DE102008037757A1 - In situ hydrophobizing agent based on native epoxide, useful e.g. in polymer concrete or grout, comprises epoxidized fatty acid ester compound, or alkoxylated form of epoxidized fatty acid ester-ether compound, as precursor substance - Google Patents

Abstract

In situ hydrophobizing agent on the basis of native epoxide, comprises: epoxidized fatty acid ester compound (I), or alkoxylated form of epoxidized fatty acid ester-ether compound (II), as a precursor substance, where (I) is formed by crosslinking polyether-ester or polycarboxylic acid polyester-ester with high crosslinking thickness, under UV-radiation. In situ hydrophobizing agent on the basis of native epoxide comprises: epoxidized fatty acid ester compound of formula (I), or alkoxylated form of epoxidized fatty acid ester-ether compound of formula (II), as a precursor substance, where (I) is formed by crosslinking polyether-ester or polycarboxylic acid polyester-ester with high crosslinking thickness, under UV-radiation. In formula (I): R 5alkOOC(CH 2) 7, alk=C 3H 5O 2- or CH 3; R 6(CH 2) 9 - 3 nor (CH 2) k-CH 3; R 718-24C-alkyl; k : 10 or 11; and n : 1-7. In formula (II): R 6(CH 2) 9 - 6 n. An independent claim is included for the in situ hydrophobization of the nature-natural material, cast stone, or wood or wood materials with the in situ hydrophobizing agent comprising processing the in situ materials via surface treatment or mass hydrophobic treatment. [Image].

Description

The The invention relates to in situ hydrophobing, suitable substances and their use and method of in situ hydrophobing. In particular, the present invention describes different hydrophobizations of porous surfaces, the mass hydrophobization for cement bonded artificial stones and hydrophobic polymer concrete as jointing mortar.

The use Hydrobhobierungsmittel according to the invention Precursor substances based on native epoxides from animal and vegetable oils. The actual hydrophobic properties are generated in situ from them thus coated surfaces or staggered masses either by polymerization by means of UV radiation, acid-catalytically with crosslinkers or by reactions with the matrix.

The hydrophobicity of chemical structures can be estimated by numerical values, so-called increments (emulsifiers for food chemistry in: Springerverlag 1985 p.14ff). In carbochemistry, there are z. B. long unsubstituted hydrocarbon chains, in 1 with type 1 and type 2 or in silicon chemistry Si-O-Si structures, in 1 marked with type 3 to 6. These basic structures are, as Table 1 identifies, used individually or in admixture as a hydrophobing agent both for surface treatment and for mass hydrophobization in cement-bound concretes (Table 1).

Although hydrophobic structural elements are a necessary, but by no means sufficient, condition that a chemical compound is used as a hydrophobing agent. Rather, substances or mixtures must have additional properties in order to be applicable as technically usable water repellents. This property profile is summarized in Tab. Table 1: Patent overview of water repellents group structure application comment patent Type 1 Natural stone surfaces sacrificial layer G 9307 701.3 UB Type 1, 2, 4 Mass, artificial stone Addition of alkali salts DE 1803079 A1 Type 2, 3 Mass, artificial stone DE 102 004 057996 A1 Type 6 Mass, artificial stone DE 19747794 A1 Type 3 Natural stone surfaces sacrificial layer DE 9207701 U1 Type 2, 3, 4 Natural stone surfaces sacrificial layer DE 3048125 A ! Type 4 Natural, work and artificial stone surfaces Addition of hexafluorosilicate DE 4037653 A1 Type 4 Mass, artificial stone Addition of hexafluorosilicate DE 1807079 A1 Type 5 Natural, work and artificial stones DE 4033155 C2 Type 2, 3 Mass, artificial stone DE 10323205 A1 Type 1, 2 Mass, artificial stone DE 19923076 B4 Type 5 surfaces deep impregnation DE 3228660 A1

For the surface treatment of any open-pore stone and wood materials, it is necessary that the hydrophobic substance can penetrate into the surface (Table 2, 1st line). That is, all known surface treatment hydrophobing agents have in common that they must be diluted with a solvent so that the active ingredient in the surface pores of the Table 2: Additional requirements for hydrophobing property Type 1 Type 2 Type 3, 5 Type 4 Type 6 penetration m. P. _{) 1} m. S. m. S. m. S. m. S. own steam pressure rel. high medium small none medium stability UV stable Bio and UV degradation UV degradation stable UV degradation colour G> 1 _{) 2} G> 2-3 G <1 G <1 G <1 odor without at biodegradation without without without environmental given given negative negative negative

