AU2005306034B2

AU2005306034B2 - Method for the production of a modified montan wax a modified montan wax and use of modified montan wax for production of an aqueous montan wax composition

Info

Publication number: AU2005306034B2
Application number: AU2005306034A
Authority: AU
Inventors: Jorg Abraham; Jutta Edel; Andreas Mieth
Original assignee: ROMONTA GmbH
Current assignee: ROMONTA GmbH
Priority date: 2004-11-17
Filing date: 2005-11-11
Publication date: 2010-12-02
Anticipated expiration: 2025-11-11
Also published as: AU2005306034A1; DE502004011828D1; CN101076568A; DK1661951T3; JP2008520776A; ATE486102T1; ES2355473T3; EP1661951A1; PT1661951E; JP4986295B2; WO2006053686A1; PL1661951T3; CN101076568B; EP1661951B1; SI1661951T1

Abstract

Preparation of a modified montan wax (I) comprises melting the montan wax first at 100-140[deg]C, subsequently adding tall resin (3-mass %) or its ester under agitation, introducing various acid groups in the presence of mineral acids with oxidizing effect under air injection to the obtained wax resin mixture, agitating at 110-150[deg]C, and converting the acid groups by adding alkali hydroxide (0.7-4.5 mass %) into corresponding salts. An independent claim is also included for (I), which is a product from a purposeful chemical reaction of tall resin or its ester mixed with montan wax, where acid groups transferred into its salts are present in molecular skeleton.

