CS262845B1 - Impregnating and laminating agent - Google Patents

Abstract

The present invention relates to a composition for the manufacture of laminated materials, impregnation of porous materials, coating of various materials for the production of waterproof, benzine-resistant and oil-resistant seals and coatings based on phenol-formaldehyde resins. The composition is comprised of condensate which is not used in the purification of 2,6-xylonel by means of phenol formaldehyde or paraformaldehyde or a solution thereof in aromatic solvents emulsified in water.

Description

The invention relates to a composition usable for impregnating porous materials, such as wood, paper, concrete, against the effects of moisture, mold, fungi and bacteria, as a coating for surface treatment or as a binder for the production of laminated materials.

Recently, very advantageous processes for refining crude xylenol by chemical means have been patented (see e.g. A.O. 230.842,

A.O. 231·085). These processes are based on the fact that the by-products accompanying 2,6-xylenol, phenol derivatives having at least one free o-position relative to the phenolic OH-group, can be practically removed by heating this mixture with paraformaldehyde, an aqueous solution of formaldehyde or with formaldehyde-releasing substances, in the presence of catalysts, ensuring their condensation with formaldehyde predominantly in the o-position.

The condensation reaction product is essentially a linear low-molecular condensate of phenol and its methyl derivatives with formaldehyde, characterized by disinfectant and fungicidal effects, easily melting usually between 50 and 80°C and soluble in common organic solvents, especially alcohols, ketones, aromatic and chlorinated hydrocarbons.

The properties of this waste condensation product can be advantageously used both in the production of laminated materials, especially paper, fabrics and wood veneers, as stated in A.O. 240372, and as an impregnating agent, as stated in A.O. 240579.

It has now been found that all the described applications and utilization of the waste condensation product can be ensured in a simpler manner if an emulsion is prepared from the waste phenol-cresol-xylenol-formaldehyde condensate and the impregnation, coating or laminate production is carried out with this emulsion.

The subject of the invention is an impregnation and laminating agent based on condensation products of phenol, cresols and xylenols with formaldehyde, which are obtained during the chemical refining of 2,6-xylenol using formaldehyde or paraformaldehyde, which contains 100 parts by weight of condensate, 5 to 100 parts by weight of emulsifier, up to 1000 parts by weight of water and up to 200 parts by weight of aromatic hydrocarbon.

The use of condensate emulsion achieves a more advantageous effect, manifested in surface treatments by higher smoothness and homogeneity of the coating, easier spreading, in impregnations and laminations by better absorbency caused by the presence of an emulsifier in the emulsion, which ensures deeper penetration of the agent into the pores of porous materials and between the fibers of textiles. This fact is particularly noticeable in laminated materials, in which there is practically no significant change in strength even after soaking in water. Laminated materials show savings in emulsion compared to the solution used, with improved mechanical properties, and it is further shown that these emulsions have a significantly wider range of uses. For example, emulsions can be added to concrete to reduce water absorption, plaster for the same purpose, used to glue various materials, at least one of which is porous, e.g. parquet on a concrete base - a water-oil-petrol-resistant joint is obtained, etc. in addition to the above economic and ecological advantages.

The preparation procedure is simple and does not deviate from the general practices of preparing emulsion systems. For example, the condensation product of a mixture of cresols and xylenols with paraformaldehyde or an aqueous solution of formaldehyde containing residual 2,6-xylenol is dissolved together with the emulsifier in an organic solvent, preferably in an aromatic hydrocarbon, e.g. in toluene or xylene, or in chlorinated hydrocarbons such as chloroform, carbon tetrachloride or trichloroethylene (chlorinated aromatic hydrocarbons can also be used) and this solution is mixed with the required amount of water. To achieve maximum concentration of solutions, it is appropriate to carry out the dissolution under heat and stirring. It is advisable to filter the solution, because the condensation product contains a small amount of catalyst (zinc salts), which do not dissolve in these solvents. The nature of the condensate allows the preparation of concentrates containing the condensate, emulsifier, possibly organic solvents and a small amount of water, from which a suitable emulsion is then prepared before use by dilution with water.

Various types of surfactants can be used as emulsifiers, anionic, cationic and non-ionic. Anionic surfactants include sodium dibutylnaphthalene sulfonate, cationic surfactants include lauryl amidoethylpyridinium chloride, and non-ionic surfactants include various oxyethylated fatty alcohols.

262,845

It is advisable to perform emulsification while warm /for faster dissolution in solution/.