• ₁ m. S. only possible with solvent _{) 2} G Gardner number

matrix can penetrate. The solvent must evaporate easily not the active ingredient itself. Its vapor pressure should be be as small as possible, ultimately so long in the surface remain. This ideal is actually only for Silicate (type 4) met, but only partially against the paraffins (Table 2, line 2). Fatty acids and their methyl esters at 1 bar boiling temperatures between 300 and 360 ° C, are so difficult to evaporate.

The Stability of Si-organic compounds becomes long-term through the penetrating about 1-2 mm deep UV radiation in Asked a question; One also speaks in this context of "sacrificial layers". Fatty acid derivatives in the structures found in the patents are also subject to biodegradation (Table 2, line 3, column 2).

The Color assessment not only means the inherent color of the water repellent, but the color difference between treated and untreated Surface.

So may not with travertine or marble stones after application Color deepening occur opposite to the untreated surface.

Further the water repellent must not have any odor which is generally given with Si compounds, even later after application by biodegradation develop, which in the previously used fatty acid derivatives, however, not given is.

After all the chemical and its manufacturing process are environmentally friendly to judge. The preparation of Si-organic compounds takes place by means of methyl chloride according to the Rochow method., So a Environmental toxin. Also hexafluorosilicates as additives in type 4 structures are not considered environmentally friendly in the manufacturing process.

Abbildung 1: Strukturelemente mit hydrophobierender Eigenschaft

Figure 1: Structural elements with hydrophobizing property

The in DE 101 51 469 B4 The hydrophobization agent disclosed consists of hydroxyepoxifatty acid glycidic esters having an EO number EO> 3 and polyphosphoric acid glycidyl esters having a hydroxyl number between 80 and 180. This two-component system is intended for the hydrophobization of disposable materials from renewable raw materials and biodegradable for a specified cycle time.

Especially in the field of natural and artificial stones, but also for wood and wood-based materials there is still a high need for hydrophobic Coatings or equipments that keep these items permanently protect. It is therefore an object of the invention, hydrophobing and to provide suitable substances which are durable and resistant to chemicals and weathering surface or equipment of household goods.

According to the invention the task by an in situ hydrophobing agent with the features after Claim 1 solved. Further embodiments of the invention In situ hydrophobing agents include the features of the subclaims 2 to 8.

mit
R5 = AlkOOC(CH₂)₇ und Alk = C₃H₅O₂-Rest oder CH₃
R6 = (CH₂)_9-3n aber auch (CH₂)_k-CH₃ mit k = 10, 11
und 1 < n < 7,
die sich dann in die Endstrukturen wandeln, wenn man mit Hilfe eines UV-Katalysators und UV-Strahlung, z. B. Sonnenlicht, sie in eine Polyetherstruktur vom Typ 8 auspolymerisiert.The essence of the present invention is to use water repellents of fatty acid epoxides or their derivatives, prepared from animal and vegetable fats and oils. In contrast to the fatty acid structures mentioned so far in the patent literature, such as fatty acid alkoxylates or fatty acid salts, however, epoxides of the fatty acids are used, and this is also completely new, compounds of the general formula (type 7) are used as precursor substances.

With
R 5 = AlkOOC (CH ₂ ) ₇ and Alk = C ₃ H ₅ O ₂ radical or CH ₃
R6 = (CH ₂ ) _9-3n but also (CH ₂ ) _k -CH ₃ with k = 10, 11
and 1 <n <7,
which then transform into the final structures when using a UV catalyst and UV radiation, eg. As sunlight, polymerized in a polyether structure of type 8.

mit R7 = PolycarbonsäurerestOn the other hand, if the epoxide type 7 is acidified with polycarboxylic acids, structure-type hydroxypolyesters 9 are formed.