Description

CERTIFIED TRANSLATION FROM THE GERMAN LANGUAGE - Page 1 WO 2006/053686 PCT/EP2005/012119 PCT/EP2005/012119 VERIFICATION OF TRANSLATION I, Regina Noack, Im Plotz 3, 07751 Zimmritz, Germany, state the following: I am the translator of the document attached and I state that the following is a true translation to the best of my knowledge and belief. B~egina Noack Signature: .Translator of Spanish and Erg Hsh or th Cou-ts and Notaries Fr"e state of Thunga (Germany) ~ Dt:15 May 2007 0 fhe Free State of Thurngia (Germany) Title Method for the Production of a Modified Montane Wax, Modified Montane Wax, and Use of Modified Montane Wax for the Production of an Aqueous Montane Wax 5 Compound State of the Art The present invention relates to a method for the production of a modified montane 10 wax, a modified montane wax that can be produced according to this method, and the use of the same for the production of an aqueous montane wax compound with hydrophobic properties. For systems with hydrophobic effect, montane wax with solid hydrocarbons in solid, finely distributed form is used according to the state of the art, as described, for 15 example, in DD 160 516. Furthermore, according to DD 205 882, montane wax and solid hydrocarbon compounds in solid, finely distributed form or as emulsion or dispersion are used for such systems. The DD 221 994 describes the treatment of products to be made hydrophobic, using an 20 emulsion of montane wax, an emulsifier consisting of ethylene oxide adducts on the basis of alkylphenols and longer-chain fatty alcohols, and water. Moreover, hydrophobising with montane wax and paraffin is mentioned in the DD 284 126. In the EP 0 669 377, the use of an aqueous emulsion, consisting of paraffinic 25 hydrocarbons, montane wax and polyvinyl alcohol, using usual emulsifiers, i.e. non ionic tensides such as alkyl-phenoxy-poly(ethylene-oxide)ethanols, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters, as well as anionic tensides, for example saponified fatty acids, and known stabilizers, i.e. alkali metal or ammonium hydroxides, has been proposed. 30 CERTIFIED TRANSLATION FROM THE GERMAN LANGUAGE - Page 2 WO 2006/053686 PCT/EP2005/0 12119 2 The WO 99/35103 depicts a montane wax emulsion with sulphatic anionic tensides, for example sulphate or sulphonate, sulphonated naphthalene-formaldehyde condensates, as polymer preferably aryl sulphonate, naphthalene sulphonate, advantageously as sodium salt, and non-ionic tensides, for example higher alcohol, 5 alkenol, alkanoic or alkenoic acid or aryl alcohol or carboxylic acid ethoxylates with at least two equivalents of ethylene oxide, ethoxylated alkyl, alkenyl, alkanoyl, alkenoyl components, alternatively also alkyl, alkenyl, alkanoyl, alkenoyl and aryl components produced by polymeric reaction with glycol, using montane wax and petroleum hydrocarbons, i.e. paraffin. 10 The US patent 4,748,196 describes an aqueous emulsion of a wax component, paraffin, montane wax or polyolefin wax, with olefin-maleic acid anhydride derivatives, alkali hydroxides and/or non-ionic emulsifiers, as well as the common stabilizers polyvinyl alcohol, polyacrylamide, methyl cellulose, carboxymethylcel lu lose or hydroxypropyl cellulose. 15 Finally, the WO 02/098816 mentions an aqueous emulsion with hydrocarbon waxes, i.e. paraffin wax, carnauba wax, polyethylene wax, synthetic wax esters, acid wax, maleic acid-modified hydrocarbons and combinations thereof, using maleic acid anhydride grafted polyolefinic polymers and polyvinyl alcohol. 20 It would be desirable to have an aqueous montane wax compound system, for example as montane wax dispersion, that, compared to the known state of the art, would feature higher stability, increased hydrophobic effectiveness in the treatment of different material systems, and a reducing effect on the formation of mould fungi. The existing systems are not or only unsatisfactorily able to achieve that. 25 30 3 Description of the Invention The present invention relates to a method for the production of a modified montane wax, a modified montane wax that can be 5 produced according to this method, and the use of the same for the production of an aqueous montane wax compound with hydrophobic properties. The solution of this task is described in the independent patent claims. The subordinated claims contain useful 10 embodiments. In an aspect, there is described a method for the production of a modified montane wax, characterised in that montane wax is firstly melted at 100 0 C to 140 0 C, that, thereafter, 3 to 30 weight% of tall resin or an ester 15 made from tall resin are added with stirring, that, thereafter, different acid groups are introduced into the existing wax-resin mixture in the presence of mineral acids with oxidising effect and with air injection and stirring at a temperature of 110 0 C to 150 0 C, 20 and that, thereafter, these acid groups are converted into the salts thereof by addition of 0.7 to 4.5 weight% of alkali hydroxides. In another aspect, there is described a tall resin or an ester made from tall resin is added to montane wax, which is 25 afterwards subjected to a targeted chemical modification. It is proposed that montane wax is firstly melted at 100 0 C to 140*C, preferably at 120'C, and that then 3 to 30 weight%, preferably 15 weight%, of tall resin or an ester made from tall resin is added with stirring. 30 Tall resin itself contains, as main components, a mixture of abietic acid, dehydroabietic acid, palustric acid, dihyroabietic acid, neoabietic acid, and primaric and isoprimaric acid. As tall resin ester, the glycerol ester is explicitly mentioned here. In the following reaction step, a 35 chemical structural change of the montane wax mixture is produced by mineral acids with an oxidising effect in the presence of oxygen and under stirring at 110 0 C to 150 0 C, 2387869_1 (GHMatters) 2518110 3A preferably at 140 0 C. For example, when using 0.5 to 4.0 weight%, preferably 2.0 weight% of concentrated sulphuric acid and adding oxygen by air injection into the molecular skeleton of the present wax-resin mixture, sulphonic acid 5 groups are introduced and further carboxyl groups are produced. After that, these groups are converted with 0.7 to 4.5 weight%, preferably 2.4 weight% of alkali hydroxides into the corresponding salts thereof. 10 According to the invention, a material system in the form of a modified montane wax is obtained, the structure of which can be influenced by the quantities and process conditions chosen and the properties of which can be varied according to the demand. 15 23878691 (GHMatters) 25/08110 CERTIFIED TRANSLATION FROM THE GERMAN LANGUAGE - Page 4 WO 2006/053686 PCT/EP2005/012119 4 Comparison measurements by means of FT-IR spectroscopy (Fourier Transform Infrared Spectroscopy) of montane wax in its initial state and the modified montane wax produced according to the invention have shown clear changes in the wave number range of about 620 cm-', 1,030 cm ', 1,1 10 cm- 1 , 1,714 cm-', and 1,735 cm-1. 5 Thermograms recorded according to the DSC method (Differential Scanning Calorimetry) showed a clear shift in the curve structure as well as a significant change in the peak maximum and the normalized enthalpy. It is furthermore proposed, according to the invention, to use the modified montane 10 wax for the production of an aqueous montane wax compound system, for example of a montane wax dispersion. Surprisingly, it has turned out that a montane wax compound system, containing a montane wax modified according to the described method instead of montane wax, shows a higher stability and a significantly increased efficiency in making 15 hydrophobic different application material systems, for example gypsum, cardboard, wood, and the like, or combinations thereof. Besides its usability in different application material systems, it stands out due to its reducing effect on the formation of mould fungi. 20 Execution example Now, the invention will be described more in detail by way of an execution example. The following components are used for the production of the modified montane wax 25 according to the invention: Montane wax 80.6 weight % Tall resin ester with glycerol 15.0 weight % Sulphuric acid (conc.) 2.0 weight % 30 Potash lye (45 %) 2.4 weight % CERTIFIED TRANSLATION FROM THE GERMAN LANGUAGE - Page 5 WO 2006/053686 PCT/EP2005/0 12119 5 The montane wax is melted with stirring at about 120'C. Tall resin ester with glycerol is added to the liquid montane wax and concentrated sulphuric acid is dosed at about 140'C with air injection. After a reaction time of about 60 minutes, potash lye is added with stirring. After the salt formation has been completed, the modified montane wax 5 produced this way is shaped. According to the described production method, the modified montane wax in question is a product obtained by a targeted chemical reaction of montane wax mixed with tall resin or an ester made from tall resin, with different acid groups converted into their salts being present in the molecular skeleton. 10 In the relevant Figures I and 2 an FT-IR comparison (Fourier Transform Infrared Spectroscopy) between montane wax in the initial state and the invented modified montane wax is shown. The changes are clearly visible especially in the wave number range of about 620 cm-', 1,030 cm-', 1,1 10 cm-', 1,714 cm ', and 1,735 cm-'. Figure 3 shows two thermograms recorded according to the DSC method (Differential 15 Scanning Calorimetry), comparing the starting component with the modified montane wax. A clear shift in the curve structure as well as a significant change in the peak maximum and the normalized enthalpy can be seen. Now, the modified montane wax, as invented, is available as starting component for 20 the production of the aqueous montane wax compound, for example in the form of a montane wax dispersion. Known methods are applied for this purpose. The compound is composed of 5 to 50 weight % of modified montane wax and 95 to 50 weight % of paraffinic hydrocarbons. It is dispersed by using the emulsifiers and stabilizers generally employed for 25 conventional non-modified montane wax systems. 30 CERTIFIED TRANSLATION FROM THE GERMAN LANGUAGE - Page 6 WO 2006/053686 PCT/EP2005/0 12119 6 The following table documents the stability, surprisingly turned out in connection with the use of a dispersion with the invented modified montane wax, compared to a dispersion with non-modified montane wax. Days of Separated layer, using Separated layer, using storage non-modified modified montane wax [mm] montane wax [mm] 5 2 0 10 4 0 15 5 20 8 1 25 11 2 30 12 2 35 14 3 40 17 4 45 18 4 50 21 4 55 22 4 60 23 5 65 27 5 70 28 5 75 30 6 80 32 6 5 When the invented modified montane wax was used as active component in the aqueous montane wax compound (dispersion), surprisingly also a significant improvement of the hydrophobic effect on different material systems, compared to the effect of the dispersion without a modified montane wax, became apparent. 10 7 These differences in the efficiency are shown in the following table by way of an application example of gypsum hydrophobising after a two-hour immersion in water. Concentration in Water absorption Water absorption gypsum using non-modified using modified [weight%] montane wax montane wax (referred to solid [weight%] [weight%] matter of the dispersion) 0.6 20.5 4.6 0.8 10.6 2.2 1.0 4.8 1.0 5 It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other 10 country. 2387869_1 (GHMatters) 25/08/10

