The pot life of the composition is a maximum of 25 minutes. The mixture can, for example, be applied with a brush or sprayed on. Above 120 ° C, the coating forms an intumescent protective layer without the formation of smoke gases. Impregnation of textiles

A 25% solution is prepared with water from the product obtained above. 100 g of this solution are mixed with 16.25 g of the above urea-formaldehyde resin. A textile fabric is immersed in this solution for 5 minutes and then removed from the solution. The excess solution is squeezed off using a rubber roller. After 30 minutes at approx. 60 ° C the coating has hardened. The textile fabric treated in this way has a somewhat higher grip, but still has a textile character. Textiles finished in this way are flame-resistant, even if the intumescence cannot be clearly observed. The good insulating effect can, however, be ascertained in the case of flaming by monitoring the temperature on the back of the coated material.

EXAMPLE 2

This example illustrates the use of fluorinated surfactants, the polysiloxane modification, the partial use of phosphorus pentoxide in the synthesis process and the epoxy modification of the amino-formaldehyde resin.

184 g of glycerol, 272 g of pentaerythritol and 60 g of fluorinated surfactant (Fluorad FC 405, manufactured by 3M) are placed in the reaction vessel described in Example 1. The fluorinated surfactant is a fluorine-modified hydroxyl-containing polysiloxane in the form of a 2% ethanolic solution. The ethanol is drawn off by applying the vacuum before the start of the reaction. (The hydroxyl group-containing polysiloxane and the fluorosurfactant need not necessarily be in the form of a single compound.)

169 g of tetraphosphoric acid are added under the same conditions as in Example 1. As soon as the addition of the tetraphosphoric acid has ended, the temperature of the mixture is lowered to 100 ° C., whereupon 105 g of phosphorus pentoxide are added so slowly that the temperature of the mixture does not exceed 115 ° C. After adding all of the phosphor pentoxide, the reaction mixture is kept under vacuum at 115 ° C. until the acid number has dropped to a constant value below 380 mg KOH / g.

For further processing, the reaction product is then transferred to a 50% aqueous solution.

In addition to a 60% aqueous solution of a commercially available melamine-formaldehyde resin (type BT 427; British Industrial Plastics) 20% of a cycloaliphatic epoxide (3,4 epoxycyclohexylιαethyl-3,4-epoxycyclohexane carboxylate, commercially available under the name ERL 4221 from Union Carbide Corporation) was added. 39 g of the resin solution thus prepared are mixed with 100 g of the above aqueous prepolymer solution. Wood and primed metal plates can be coated with this mixture. The pot life is approximately 30 minutes. After curing in air at room temperature or at a maximum of 60 ° C., a hard, non-sticky, water-insoluble clear lacquer with intumescent properties is formed. In greater dilution, this formulation can also be used for the flame-retardant finishing of textile materials according to the method described in Example 1, the fabric retaining its textile character.

EXAMPLE 3

124 g of ethanediol, 272 g of pentaerythritol, 0.5 g of Fluorad FC 481 (3M) and 10 g of LA 157 (Th. Goldschmidt) are added to the apparatus described above.

Fluorad FC 481 is a fluorinated surfactant, while LA 157 is a hydroxy-functional polysiloxane.

335 g of the above mixture are added slowly and with stirring

Tetraphosphoric acid is added, the temperature of the reaction mixture not exceeding 100 ° C. After adding the whole

The amount of acid is raised to 115 ° C and. the reaction mixture is kept at this temperature Vacuum held until the acid number has reached a constant value below 494 mg KOH / g.

A 50% aqueous solution is prepared from the prepolymer thus obtained.

A 60% solution is also produced from a melamine-formaldehyde resin (type BT 427, British Industrial Plastics). This solution is modified in the same manner as in Example 2 with cycloaliphatic epoxy.

45 g of modified resin solution are added to 100 g of the aqueous solution of the prepolymer prepared above. This mixture can be used to coat wood or primed metal plates. The pot life is approximately 30 minutes. After the coating has hardened in air at room temperature or at a maximum of 60 ° C., a hard, non-sticky, water-insoluble clear lacquer is obtained. In the event of fire exposure, the coating obtained in this way acts as an intumescent lacquer that protects the substrate.

The following formulation can be used to coat steel structures:

Composition A

Prepolymer as prepared above 50 g

Water 47 g

Titanium dioxide (rutile type) 3 g

Composition B

Resin (BT 427) 19 g

Epoxy (ERL 4221) 9 g

Water 11 g

Aluminum silicate (Ketjensil SM 405; Akzo) 9 g mineral fibers 2 g Two parts of composition A are mixed with one part of composition B. With this material, primed steel (plates or supports) can be provided with an intumescent coating of up to 2 mm layer thickness. This coating cures completely overnight at room temperature.