with R7 = polycarboxylic acid residue

Although the precursor substance type 7, but especially the resulting synthesis products of types 8 and 9, already have more oxygen atoms, even hydrophilic OH groups, they unexpectedly possess strong hydrophobic properties. Of course, the radicals R5 and R6 themselves are hydrophobic, as in the known type 2 fatty acid derivatives. But this alone can not be the cause of their much greater hydrophobicity compared to the simple fatty acid derivatives. Rather, the crosslinking results in the formation of 3-dimensional molecular polyether or polyester networks which are not permeable to the water molecules (H ₂ O) _x which are intrinsically polymeric. The epoxides must by no means react only with themselves or with polycarboxylic acids, but also form compounds with the matrix molecules, eg. For example, build silicates from the rocks networks:

Of the serious difference to the state of the art is that the hydrophobic Only in situ, ie only after application of the hydrophobizing agent formed by full-strength chemical reactions becomes. These polymerization reactions both vaporize as well as migrating the hydrophobing agent completely impossible. Also the biological degradation of the structures of the Type 8 and 9 is not possible due to the high degree of cross-linking although the precursor substances themselves are biodegradable. There the oxyran number (ORZ) of the epoxides in the region 6 <ORZ <7 is, for the spatial networking but only maximum 3 are necessary, remain 3 to 4 Oxyranringe as sacrificial structures against the penetrating UV rays or for the formation of matrix reactions according to Eq. 1.

specially in the case of polyether structures, an extraordinary one is observed pH resistance in the range 2 <= pH <= 13.7, but also a high solvent stability. Ie., Polyether layers are neither by lytic solvents still to be removed by swelling with solvents.

Unexpectedly, polyether structures of type 8 give extremely hydrophobic surface coatings such that when spraying graffiti dyes, pigment and polymer bodies separate during the spraying process due to gravity, the graffiti image is distorted. Even after several weeks, even with crosslinking graffiti paints, the ink residue is relatively easily removable with acetone without destroying the protective layer. This applies to stone and wooden surfaces. Table 3: Dissolution and swelling experiments of polyethers Acids / alkalis findings Solvent ₁₎ findings other chemicals findings 0.01 n KOH pH = 12 if. H ₂ O if. biodiesel if. Formic acid 98% if. diethyl ether if. Tetrahydrofuryl-2-methyl acetate if. Acetic acid 98% if. acetone if. glycerol triacetate if. H ₂ SO ₄ pH = 1.54 if. n-heptane if. citric acid if. chloroform if. Mastofflösung if. methanol if. ethanol if.

• ₁₎ Test time 6 weeks o. B. without findings

A further advantage of the hydrophobizing agents according to the invention over the fatty acid salts known from the literature is that they have no, stones-decomposing cations. In addition, their synthesis process, in contrast to the synthesis of Si-organic compounds environmentally friendly, because the main raw materials are animal or vegetable oils and H ₂ O ₂ ; Air or water emissions with environmental toxins do not take place.

Artificial stones Cement-bound concretes can be mixed with the epoxide derivative Hydrophobic type 10 mass. In conjunction with a plasticizer can you z. B. the mixing water bound for the cement Limit concrete to the amount of water of crystallization. This is greatly reduced the possibility of capillary formation in the concrete. The sub-concrete is thus hydrophobic.

mit
R6 = (CH₂)₉-6n, R7 = C₁₈ bis C₂₄-AlkylrestFinally, it is possible to use the precursor of this etherification reaction to the alkoxylated fatty acid methyl esters, the white oil methyl ester epoxides themselves, as water repellents.

With
R 6 = (CH ₂ ) ₉ -6n, R 7 = C ₁₈ to C ₂₄ -alkyl radical

Instead of white fat methyl ester epoxide can be used effectively the Krambemethylester epoxide. It is characterized by a high proportion of about 55% of C ₂₂ fatty acids and by a small proportion of C ₂₄ fatty acids, is therefore in its hydrophobing effect better than the C ₁₈ fatty acid derivatives, but also priced more expensive.

In Ethanol dissolved to 40 to 60% can both epoxides (Type 7 and Type 10) used for the hydrophobization of limestones become. Color differences of treated and untreated surfaces do not occur. In sandstones penetrate the said water repellents several mm deep. The treated stone remains gas-tight, d. H. also permeable to water vapor, which is for the Protection of historic buildings is of particular interest (Table 4, Line 1).

