DE4427879A1 - Biodegradable wax compsn. - Google Patents

Abstract

A biodegradable wax compsn. contains (a) 90-70 pts. of a functionalised synthetic wax and/or paraffinic hydrocarbon with mol. wt. 500-5000, 5-50 mmols of COOH/mol CH2, 5-50 mmols OH/mol CH2, and 0-100 mmols of other oxygen-contg. gps./mol CH2, and (b) 10-30% of plant oils and/or fatty acids or fatty alcohols obtd. from them.

Description

The invention relates to biodegradable wax compositions and wax emulsions prepared therefrom, which are known to all Wax applications are used.

Since the beginning of the 60s, the production of the soge called synthesis waxes, usually low molecular weight Ethylenpolymeri sate, known and described; as well as the extraction of paraf petroleum hydrocarbons (Ullmann, Encyklo pädie Weinheim, Verlag Chemie, 1983, pp. 36-45).

It is also known that oxygen-containing functional groups in to introduce the wax molecule by oxidation (DD 1 16 625) and by further modification of the waxes or wax oxidates Saponification or esterification to expand the range of applications (for example DD 2 20 186, DD 2 54 732). These modifications, however, are z. T. very costly and with significant environmental impact connected.

These waxes or wax oxidates have a wide range of uses spectrum. They generally have no harmful effects Characteristics, however, are largely inert and are of Microorganisms attacked only very slowly. Therefore match these known waxes are not the most recent of the final biodegradability of the basic products or forbid because of the difficulties in mining in biological water purification systems or in receiving waters from the front in some application areas. Thus divorce also Möglichkei th the recycling cycles, such. B. composting, from.

The object of the invention is the development of in-situ Wax compositions that contrast with the conventional wax sen through the ability of controlled biodegradation draw and in a wide range of characteristics, in particular in terms of hardness, flexibility and viscosity, targeted can be set, with the property setting without World damaging operations should be possible.

The object is achieved by an insitu wax composition containing
90 to 70 parts by weight of functionalized synthesis waxes and / or paraffinic hydrocarbons having the following characteristics:

• - average molecular weights of 500 to 5000
• - Carboxyl groups of 5 to 50 mmol / mol CH₂
• - Hydroxyl groups of 5 to 50 mmol / mol CH₂
• - further oxygen-containing groups from 0 to 100 mmol / mol CH₂ and

10 to 30 parts by weight of vegetable oils and / or recoverable from them Fatty acids or fatty alcohols.

To prevent segregation, can still 0.1 to 3 Gewichtsan parts of a Compatibilizers be added. As vegetable oils In particular, domestic vegetable oils such. B. rapeseed oil or sunflower oil. But other oils, such as coconut oil or jojoba oil, can be used. As Compatibilizer occur preferably epoxidized vegetable oils, e.g. B. epoxidized soybean oil or epoxidized rapeseed oil or rapeseed alkyl esters, such as rapeseed methyl ester, into consideration.

The process according to the invention is such that in the first process a functionalization of the synthesis waxes (preferably PE, PP or EVA waxes) or paraffins by oxidation  known oxidation processes in the melt by means of Air or oxygen takes place, advantageously z. B. after DD 1 16 625.

For example, a produced by the high pressure process Polyethylene wax with a molecular weight of 4350 or a paraffin melted at about 160 ° C and through the melt with stirring an oxygen flow of about 250 l / h passed. The oxidation breaker tion is achieved by targeted addition of cold water, the continuous dosed into the wax melt and with intimate mixing the components is removed with the reaction gases, ge controls. After completion of the reaction is cooled and the like functionalized waxes by in-situ compounding with the native components vegetable oils and / or fat derived from them acid or fatty alcohols and optionally 0.1 to 3 parts by weight coupled to a compatibilizer. The in-situ compounding he follows in a stirred reactor at temperatures of 5 ° C above the Melting point of the respective wax up to temperatures of maximum 200 ° C and under inert conditions.

Surprisingly, it was found that by the invention proper in-situ compounding a homogeneous wax composition ent stands, whereby the components by physico-chemical Ad are linked to each other. The polarization microscope research shows that the native components in the Sphärolith crystal structure of the functionalized wax are bedded. The resulting wax compositions can be as usual process and find in the most diverse Fields of application, such. B. in the paper coating, to Her position of tree wax or in paint, paint and corrosion protective formulations and for paraffin finishing use, wherein the advantage of controlled biodegradation is the compost tion as possible disposal and thus material cycles getting closed.  