Various additives (soluble in these solvents) can also be added to solutions of waste condensation products in aromatic or chlorinated hydrocarbons /depending on the type of material being treated/, e.g. plasticizers such as tricresyl phosphate or dibutyl phthalate, to increase the elasticity of the paint layer, various flame retardants, e.g. Retar 131 /diphenylisopropylphenyl phosphate/.

Materials treated with this suspension are smooth, shiny, mechanically and weather resistant, and transparent. Transparency allows the use of coatings where it is important that the structure of the original material remains visible. However, the waste condensate emulsion can also be modified as desired, such as dyeing, using a variety of organic dyes and inorganic pigments, stabilizing, plasticizing, etc. The invention will be illustrated by the following examples, # in the examples are by weight.

Example 1

500 g of 2,6-xylenol were refined by the method described in AO 231085, example 1. The xylenol used for refining contained 20.2% of other methyl derivatives of phenol.

After the described refining process and distillation of pure xylenol, the residue in the reboiler was mixed with 150 g of toluene and the resulting solution of the condensation residue was separated from a small amount of solid phase by filtration. 308 g of solution was obtained. The concentration of the waste product dissolved in toluene was determined by evaporation and was 51.36%. 20 g of Slovasol 0 was dissolved in the solution thus obtained at a temperature of 40°C and the whole mixture was poured into 308 g of water heated to 65°C with constant stirring. The resulting emulsion can be diluted several times without breaking.

A wooden cube with an edge of 6 cm made of dried fir wood was impregnated with the prepared emulsion diluted with water to 2 times its volume. After the coating had dried, it was alternately wetted with water /30 min/ and after wiping the water from the surface, it was dried freely in a stream of air. The maximum weight gain of the impregnated cube after 30 cycles was 2.2%. The condensate coating on the walls of the cube remained unchanged.

The weight gain of the same unimpregnated test specimens ranges between 18 and 25%. After several cycles, the specimens crack.

The ability to use the prepared emulsion for the production of laminates was confirmed by the following procedure: the emulsion was impregnated at 35°C

- 4,262,845 strips of cotton fabric measuring 100 mm x 100 mm and individual slices dried at 55°C. The slices were pressed together in 6 pieces at a temperature of 70-80°C, with a pressure of 7.5 kg/ ^cm2 , and from the pressing, double spoon-shaped tearing bodies were punched out, which had a width of 6 mm in the narrowest part. The exact height of the bodies was measured before the tearing test for each body separately /tab. 1/.

The tear test was performed on 10 bodies immediately after their manufacture and on 10 bodies after 60 hours of soaking in a 30°C water bath. The measured values shown in Table 1 are averages from the entire set of measurements and are compared with the values obtained when tearing the base material and the values obtained from laminated bodies with a condensate solution, described in AO 240372 example 1.

The results show that lamination using emulsion achieves higher strength and is little affected by long-term exposure to water.

Table 1

Sample Result of bursting tests Tensile strength of the specimen After exposure in o kg/mm water Without soaking 2 kg/mm Basic material 2.6 3.2 I Laminated material in the form of body-lamination performed according to AO 240372 4.4 4.6 Laminated material in the form of body-lamination done using emulsion 4.8 5.2

Example 2

1000 g of crude 2,6-xylenol was refined by the method described in Example 4 of AO 230842. The xylenol used for refining contained 20.2% of other methyl derivatives of phenol.

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After the refining process and distillation of xylenol, the residue in the reboiler was mixed with 700 g of xylene and the resulting solution was filtered.

999 g of solution was obtained, which, according to the determination by evaporation, contained 300 g of dry matter. 160 g of Slovasol 905 was dissolved in this solution with stirring at a temperature of 48°C and the obtained mixture was gradually diluted with water with stirring at a temperature of 55°C to a final volume of 3000 ml.

Tests of the effectiveness of emulsion impregnation were carried out as described in Example 1.

The maximum weight gain of the impregnated cube after 30 cycles was 1.8. The condensate coating on the cube walls remained unchanged.

Example 3

1000 g of crude 2,6-xylenol was refined by the method described in example AO 230842. The xylenol used for refining contained 20.2% of other methyl derivatives of phenol.

After the refining process and distillation of xylenol, the residue in the reboiler was mixed with 36 g of Slovasol 905 under stirring and at a temperature of 87°C and after thorough mixing, the entire contents of the reboiler were gradually added to 1 l of boiling water. Differential weighing revealed that 254 g of a molten mixture of phenol-formaldehyde condensate with Slovasol 905 had been added to the water. The resulting emulsion could be diluted with water as desired without causing the emulsion to break up. The emulsion impregnation tests were carried out in the same way as in example* 1.