Worth mentioning in connection with the hydrophobing is that you can use polymer concrete instead of the usual lime mortar when laying natural or natural stones. Type 9 hydrophobic polymer concrete protects the stone against rising damp. (Table 4, line 3). Table 4: Applications of epoxy-based water repellency and application examples application of reaction applications eluent structure type porous surfaces matrix reaction Sand and limestones ethanol 7 porous surfaces (antigraffiti) photopolymerization Marble, wood, masonry reactive diluent 8th masses acidic polymerization Grout for any stones o. Fired clay without 9 masses matrix reaction Cement-bound concretes H ₂ O 10

The mode of application of the above-mentioned water repellents may be quite different. Table 5: Application method of in situ hydrophobing operation area Aplikationsart eluent surface Spraying, brushing, rolling of Type 7 or Type 8 compounds + Gap Mix finely ground aggregates with epoxy resins type 9 - Dimensions Incorporation of Type 10 structures in cement mortar -

For the surface treatment of stones or woods The Precursorepoxidharze type 7 and 8 (Tab. 5, line 1). The surface of Type 7 applications can be both indoors and outdoors, for Type 8 applications dominant in the outdoor area because of Initiation of the photochemical reaction by UV radiation.

hydrophobic Grouts once protect the stone against rising Water from the ground in the outdoor area. Indoors are the hydrophobic grouts for wet cell construction advantageous used. Since the epoxy resins presented cold-curing are a laying in the temperature range 10 <= T <= 25 ° C appropriate.

to Hydrophobization of cement-bound concretes is done in mixing water the agent of type 10 was added (Table 5, line 3). Is advantageous doing the additional use conventional Flow improver, optionally in combination with depolymerized Water to the amount of mixing water as low as possible to keep.

Based Illustrations attached are exemplary embodiments the invention explained in more detail. Showing:

1 Red wine stoned marble stone with hydrophobic surface

2 Stone sprayed with graffiti paint with a hydrophobic surface

3 Stone after 2 after first wiping

Experimental Procedure

A Preparation of the UV coating mixture

High Omega Leinölglycidester-epoxide Type Ep-10/1 with the EO number of EOZ ≥ 12.5 is included 1% Triarylsulfoniumhexafluorantimonat added. To the mixture acetone is added in the ratio 1: 1 or methyl ester epoxide as reactive diluent in the ratio 4: 1. You brush or splashes the surfaces of limestones (marble, travertine, Limes toner). The treated surface hardens in daylight after about 20 to 30 'depending on the sunlight.

B Preparing the hydrophobicized Surfaces with red wine and graffiti paint

The surfaces prepared according to the instructions A are doused with red wine or sprayed with graffiti (see also 1 to 3 ). The prepared surfaces are cleaned in the case of red wine with H ₂ O ( 1 ) or with acetone in graffiti coatings. In both cases, the surfaces can be easily cleaned without scratching or carving ( 1 respectively. 3 ).

C Preparation of alkoxylated fatty acid methyl esters

1 mole of fatty acid methyl ester consisting of about 40% of saturated fatty acid moieties, especially stearic acid, are reacted with the adequate amount of performic acid to form the epoxide. This Methylesterfettsäureepoxidgemenge is reacted with equimolar parts of a C ₁₈ -alkanol in the presence of 2% ZnC ₁₂ as a catalyst and stirred for about 16 hours at about 80-90 ° C. Thereafter, the catalyst is washed with H ₂ O and the product is distilled to freedom from water. This gives alkoxylated fatty acid methyl esters.

D Mass of hydrophobic concrete

150 g of Liquiment (cement) are mixed with 50 g of H ₂ O. The mixing water (only the amount of water of crystallization) is added to 1 g of flow agent and 0.5 to 2 g of alkoxylated fatty acid methyl ester according to regulation C. The water absorption of this cement-bound concrete is ≤ 3% after repeated heating at 200 ° C.

E Determination of water penetration according to DIN 52 617

In this test, immerse the specimen about 3 mm deep in a filled with H ₂ O shell. The side surfaces are sealed with epoxy resin.

Gravimetrically the water absorption in kg / m ^{2 is determined} in the time [kg / m ² · h1 / 2].