The invention thus also opens up further high-quality use possibilities for vegetable oils in the chemical-technical field, in the hitherto mainly only the use for the production of bio diesel, biolubricants and surfactants was known and creates so conditions for the extended cultivation of renewable Raw materials.

The invention also relates to aqueous emulsions based on he according to the invention in situ wax compositions. The invention aqueous emulsions

• a) 10 to 40 parts by weight of the insitu wax according to the invention composition
• b) 90 to 60 parts by weight of water, preferably desalted Water,
• c) 0 to 15 parts by weight of a saponification agent.

Particularly preferred are those wax emulsions whose waxy com position according to a) 3 to 20 parts by weight of fatty acid, and here again preferably oleic acid or erucic acid.

The addition of saponification agents may prove beneficial prove. If necessary, these can be used in quantities of up to 15 Be added by weight of the emulsion. To use such suitable saponification agents are preferably triethanolamine and / or aqueous alkali metal hydroxide, such as sodium hydroxide or Potassium hydroxide solution. Likewise, the addition of further emulsifiers, preferably based on alkyl glycol ethers or alkoxylates Base of rapeseed oil, done. The percentage of this additional emul gators can be up to 15 parts by weight. The addition he follows as a function of the HLB value (measure of the affinity of Surfactant to aqueous or hydrophobic phase, the behavior from hydrophilic to lipophilic regions in the molecule).  

The emulsions are produced both after the wax-up Wax as well as the water-to-wax method. It can do so probably be depressurized as well as under pressure. benefit working under pressure up to a maximum of 6 bar at a temperature of 110 to 150 ° C. In these conditions is stirred intensively and homogenized. After that, on tempera Chilled from 35 to 40 ° C and filtered.

The use of the aqueous emulsions according to the invention Basis of the in-situ wax compositions, especially wax wax data with a specific content of carboxyl and hydroxyl groups, Vegetable oils and vegetable fatty acids, such as oleic acid, erucic acid, so such as a compatibilizer, is extremely diverse. You can u. a. used for the production of floor, Car and furniture care products, printing inks, varnishes, aqueous wood glazes, in the paper industry and in the plastic industry processing.

embodiments

The invention will be closer to him based on the embodiments purifies.

example 1 1. Preparation and Characterization of the Functionalized waxes

The oxidation of the waxes takes place in the melt by means of acid substance or oxygen-containing media, being advantageous is moved according to DD 1 16 625. In Table 1a, those for the In-situ compounding used oxidized waxes and their Characteristics collected:

Table 1a

The experimental conditions for gel permeation chromatography graphical measurements are in plastic and rubber 24 (1977) No. 7, p. 463.

The concentration of the functional groups was determined by the Extinction of typical bands in the IR spectrum determined:

• Hydroxyl groups: 3400 cm ^-1
• - Carboxyl groups: after reaction with thionyl chloride to acid chlorides based on the resulting band at 1798 cm ^-1 .

The IR spectroscopic measurements were on test slides (Thickness approx. 0.05 mm), which is self-supporting in an IR Spectrometer Perkin-Elmer were measured.

2. Native resources

The native components used are summarized in Table 1b posed:

Sample No.. natively Type of product native 1 Rapeseed oil, variety 00 (erucic acid-poor) native 2 Sunflower oil native 3 Rapeseed oil (erucic acid-rich) native 4 Rapeseed oil, variety 00 / oleic acid (1: 1) native 5 Rapeseed oil, variety 00 / erucic acid (2: 1) native 6 Oleic acid / oleyl alcohol (1: 1)

3. in-situ compounding

A 2.5 liter reactor equipped with a mechanical stirrer is, with 900 g of a previously functionalized synthesis wax or paraffin loaded. The functionalization of the Wax takes place in the melt at temperatures of about 160 ° C. passing an oxygen stream according to the method Example of the DD 1 16 625. The characteristics of the waxes used are contained in Table 1a.

To this wax melt whose temperature is between 120 to 160 ° C is then added, then the addition of the native component and optionally of the compatibilizer. The used native components are summarized in Table 1b. The reaction takes place under intensive stirring at atmospheric pressure and under inerting by means of weak nitrogen flow. It is after about 2 hours completed. The yield is quantitative.