If samples coated in this way are subjected to a fire test with a temperature curve according to BS 476, part 20, significantly higher values are found with regard to the temperature increase of the substrate compared to a conventional phosphate-catalyzed system with the same dry film thickness.

The coating obtained by the above process is hard, flexible and glossy and resistant to water and moisture. Such coatings can also be applied to wood in dry film thicknesses of 50 to 60 µm, giving a hard, glossy, decorative protective layer.

EXAMPLE 4

This example explains the modification of the partial phosphoric acid ester with carboxylic anhydride.

The apparatus described in Example 1 is modified so that reflux distillation is possible. A way of sampling the condensate is also provided. The vacuum line should be connected to the cooler.

The reactor is charged with 87 g of ethanediol, 76 g of 1,3-propanediol, 82 g of pentaerythritol and 90 g of 1,4-butanediol. 335 g of tetraphosphoric acid are slowly added under a slight vacuum (800 mbar). When all the acid has been added, the mixture is heated to 130 ° C. and the pressure is reduced such that the reaction mixture is boiling at reflux. The boiling point of the approach rises slowly. If the reaction mixture boils at 130 ° C and about 200 mbar, only water can be found in the condensate, simply by measuring the density or the refractive index can be identified. The apparatus is then brought back into the form described in Example 1. As soon as 60 to 62% of the total consumption of lye is accounted for by the first end point in the titration described above, 133 g of phthalic anhydride are added to the reaction mixture. After the phthalic anhydride has dissolved, the vacuum distillation is continued as described until the ratio of the end points of the titration is not more than 1% higher than before the phthalic anhydride was added. This phosphoric acid partial ester modified with aromatic groups can be used for the production of intumescent coatings on steel by reacting it with melamine-formaldehyde resin as described in Example 1. In this case, the epoxy modification of the melamine-formaldehyde resin can be used. The hardened coating shows a significantly improved resistance to moisture and becomes a rigid intumescent layer when exposed to flame.

EXAMPLE 5 A prepolymer is prepared by the method of Example 1, the molar ratio of orthophosphoric acid: glycerol: pentaerythritol being 2: 0.75: 0.75.

A Soxhlet apparatus is placed on a 500 ml round-bottomed flask. A stirrer, preferably an anchor stirrer, is used which keeps the contents of the piston in constant motion and presses up on the walls of the piston. The piston is heated. A desiccant is placed in the Soxhlet apparatus and a cooler is connected. 280 g of the above prepolymer are placed in the flask, whereupon 140 g of styrene-allyl alcohol resin (Monsanto RJ 100), dissolved in 140 g of methyl isobutyl ketone (MIBK), are added. The stirrer is started and the mixture is refluxed for 4 hours, the MIBK passing through the desiccant for dewatering.

The Soxhlet apparatus and the cooler are then removed and replaced by a vacuum distillation apparatus. you distills the MIBK so that the temperature of the prepolymer does not exceed 115 ° C. The end product is a water-soluble, soft, slightly pink colored product. This product forms clear, hard coatings with urea and melamine-formaldehyde resins, as described in the examples above. These coatings intumesce far less than the coatings that were described in the previous examples, but are also non-flammable and do not develop any smoke gases. They can be used for clear lacquers and coatings for eg wood.

The method just described can be used as an alternative to the purification method described above with a column to lower the acid value in the thin-film evaporator.

Claims

PATENT CLAIMS

1. Composition with integrated intumescent properties, characterized in that it is obtainable by combining (a) one or more amino-formaldehyde resins and

(b) a mixture of mono- and diesters of orthophosphoric acid, optionally modified with carboxylic acid anhydride, with one or more polyols, the average hydroxyl group content of these polyols being at least 40% by weight

The molar ratio of monoester / diester does not exceed 12: 1 and the phosphorus content of the mixture is at least 10% by weight.

2. Composition according to claim 1, characterized in that component (a) is selected from optionally modified melamine-formaldehyde resin, optionally modified urea-formaldehyde resin and mixtures thereof.

3. Composition according to claim 1, characterized in that its phosphorus content after curing is at least 8 wt .-%.

4. Composition according to claim 1, characterized in that it is in the form of an aqueous or water-containing solution or dispersion.

5. Composition according to claim 1, characterized in that component (b) is derived from at least two polyols.

6. Composition according to claim 5, characterized in that each polyol has a hydroxyl group content of at least 40% by weight.

7. The composition according to claim 5, characterized in that one or more polyols have a hydroxyl group content of less than 40 wt .-% and no more than 15% of all polyol hydroxyl groups come from such polyols.