Clear are the water penetration numbers in the hydrophobized materials smaller than in the untreated (Table 6, lines 2, 4, 6, 8 and 10).

Table 6: Water penetration numbers according to DIN 52 617

• ₁₎ The hydrophobization by means of UV varnish is characterized by UV, those with white fat methyl ester poxides in ethanol with W, the mass hydrophobized concrete with MB.

F Polymer concrete with hydrophobic property

3 g of glycidester epoxide are mixed with a mixture of 0.4 g of maleic acid, 0.3 g of methyltetrahydrophthalic anhydride and 0.45 g of pyromellitic anhydride touched. The processing time at 20 ° C is approx. 45 ', the setting time until dimensional stability approx. 6 H.

G Preparation of methyl ester epoxides

Weißfett- or Crambemethylester be with performic acid in Epoxidized known manner. The epoxidation can be in equimolar Quantities are made. As a reactive diluent for application A are also smaller Epoxierungsgrade for reasons of viscosity useful.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - G 9307701 [0004]
• DE 1803079 A1 [0004]
• - DE 102004057996 A1 [0004]
• - DE 19747794 A1 [0004]
• - DE 9207701 U1 [0004]
• - DE 3048125 A [0004]
• - DE 4037653 A1 [0004]
• - DE 1807079 A1 [0004]
• - DE 4033155 C2 [0004]
• - DE 10323205 A1 [0004]
• - DE 19923076 B4 [0004]
• - DE 3228660 A1 [0004]
• - DE 10151469 B4 [0012]

Claims (12)

In situ hydrophobing agents based on native epoxides, wherein the hydrophobizing agents as precursor substances epoxidized fatty acid esters of the general formula (type 7)

with R5 = AlkOOC (CH ₂ ) ₇ and Alk = C ₃ H ₅ O ₂ radical or CH ₃ R 6 = (CH ₂ ) _9-3n but also (CH ₂ ) _k -CH ₃ with k = 10, 11 and R7 = C ₁₈ -C ₂₄ alkyl radical and 1 ≦ n ≦ 7 or in alkoxylated form epoxidized fatty acid ester ethers of the general formula (type 10)

with R6 = (CH ₂ ) ₉ -6n, where the type 7 compounds form UV-crosslinking polyether esters or polycarboxylic acids polyester esters of high crosslinking density. Hydrophobing agents according to Claim 1, characterized in that they have in situ the structure of polyether esters of the general formula of Type 8

or the structure of polyester-ester of general formula type 9

form with R7 = polycarboxylic acid radical. Hydrophobizing agents according to claim 1 or 2, characterized characterized in that the epoxidized fatty acid ester is selected is an epoxidized fatty acid ester of white or bone grease or flax, scorpion fish, fish or rotten oil. Water repellents according to one of the claims 1 to 3, characterized in that at UV initiation type Crosslink 7-compounds with themselves to polyether esters. Water repellents according to one of the claims 1 to 3, characterized in that for crosslinking polycarboxylic acids or their anhydrides are used and the polycarboxylic acids or their anhydrides preferably maleic acid, oxalic or Tartaric acid, pyromellitic anhydride or methyltetrahydrophthalic anhydride are. Water repellents according to one of the claims 1 to 3, characterized in that for the type 7 compounds a flow agent is used and that the flow agent is selected from acetone or ethanol. Water repellents according to one of the claims 1 to 3, characterized in that they are UV-initiated Curing as a reactive diluent a fatty acid methyl ester or its epoxide having a concentration of ≤ 10%. Use of in situ hydrophobing after one of claims 2 to 7 for the hydrophobization of natural natural or artificial stones or wood or wood-based materials. Use of in situ hydrophobing after Claims 1 and 2 for polymer concrete or joint mortar. Use of in situ hydrophobing agents according to Claims 4 and 7 as Antigraffitischutzschicht. Process for the in situ hydrophobization of natural natural products or artificial stones or wood or wood-based materials with an in situ A hydrophobing agent according to any one of claims 1 to 7, characterized in that the processing of in situ substances by surface treatment or mass hydrophobization he follows. Process for the in situ hydrophobization according to claim 11, characterized in that in the case of cement-bound concretes a mass hydrophobization by means of compounds of the general Formula (Type 10) takes place.