FI60881C - SAETT ATT FRAMSTAELLA FENOL-ALDEHYDSKUMPLASTER - Google Patents

Description

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• »TjLV C / ^ jv Patent granted on 13 04 1932 jSstfijb Patent meddelat T (51) Ky.ik? /Int.ci.3 c 08 J 9/00 // C 08 L 61/08 FINLAND - FINLAND (21) ' '«•" «' t '*' * · ™ · - P» twt »n» eknln | 190U / 71 (22) HtkemUpWvI - An «eknlnpdax 06.07.71 (23) Alkupiivt - Giltlghetadag 06.07 · 71 (41) Tullut lulklMkal - Bllvlt offantllg 07 * 01.72

National Board of Patents and Registration .............,. , ^. , ^ ^, (44) NihtivUulpaneo | a moonLjulkalsun pvm. - ..,

Patent- oeh regiaterstyrelsen · Ansökan utiagd och utl. «Krift« n pubitcarad 31.12.81 (32) (33) (31) Privilege claimed —Begird prlorttet 06.07 * 70 06.07.70 USSR (SU) 1 ^ 5309 ^, 1 ^ 53095 (71) Vladimirsky Nauchno-Issledovatelsky Institut Sinteticheskikh Smol, ulitsa Frunze, 77, Vladimir, USSR (SU) (72) Viktor Alexeevich Novak, Vladimir, Jury Semenovich Murashov, Vladimir, Vasily Dmitrievich Valgin, Vladimir, USSR (SU) (7I * ) 0y Kolster Ah (5I *) The way to make phenolic aldehyde foams - Sätt att framställa fenol-aldehydskumplaster

The present invention relates to a process for producing a foam having reduced brittleness and improved strength properties by mixing resole-type phenolic aldehyde condensation products or aldehydes with novolac-type phenol aldehyde condensation products, foaming and curing the mixture with acid. These foams are used as insulation and building materials, in the refrigeration industry, and in various transports to pipe insulation, etc.

In a known process for the preparation of foams on the basis of novolak-type phenol-aldehyde resins, solid compounds obtained by mixing the novolak resin with a blowing agent and hexamethylenetetramine are treated at high temperatures.

The foaming, curing and shaping of such compositions takes place in a basic medium provided by ammonia which is liberated by the decomposition of hexamethylenetetramine under the influence of temperature.

2 60881

Also known is a process for preparing foamed materials from resole-type phenolic aldehyde resins, in which liquid resoles are mixed with a blowing agent and the reaction mixture is then allowed to swell, cure and form in an acidic medium.

With this known method, it is possible to prepare a foam both by heating the reaction mixture and without introducing external heat.

Both of the above methods have serious drawbacks.

One method of treating novolak resin is characterized by a high temperature and long lasting forming step because the compositions are foamed in molten novolak resin at 100-120 ° C and cured at 1L0-160 ° C for several hours.

In addition, the above method is stationary and batch-operated and requires a long forming step to foam the solid at a relatively high temperature, in addition to which complex equipment is required for fine grinding of the solid components and solidification of the foam as a solid.

The low economic return of the technological processes, the relatively high cost and the limited amount of finished foam are explained due to the above-mentioned disadvantages characteristic of the known flotation process of novolak-type phenolic aldehyde resins.

The disadvantages associated with the known process for the production of resole-type phenol-aldehyde foams are: - Low chemical activity of the resins during foaming and relatively long foaming time, especially in structures and molds made of high heat capacity materials (metals, etc.) or temperatures below 20 ° C; - A sufficient amount of acidic substance must be developed to foam and cure the mixture for several minutes at temperatures below 100 ° C, as a result of which the corrosion activity of the foamed plastic is determined when the plastic is in contact with a large number of building materials in practice; - Poor stability of "Resoli" resins during storage and transport (usually for several weeks), which prevents their further processing into a foam with a very low density, especially in cases where foam formation should take place "in situ".

In addition, foams based on resole-type phenol-aldehyde resins lag behind foams derived from novolak resins in terms of moisture and flame resistance, GB Patent 1,130,067 and DE Patent 1,236,183 disclose compositions and methods for curing resole-type phenol-formaldehyde resins. However, the resulting foams are brittle (see FR patent 1,583,857) and have a high corrosive effect (see DE patent 1,236,183). According to said GB patent 1,130 Ο67, the resins are cured with strong inorganic acids and the novelty of the process is that a nitrogen compound is incorporated into the resole resin, part of which decomposes under the heat of exothermic curing of the resole, making the foam more by an inorganic acid and cannot be present in the free state and thus is not a forrn aldehyde acceptor.