Claims

1. A method for the production of a modified montane wax, characterised in that montane wax is firstly melted at 5 100 0 C to 140 0 C, that, thereafter, 3 to 30 weight% of tall resin or an ester made from tall resin are added with stirring, that, thereafter, different acid groups are introduced into the existing wax-resin mixture in the presence of 10 mineral acids with oxidising effect and with air injection and stirring at a temperature of 110 0 C to 150 C, and that, thereafter, these acid groups are converted into the salts thereof by addition of 0.7 to 4.5 weight% is of alkali hydroxides.

2. The method for the production of a modified montane wax according to claim 1, characterized in that montane wax is melted at 120 0 C, 20 that 15 weight% of tall resin or an ester made from tall resin are added to the melt, that the temperature during the introduction of the acid groups is 140 0 C, and that, finally, 2.4 weight% of alkali hydroxides are added. 25

3. The method for the production of a modified montane wax according to any one of the preceding claims characterised in that the introduction of acid groups into the molecular skeleton takes place by using 0.5 to

4.0 weight%. 30 4. The method for the production of a modified montane wax according to claim 3, characterised in that the introduction of acid groups into the molecular skeleton takes place by using 2.0 weight% of concentrated 35 sulphuric acid.

5. The method for the production of a modified montane wax 2387869_1 (GHMatters) 25/08/10 9 according to any one of the preceding claims characterised in that glycerol ester is used as tall resin. 5

6. The method for the production of a modified montane wax according to any one of the preceding claims, characterised in that the modified montane wax is a product obtained from a targeted chemical reaction of montane wax mixed with tall resin or an ester made from 10 tall resin, with the presence of acid groups converted into the salts thereof that had been introduced into the molecular skeleton.

7. The method for the production of a modified montane wax 15 according to any one of the preceding claims, characterised by the use of the modified montane wax for the production of an aqueous montane wax compound with hydrophobic properties. 20

8. The method for the production of a modified montane wax according to claim 7, characterised by the use of the modified montane wax for the production of an aqueous montane wax compound system in the form of a dispersion, mainly consisting of 5 to 50 weight% of modified montane 25 wax, 95 to 50 weight% of paraffinic hydrocarbons, and known emulsifiers and stabilizers.

9. The method for the production of a modified montane wax substantially as herein described with reference to the 30 accompanying drawings. 23878691 (GHMatters) 16/09/10