8. The composition according to claim 1, characterized in that the polyols are selected from aliphatic and cycloaliphatic polyols having 2 to 12 carbon atoms.

9. The composition according to claim 8, characterized in that the polyols have 2 to 6 carbon atoms.

10. The composition according to claim 8, characterized in that the polyols are selected from glycerol, trimethylolpropane, pentaerythritol, inositol, ethanediol, propanediol and mixtures thereof.

11. The composition according to claim 8, characterized in that additionally hydroxyl-containing polymers and / or aromatic polyols are used as polyols.

12. The composition according to claim 1, characterized in that component (b) is in a form modified with aromatic and / or alicyclic carboxylic anhydrides.

13. Composition according to claim 12, characterized in that the carboxylic anhydrides contain carbon six-membered fragments of the formula C _g R. or C _g R ₁₀ , in which the radicals

R can be the same or different and represent hydrogen, halogen or methyl.

14. The composition according to claim 1, characterized in that it additionally contains nitrogenous blowing agents.

15. Composition according to claim 14, characterized in that the nitrogen-containing blowing agents are selected from urea, melamine, derivatives of these compounds and mixtures thereof.

16. The composition according to claim 1, characterized in that it additionally contains hydroxyl-containing polysiloxanes and / or fluorosurfactants.

17. Composition according to claim 16, characterized in that the polysiloxanes are present in such an amount that the SiO "content of the dried and hardened composition resulting therefrom is not more than 2% by weight.

18. The composition according to claim 2, characterized in that the resins (a) are modified with aromatic glycidyl ethers and / or cycloaliphatic epoxides.

19. The composition according to claim 1, characterized in that it additionally contains fillers and / or pigments.

20. Composition according to claim 19, characterized in that the fillers and / or pig: ^* --nt are selected from mineral substances.

21. Use of the composition according to claim 1 for the manufacture of coatings.

22. Use of the composition according to claim 1 for coating objects made of wood, plastics, cellulose materials, rubber and metal and for impregnating textiles.

23. Mixture of partial esters of phosphoric acid, characterized in that it is a mixture of mono- and diesters of orthophosphoric acid with one or more, optionally modified with carboxylic acid anhydrides It deals with polyols, the average hydroxyl group content of the polyols being at least 40% by weight, the molar ratio of monoester / diester not exceeding 12: 1 and the phosphorus content of the ester mixture being at least 10% by weight.

24. Mixture according to claim 23, characterized in that it is derived from at least two polyols.

25. Mixture according to claim 24, characterized in that each polyol has a hydroxyl group content of at least 40 wt .-%.

26. Mixture according to claim 24, characterized in that one or more polyols have a hydroxyl group content of less than 40 wt .-% and no more than 15% of all polyol hydroxyl groups come from such polyols.

27. Mixture according to claim 23, characterized in that the polyols from aliphatic and cycloaliphatic

Polyols having 2 to 12 carbon atoms are selected.

28. Mixture according to claim 27, characterized in that the polyols have 2 to 6 carbon atoms.

29. Mixture according to claim 27, characterized in that the polyols are selected from glycerol, trimethylolpropane, pentaerythritol, inositol, ethanediol, propanediol and mixtures thereof.

30. Mixture according to claim 27, characterized in that additionally hydroxyl-containing polymers and / or aromatic polyols are used as polyols.

31. Mixture according to claim 23, characterized in that it is present in a form modified with aromatic and / or alicyclic carboxylic acid anhydrides.

32. Mixture according to claim 31, characterized in that the carboxylic anhydrides contain carbon _six- _{membered fragments of} the formula C _fi R. or C ₆ R ₁₀ , in which the radicals R may be the same or different and represent hydrogen, halogen or methyl.

33. Mixture according to claim 23, characterized in that it additionally contains nitrogenous blowing agents.

10

34. Mixture according to claim 33, characterized in that the nitrogen-containing blowing agents are selected from urea, melamine, derivatives of these compounds and mixtures thereof.

15

35. Mixture according to claim 23, characterized in that it additionally contains hydroxyl-containing polysiloxanes and / or fluorosurfactants.

36. Use of the mixture according to claim 23 for the preparation of coating compositions with integrated intesive properties.

37. A process for the preparation of the mixture as claimed in claim 23, 25, characterized in that it comprises the reaction of polyphosphoric acid with the polyol (s) at elevated temperature and reduced pressure.

38. The method according to claim 37, characterized in that 30 the reaction is carried out at a temperature of 100 to 150 ° C.

_Λ 39. The method according to claim 37, characterized in that the reaction is carried out at a pressure of 160 mm Hg or below _• 35. 40. Coated materials, characterized in that the coating comprises a hardened composition according to claim 1.