It is an object of the invention to provide a process for the production of foams based on phenol-aldehyde condensation products which makes it possible to process both novolak and resole type products by rapidly forming a liquid composition in a cavity of virtually any geometric shape, and which can be carried out at temperatures below 100 ° C, preferably at 10-20 ° C, in a short time, i.e. in a few seconds or a few minutes.

The process according to the invention preferably uses Novo-lacquer-type phenolic aldehyde resin flowing in combination with arylsulfonic acid and aldehyde condensation products as sulfonated novolac-type phenol-aldehyde condensation products. The use of such compounds makes it possible to obtain foams with a significantly reduced corrosive effect.

It is further preferred that organic nitrogen compounds be added to the mixture used according to the invention as such, either as a single compound or as a mixture of several compounds or as a reaction product of reaction with arylsulfonic acids and / or aldehydes. .

The invention is characterized in that Novo lacquer-type phenol-aldehyde products sulfonated in the ring are used, wherein the weight ratio of novolak-type phenol-aldehyde products sulfonated in the ring to resole-type products is between 85:15 and 15:85 on a dry matter basis. is between 95: 5 and 60: Uo calculated on a dry matter basis.

The process according to the invention offers the following advantages in the preparation of phenol-aldehyde foam compared to known processes: a liquid reaction mixture can be used which forms rapidly and hardens slightly with heating (below 100 ° C) or without external heating, which makes the process versatile.

11 60881

The process according to the invention can also be used to produce foams based on both resole and novolak-type phenol-aldehyde condensation products for foams which can be formed by continuous or semi-continuous equipment. In addition, the described method largely overcomes the difficulty of processing phenol-aldehyde condensation products into high quality foams virtually regardless of the manufacturing process of the condensation products.

The latter makes it possible to relocate the production of foams to applications far from the phenol-aldehyde resin production site.

The novolak and resole type phenol-aldehyde condensation products used in the invention are the reaction products of phenol and its homologues with aliphatic or aromatic aldehydes.

The general manufacturing principles of such products have been extensively described in the technical literature. Phenol-aldehyde novolak substances are usually prepared by condensing a molar excess of phenols with aldehydes in an acidic medium.

The liquid form of aggregation of such products results, for example, from their incomplete drying until the content of the basic substances they contain is 80-90%.

Novolac-type phenol-formaldehyde condensation products are known to be a commercial mixture of compounds of the formula

Ar - CH_-Ar - OHo-Ar, 2 n 2 'where Ar is oxyphenyl, n = 0-10, the CH 2 bonds are located in the o- and / or p-positions relative to the phenol hydroxyl. They also contain a certain amount of free phenol and formaldehyde.

Analogs of novolak-type phenol-formaldehyde resins include inventive polynuclear compounds such as dihydroxydiphenylmethane.

The most widely used method for preparing resoles is by carrying out alkaline catalysis conditions using an excess of aldehyde reagent.

Resole-type phenol-aldehyde condensation products include a polydispersed mixture of methylol derivatives of these substances in which the methylol groups are ortho and / or para to the phenol hydroxyl, as well as isomeric phenol alcohols having a phenyl radical, 2-o-alcohols, 6-dimethyl-o-phenols, 2,4,6-trimethyl-o-phenol).

According to the invention, the resolution-type condensation products in the foamable mixtures can be replaced by individual aldehydes or mixtures thereof, which (when forming the foam) act as crosslinking agents for novolac-type condensation products in an acidic medium. In this case, formaldehyde, acetaldehyde, benzaldehyde, etc. can be used, although formaldehyde as aqueous solutions is preferable.

According to the invention, the components of phenolic aldehyde condensation products of the resole and novolak type are also useful both as mixtures and as individual analogues. Instead of Novolaka, the swellable combinations may contain one of the isomeric dioxophenylalkanes, for example In exactly the same way, the resole in the mixture can be substituted with 2,6-6,6-trimethylolphenols, 2,2,6,6'-tetramethylol, 1+'-dioxidediphenylalkanes, etc.

These compounds are generally considered to be individual analogs of resole-type phenol-formaldehyde resins.