The maximum weight gain of the impregnated cube after 30 cycles was 1.9%. The smooth, homogeneous condensate coating on the cube walls remained unchanged.

Example 4

Xylenol, which contained 3.6% of other ethylated methyl derivatives of phenol, was refined by the method given in the descriptions of the inventions according to Table 2, line 2, dealing with the chemical refining of xylenol. From 100 g of the residue after refining, emulsions were prepared in the manner given in Example 1 for the production of laminates from various materials. Test specimens for tear tests were made from the laminates. The production of laminated materials and bodies was carried out as given in Example 1. The emulsions were prepared from solutions as given in Example 1 or melts as given in Example 3. The concentration and nature of the substances used are given in Table 2. The tear tests were carried out according to Example 1. The summary of the results is compared with the values given in

262 84S tni in AO 240372 (line 14 and 14a in table 2).

Table 2

Line Significance 1 Attempt number 2 Refining carried out according to AO 3 Example number 4 Condensate emulsion for lamination Condensate mass g 5 solvents g 6 solvent 7 emulsifier weight g 8 emulsifier 9 method of preparing emulsion according to example 10 mass of water g 11 Lamination method of applying condensate 12 laminated material 13 Laminate tensile strength kg/mm^ without soaking 13a after soaking 14 Tensile strength of laminates kg/mm^ without soaking

prepared according to AO 240372

14a after soaking

Tensile strength of base material kg/mnr

1. 1 2 3 4 5 6 2. AO 232834 AO 236607 AO 232,870 AO 235679 AO 235608 AO 236128 3. 3 13 4 1 5 7 4. 50 50 50 50 50 50 5. 50 20 0 0 150 200 6. walking walking - - xylene xylene 7. 25 10 30 30 30 30 8. Slovasol 6018 Slovasol 802 Slovasol 6018 Slavonic p _v 370 Slovasol 0 Slovasol 81 9. 1 1 3 3 1 1 10. 300 200 1 000 300 300 500 11. by soaking by spraying by soaking by soaking paint by soaking 12. cotton fabric cotton fabric paper paper oak foil oak foil

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13. 4.7 4.5 1.1 1.2 5.7 5.9 13a 4.7 4.5 0.9 1.2 5.2 5.8 14. 4.5 4.5 0.9 0.9 5.6 4.1 14a 4.4 4.2 0.7 0.7 4.0 3.2 15. 3.2 3.2 0.4 0.4 2.8 2.8

Notes: 1/ Average value from 6 measurements /line 13 to 15/.

Example 5

1200 g of crude 2,6-xylenol was refined by the method described in Example 4. AO 230842. The xylenol used for refining contained 20.2% of other methyl derivatives of phenol. After the refining process was completed and the xylenol was distilled off, the residue in the reboiler was mixed with 770 g of xylene and the resulting solution was filtered.

1158 g of solution was obtained, which, according to the determination by evaporation, contained 328 g of dry matter. 200 g of Neokalu was dissolved in this solution with stirring at a temperature of 60°C and the obtained mixture was gradually diluted with water with stirring and a temperature of 60°C to a final volume of 1,600 ml.

Tests of the impregnation efficiency of the emulsions were carried out in the same way as in Example 1, however, the resulting emulsion was diluted with three times the volume of water.

The maximum weight gain of the impregnated cube after 30 cycles was 1.8%. The condensate coating on the cube walls remained unchanged.

Example 6

1,200 g of crude 2,6-xylenol was refined by the method described in Example 4. AO 230842. The xylenol used for refining contained 20.2% of other methyl derivatives of phenol.

After the refining process and distillation of xylenol, the residue in the reboiler was mixed with 40 g of Katexol 298 under stirring and at a temperature of 87°C and after thorough mixing, the contents of the reboiler were gradually dissolved in 1 l of boiling water. Differential weighing revealed _that 275 g of a molten mixture of phenol formaldehyde condensate with Katexol 298 had been added to the water. The resulting emulsion could be diluted with water as desired without breaking the emulsion. The emulsion impregnation tests were carried out in the same way as in example 1, however, the resulting emulsion was diluted with 2.5 times the volume of water.

The maximum weight gain of the impregnated cube after 30 cycles was 2.1%. The smooth, homogeneous condensate coating on the cube walls remained unchanged.

Claims (1)

262 845 Impregnating and laminating agent based on the condensation products of phenol, cresols and xylenols with formaldehyde> falling off in the chemical refining of 2,6-xylenol with formaldehyde or paraformaldehyde, characterized in that it contains from 5 to 50 parts by weight of condensate? up to 1000 parts by weight of water and up to 200 parts by weight of aromatic hydrogen.