Table 2

4. Testing the biodegradability of the in-situ compositions

The biodegradability studies were carried out on the insitu wax composition No. 6 according to the invention. With the manometric method according to Warburg (description see micro Bielle Corrosion of Plastics and Their Ingredients, Akade Mie-Verlag, Berlin, 1963) was the dissimilatory degradation of followed wax composition according to the invention. The manometric Observation extended over 8 hours at 30 ° C with a Oscillation number of 90 per minute. The evaluation was carried out after Oxygen consumption in pl.

For comparison V1, batches without organic carbon were used. Source (pure nutrient solution for microorganisms) for recording the Zero value of endogenous respiration of bacterial cells. In V2 were Batches with a PE wax of molecular weight (mean Mn) of approx. 800 g / mol used.  

In Table 3, the measurement results of the biodegradation of the invention insitu wax composition No. 6 and the United are equivalent substances by
Pseudomonas aeruginosa, strain Hpa,
Batch without preculture,
Germ content per ml mixture: 1.1 × 10⁹
shown.

Table 3

Thus, the products of the invention in biological Reini very well degradable.  

Example 2 Composition and preparation of aqueous emulsions biologically degradable wax compositions

Table 4

Overview of the type and quantity of the components used

All of them are suitable for the preparation of the emulsions according to the invention usual wax emulsification process. The emulsification of the above be written formulations was carried out as follows:

The apparatus used consists of a 2 l stirred reactor (stirring drive up to 200 rpm, Ultra-Turrax with dispersing tool) made of stainless steel. The apparatus allows emulsification under Pressure up to max. 6 bar.  

The amount of water given in Table 4 is inclusive of possibly added emulsifier and saponification agent in the Filled reactor. Thereafter, the in-situ wax composition becomes dosed. This mixture is within a time of about 70 min heated to 120 ° C and at this temperature for 30 min homogeni Siert. After this time, the emulsion within 20 to 30 min cooled to 35 to 40 ° C and filtered.

Claims (12)

1. Biodegradable wax compositions containing
90 to 70 parts by weight of functionalized synthesis waxes and / or pa raffinic hydrocarbons having the following characteristics:

• - average molecular weights of 500 to 5000
• - Carboxyl groups of 5 to 50 mmol / mol CH₂
• - Hydroxyl groups of 5 to 50 mmol / mol CH₂
• - Further oxygen-containing groups from 0 to 100 mmol / mol CH₂ and

10 to 30 parts by weight of vegetable oils and / or from it ge Winnable fatty acids or fatty alcohols. 2. wax composition according to claim 1, characterized in that the vegetable oil is rapeseed oil or sunflower oil. 3. wax composition according to claim 1 and 2, characterized net, that ent. 0.1 to 3 parts by weight of a Compatibilizers ent are holding. 4. wax composition according to claim 3, characterized in that the Compatibilizer an epoxidized vegetable oil or a rapeseed alkyl ester. 5. Aqueous emulsion of biodegradable wax compositions containing

• a) 10 to 40 parts by weight of the wax composition according to claims 1 to 4
• b) 90 to 60 parts by weight of water
• c) 0 to 15 parts by weight of a saponification agent.

6. Aqueous emulsion according to claim 5, characterized in that

• a) is a wax composition containing 3 to 20 parts by weight of fatty acid.

7. Aqueous emulsion according to claim 6, characterized in that the fatty acid is oleic acid or erucic acid. 8. Aqueous emulsion according to claim 5, characterized in that

• c) triethanolamine and / or an aqueous alkali metal hydroxide.

9. Aqueous emulsion according to claims 5 to 8, characterized records that up to 15 parts by weight of other emulsifiers are included. 10. Aqueous emulsion according to claim 9, characterized in that the emulsifiers are based on alkyl polyglycol ethers or alkoxylates based on rapeseed oil. 11. Process for producing biodegradable wax composite tions according to claim 1, characterized in that the Syn thesewachse or paraffins in an upstream Verfah targeted with oxygen-containing functional Groups and then the in-situ Compounding with the vegetable oils or with herge made fatty acids or fatty alcohols under inert conditions at temperatures of at least 5 ° C above the respective Melting range of the waxes up to temperatures of maximum 200 ° C is carried out, with the occurrence of segregation shear a compatibilizer is added.