The ring-sulfonated novolak-type condensation products used according to the invention in the form of novolak resins can be prepared, for example, by: a) sulfonating a dehydrated novolak resin with a known sulfonating agent (sulfuric acid, sulfur trioxide, etc.) using up to 1 mole of novolac ) by combining a liquid novolak-type phenol-aldehyde resin in the reaction mixture with condensation products of arylsulfonic acids and aldehydes.

Preferred arylsulfonic acids include both pure compounds such as naphthol, anthracene, phenol, benzene, toluene and naphthalenesulfonic acid and technical products obtained by sulfonating the corresponding aromatic compound with a known sulfonating agent.

According to the invention, the foamable compositions may contain, in addition to or instead of resole-type condensation products, aldehydes which act as a crosslinking agent for novolak-type condensation products in an acidic medium in the production of foams. Formaldehyde, acetaldehyde, benzaldehyde or the like may be used; formaldehyde in aqueous solution is most preferred.

The nature of the phenols and aldehydes used in the preparation of phenolic formaldehyde condensation products of the novolak and resole type is not of primary importance over what is essential to the invention. For example, satisfactory results have been obtained using, with the exception of phenol itself, isomeric cresols, xylene and other phenols having at least 6 60881 unsubstituted (ortho-ortho or ortho-para) positions to the phenol hydroxyl in the ring, and acetaldehyde compounds of the aldehyde / form-aldehyde type and small polymer modifications of benzaldehyde. It is most preferred to use phenol and formaldehyde because they are low cost and readily available.

According to another embodiment of the invention, the sulfonovolac-phenol-aldehyde condensation products together with the aldehyde component are included in the mixture in a weight ratio between 95: 5 and 60: k0.

By the process of the invention, the foam is expanded and cured under acid-catalyzed conditions.

The ring-sulfonated phenol-aldehyde condensation products described above generally act as acid catalysts. However, if necessary, in addition to these ring-sulphonated products, other acidic substances may be added to the mixture which, when added to the foamable composition, make it possible to adjust the pH to below U. Such substances include: - mineral acids (hydrochloric, sulfuric, orthoboric, orthophosphoric, hydrofluoric silicic acid) and so on.); - organic mineral acids (complex acids based on boric acid esters and oxyacids such as oxalic acid, arylsulphonic acid, etc.); - anhydrides and salts of mineral acids P2 ^ 5 * al™™inikals; ‘- umrau’ta“ chlorides, etc.).

All of the above compounds can be used alone or in admixture with each other.

The preferred acidic product is the condensation product of arylsulfonic acids with aldehydes together with novolak resins, the total amount of acidic substance in the mixture being 1-50% by weight.

Suitable aryl sulfonic acids for the process according to the invention are a large number of compounds which can be both pure products, e.g. naphthol, anthracene, phenolbenzene, toluene and other naphthalenesulphonic acids, and commercially available sulphonation products of the corresponding aromatic compounds with sulphonating agents.

Of the carbonyl-containing compounds, acetaldehyde, acetone, methyl ethyl ketone and furfural are used, but formaldehyde is most preferred as the aqueous solutions used. The treatment conditions for arylsulfonic acids with carbonyl-containing compounds can vary within wide limits depending on the chemical origin of these substances. Generally, this treatment is carried out at temperatures not exceeding 150 ° C for a period ranging from a few minutes to several hours.

7 60881

Flotation of mixtures based on ring-linked sulphonated and novolac-type phenol-aldehyde condensation products or condensation products of substances of similar nature and resole-type substances with or with alcohols such as aldehyde can be carried out in the presence of an acid catalyst. , aliphatic esters and ketones, saturated aliphatic hydrocarbons, fluorochlorohydrocarbons ("Freons"), halogenated hydrocarbons, gasolines, etc.

According to the invention, it is preferred to use for this purpose a petroleum ether fraction having a boiling point of 35-50 ° C at a pressure of j60 mm Hg.

A good foam structure with sufficiently closed pores is obtained by using such a petroleum ether fraction and also fluorochlorohydrocarbons, for example 1,1,2-trifluoro-2,2,1-trichloroethane.

The low boiling solution is introduced into the mixture in an amount of 0.5 to 30% by weight, preferably 2 to 10% by weight, depending on the desired density of the foam.

According to the invention, novolac-type ring-sulphonated phenolic aldehyde condensation products or substances of a similar nature and / or substances obtained by treating arylsulphonic acids with compounds containing carbonyl groups are mixed with pre-saturated hydrocarbons and / or fluorocarbons ° and + 80 ° C, with such combined products acting simultaneously as both a hardening and a foaming agent during foaming. Such composite products are sufficiently stable during storage and act when mixed with resole-type phenol-aldehyde condensation products and / or aldehydes.

It was found that organic substances with a pKa of less than 8 and containing at least one amino, amido, cyanamide, or nitrile group are able to form phenol-containing compounds and / or bind formaldehyde in order to reduce the toxic effect of the foamed plastic and to improve the sanitary conditions of foam production. These compounds are added to the mixture in an amount of 0.5 to 50, preferably 1 to 20% by weight. These compounds include melamine, urea, acrylonitrile di-cyanodiamide, m-phenylenediamine, aniline, thiourea and some others.

Most of the above-mentioned organic nitrogen compounds are solid at room temperature and poorly miscible with the other components of the foamable mixture. It has been found that these compounds must be added to the mixture as a solution, aqueous emulsion, aqueous dispersion or dissolved in a suitable organic solvent such as an alcohol. However, it is more preferable to use these compounds in the form of derivatives, such as: - in complexations with mineral or arylsulfonic acids - as resins containing condensation products of urea melamine dicyandiamide, etc. with formaldehyde in a basic or acidic medium.

Hydrochloric urea, salts of urea with aryl sulfonic acids, urea and melamine formaldehyde resins, as well as formaldehyde aryl sulfonic acid condensate and organic compounds containing at least one amino, amido, cyanamide, or nitrile group can be used as examples of such derivatives.

According to the invention, the fine-cell structure of the foamed plastic can be improved and the density reduced if surfactants are added to the foamed mixture.

The best results have been obtained by using nonionic surfactants which are added to the mixture in an amount of 0.1 to 10, preferably 1 to 3% by weight. Suitable surfactants include silicone oils; polymerization products of ethylene oxide with alkylphenols or higher fatty acids; cellulose ethers such as methylcellulose, carboxymethylcellulose, oxyethylated castor oil, etc.

Partial heat loss occurs in the flotation mixture when low boiling liquids are used as the foaming agent due to evaporation of the liquids.

The thermal equilibrium of the process can be improved by adding to the mixture compounds which release heat upon chemical contact with water or with acidic additives in the flotation mixture at a temperature of 20 to 10 ° C.

The best results were obtained by adding compounds from the following groups to the mixture: - carbonates, bicarbonates, nitrites of alkali and alkaline earth metals and ammonium carbonate; - meta-hydrides and metal carbides of the second and third groups of the Periodic Table of the Elements; - powdered metals above hydrogen in a series of electrical voltages; - Β ^ Ο ^ and P205 - type acid anhydrides; - alkyl chloride silanes (trichloromethylsilane, etc.).

The listed substances are added to the mixture in an amount of 0.1 to 20, preferably 0.5 to 10% by weight.

Most preferred are fine (not more than 200 mesh) metal powders in a series of electrical voltages above hydrogen, such as iron, aluminum, magnesium, cadmium, and zinc powders, and especially aluminum and magnesium powders or mixtures thereof.

9 60881

It is convenient to introduce the foaming agent into the mixture in the form of a storage-stable combination comprising a novolak-type compound containing sulpho groups.

According to the invention, 0-50% by weight of organic compounds containing at least one amide, amino, cyanamide and nitrile group with a pKa of less than 8 and capable of reacting with formaldehyde and / or forming complexes are introduced into the mixture. with phenol.

It is also preferred to add the compounds to the mixture in the form of derivatives, for example as intermediates with arylsulfonic acids and / or aldehydes.

It is also possible to add surfactants as foam regulators to the mixture, and thermal activators which are able to release heat when in contact with the components of the mixture.

The technology for the production of foams for phenol-aldehyde condensation products is based on a mixture of said components with a certain weight ratio and on the dosing of the resulting liquid mixture into the space to be filled with foam.

The mixing and dosing of the components can be performed with similar equipment used in the production of polyether urethane foam.

The mixture is foamed and cured for a few minutes at a temperature close to room temperature or by heating the mixture and / or mold to below 100 ° C.

The compositions of the foam mixtures according to the invention are shown in the following table: No. Components of the foamable mixture Composition

Embodiment Embodiment 1 Form 2 ----— I - .. - »- + III",, I „m. 1 I« iii ^ ii I "—— - 1a Resole-type phenol-aldehyde condensation products 15-85 (resole resins, oxymethylphenols or mixtures thereof), parts by weight 1b Aldehydes, parts by weight 5-1 + 0 2 Ring-sulphonated phenol-aldehyde condensation products 85-15 95-60 (in the form of sulphonated novolac resins together with condensation products of arylsulphonic acids, or mixtures thereof, by weight) of the mixture 3 Acidic substance (condensation products of arylsulfonic acid 0-50 0-50 with aldehydes in the presence of organic nitrogen compounds, inorganic acids), by weight # of the mixture k Blowing agent (aliphatic saturated hydrocarbons, 0-30 0-30 halogenated hydrocarbons, chlorofluorocarbons, chlorofluorocarbons) 10 and +80 C), by weight # of the amount of mixture (continued) 10 60881 No. Components of the mixture to be foamed Composition

Execution Execution __________form 1 Form 2_ 5 Organic nitrogen compounds having a pKa ^ 8 0-50 0-50 of amines, cyanamines or nitriles, by weight # of the mixture 6 Non-ionic surfactants, by weight 0-10 0-10 of the amount of mixture 7 "Thermal activators" (metal powders; 0-10 0-10 alkali metal or alkaline earth metal carbonates, bicarbonates, nitrates, hydrides and carbides and similar ammonium compounds

In the practice of preparing foam in accordance with the invention, two or three blend components are treated instead of the six or seven components shown in the table, as some of the components in the table can be mixed together into permanent stock products which are then combined at the site before use.

The phenol-aldehyde foams of the invention have similar physical-mechanical and thermophysical properties to known materials of the same type, but are also more flexible and refractory than the latter.

The following examples will help one skilled in the art to understand the details and modifications of the invention,

The following describes the manufacture of foam compound components and the meanings of the trademarks used

A. Manufacture of condensation products of the novolak type Product I

Preparation of Novolak Resins No. 1 and No. 3 1 mole of phenol was condensed with 0.9 moles of formaldehyde, which was used as a 37% by weight aqueous solution. The catalyst was sulfuric acid. When the synthesis was complete, some or all of the water (resin 1) was removed from the resulting resin.

Resin No. 1 has a viscosity of 5,600 cP at 20 ° C and contains 11 # water and 10 # free phenol.

Resin No. 3 has a droplet drop point of 109 ° C and the resin contains 6 # phenol but no water at all.

Product II

Preparation of liquid novolak resin 1 mole of phenol was condensed with 0.7 moles of formaldehyde in the presence of a zinc acetate catalyst.

11 60881

After 90% of the formaldehyde had reacted, sulfuric acid was added in such an amount that the pH of the medium became 1 and condensation was allowed to proceed at 100 ° C for 2 hours. Part of the water was separated from the obtained gauze. This resin has a viscosity of h 200 cP and contains 12% phenol and 13% water.

Product III

Preparation of sulfonovolac resins N1, N2 and N3

The novolak resin obtained by condensing 1 mole of phenol with 0.65 moles of formaldehyde and dehydrated was sulfonated.

Sulfonation was performed with 96% sulfuric acid at 90-120 ° C for one hour. The resulting sulfo resin was diluted to 25% by weight with water.

The analysis results are shown in Table 1.

Sulfo resin Moles of H 2 SO 4 per 6 ° C - alcohol solution - Free phenol CH 2 O-, calm. , its viscosity, cP content .. · * mole of free and r ~% concentration- bound resin _phenol____ 1 0.3 21 10.2 not detected 2 0.6 23 6.2 "31 25 not detected"

The sulfonated isomeric mixture of dioxydiphenylmethanes is obtained by the same preparation method.

B. Manufacture of resole type condensation products

Product IV

Liquid resole resins

Resole resins No. 1 and No. 2 were prepared by condensing 1 mole of phenol with 1.5 moles and 2.5 moles of formaldehyde, respectively, at a pH of 8.9 (as NaOH catalyst), a synthesis temperature of 75 ° C and a reaction time of 1, After 5 hours, the resins were neutralized to pH 7 to 0.1 and dewatered in vacuo to a dry matter content of 82%.

Resin number Höppler viscosity Free phenol content 1 3 5U0 8.9 2 2 890 5.6

Product V

Triraetylolifenoli

Trimethylolphenol was prepared by condensing 1 mole of phenol with 3 moles of formaldehyde in a strongly basic medium. The aqueous solution of trimethylolphenol was dried in vacuo. The analytical values of the trimethylolphenol obtained are as follows: 1) Dry matter content = 85%

2) Höppler viscosity = 5,600 cP

3) Free phenol content = 1.2% 60881 C. Manufacture of combined products

Product VI

Combined products

Compounds with ring-containing sulfur groups were treated with petroleum ethers or "Freon-113" at a temperature not exceeding U0 ° C.

This treatment resulted in white storage-stable products.

5% by weight of the low boiling liquid can be added to the sulfonated resins, while the condensation product of sulfophenol, urea and formaldehyde can be easily mixed with 20% by weight of the low boiling liquid to form stable products. The condensation products of ethylene oxide and alkylphenols ("OP", "OP-7" and "OP-10") can be used to control the cell size of the foam to be produced. The blowing agent used was 1,1,2-trichloro-2,2,1-trifluoroethane ("Freon-113") and fluorotrichloromethane ("Freon-11").

For an overview, Examples 1-3U, which illustrate the preparation of phenol-aldehyde foams according to the invention, are grouped in Tables 1-U. In each case, the foam was prepared by mixing together the components shown in the tables.

The resulting mixture was foamed and shaped without external heat or in an oven at a preselected temperature.

The foaming and curing time was a few minutes and in none of the examples was more than 30 minutes.

The initial mixing temperature is the same in all examples and about 20 ° C.

The time that elapses after all the components of the mixture were mixed until foaming begins is referred to herein as the "foaming induction time."

The strength properties, density, acid number of the foam foam aqueous extract (acids are extracted from 1 g of foam in 100 ml of water at 20 ° C for 8 hours) and flame resistance were also determined.

Examples 1-6 (Table 1) show the possibility of forming a foam from a mixture containing various phenol-aldehyde condensation products, various acidifying agents, foaming agents, foaming agents. Nitrogen-containing organic substances, and special additives.

Examples J-T2 (Table 2) show the possibility of preparing foam from novolak-type or analogous sulfonated phenol-aldehyde condensation products. It is also shown that the mixture may contain various products of your type, aldehyde and special additives for foaming.

13 60881

Particular emphasis must be placed on high flexural strength. These properties are 2-3 times higher than the corresponding properties of previously known similar products.

Examples 13-23 (Table 3) show the possibility of using different weight ratios between novolak and resol type phenol-aldehyde condensation products.

Examples 2 ^ + - 3 ^ (the table show the possibility of using different weight ratios between an aldehyde and a novolac-type sulfonated phenol-aide hydrocondensation product in a ring. The foam is characterized by not glowing when heated by a gas burner flame for 5 minutes, while known substances without flame retardant additive, glow for several minutes after being removed from the fire.

'U 60881

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Claims (6)

1. A process for preparing a foam having reduced brittleness and improved strength properties by mixing resole-type phenol aldehyde condensation products or aldehydes with novolacate-type phenol aldehyde condensation products using The weight ratio of aldehyde products to resole-type products is between 85:15 and 15:85 on a dry matter basis, and the weight ratio of novel lacquer-type phenolic aldehyde products sulfonated in the ring to aldehydes is between 95: 5 and 60:40 on a dry matter basis. Process according to Claim 1, characterized in that liquid novolac-type phenolic aldehyde resin is used as the sulfonated novolac-type phenolic aldehyde condensation products in the ring in combination with aryl sulfonic acid and aldehyde condensation products. Process according to Claim 1 or 2, characterized in that the phenolaldehyde novolac condensation products sulfonated in the ring are used after premixing with aliphatic hydrocarbons and / or halogenated hydrocarbons having a boiling point between -10 and + 80 ° C. Process according to one of Claims 1 to 3, characterized in that urea, melamine, dicyandiamide, acrylonitrile, aniline, thiourea and m-phenylenediamine are additionally used in an amount of 1 to 20% by weight, based on the total amount of the mixture. Process according to Claim 4, characterized in that urea, melamine, dicyandiamine, acrylonitrile, aniline, thiourea and m-phenylenediamine are pretreated with arylsulfonic acids and / or aldehydes. Process according to one of Claims 1 to 5, characterized in that the surfactant is added in an amount of 1 to 3% by weight, based on the total amount of the mixture, and / or a foaming agent having a boiling point of between -10 and + 80 ° C in an amount of 0.5 -10% by weight based on the total amount of the mixture.