DE1235281B - Process for the production of hard waxes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C07c

German class: 12 ο - 5/09

1235 281
F46581IVb / 12o
July 13, 1965
March 2, 1967

An important performance property of waxes is their solubility in the Wax processing common solvents, since the use of soluble waxes is often considerable Brings advantages over the use of wax emulsions or suspensions. So wax solutions can be sprayed, for example; it is also easier with them than with emulsions or suspensions to produce a homogeneous protective layer.

In practice, particular interest is shown in waxes that are good Solubility also have high hardness. The combination of those two properties is so far but has only been achieved with certain polyvinyl ethers, but their production is complicated and is costly. All other hard waxes known to date are insoluble in organic solvents; The softer waxes, which are soluble, can often use the application-technical ones Failure to meet requirements.

A process for the production of hard waxes has now been found which is characterized by this is that glycidyl ethers of aliphatic alcohols having 16 to 30 carbon atoms are polymerized.

Those obtainable by the process according to the invention Hard waxes are in the organic solvents common in wax processing, such as turpentine oil, gasoline or trichlorethylene, easily soluble and remain after the evaporation of the Solvent as hard, glossy films.

For the claimed process, glycidyl ethers of aliphatic alcohols with 16 to 30, in particular with 16 to 24 carbon atoms are used. Particularly suitable are those of the cetyl, stearyl and Behenyl alcohol and mixtures thereof, and also the glycidic ethers obtained through the Alfol synthesis Alcohols with about 16 to 24 carbon atoms.

The preparation of the monomeric glycidyl ethers used as starting materials can be carried out in both two stages by reacting the alcohols with epichlorohydrin and subsequent dehydrochlorination the chlorohydrin ether as well as in only one stage according to the same reaction principle.

The glycid ethers available are colorless products with an epoxy content of around 65 to 85% theory and a chlorine content of 1 to 1.7% and can be used without further purification processes, such as such as distillation or recrystallization, can be used for the polymerization.

The polymerization of the glycidyl ether is preferably carried out directly in bulk, with Process for the production of hard waxes

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning, Frankfurt / M.

Named as inventor:

Dr. Josef Kaupp, Wiesbaden;

Dr. Karl Petz, Westheim near Augsburg

Atmospheric pressure, reduced pressure or elevated pressure can be used. Of course the polymerization reaction can also be carried out in the presence of inert solvents or diluents, z. B. ethers or hydrocarbons.

The so-called Friedel-Crafts catalysts, as well as organometallic catalysts, are suitable as catalysts Links. Particularly suitable catalysts are boron fluoride, tin tetrachloride and antimony pentachloride or mixtures thereof. Boron fluoride, for example, can also be advantageous in the form of an ether or Water complex as well as diluted with a solvent, e.g. B. dioxane, added to the monomers will. The initiators are the glycid ethers in a concentration of 0.01 to 3 percent by weight, preferably 0.1 to 1.5 percent by weight added, but also higher concentrations do not harm during the polymerization.

The way in which the catalyst is added to the monomer is not essential for the success of the polymerization decisive. The entire amount of catalyst can be added at the beginning of the polymerization, but you can also work in such a way that the polymerization process is started by adding a portion of the catalyst initiates and the remainder yields in portions during the polymerization. Also is it is possible to add more glycidyl ether to the polymerization mixture.

The polymerization is carried out at temperatures between 40 and 200 ° C, preferably 50 to 100 ° C carried out. Since the reaction is highly exothermic, it is generally necessary to keep the reaction vessel open for the entire duration of the polymerization to cool. However, it is not absolutely necessary to work at a constant temperature, on the contrary, it has occasionally proven expedient

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pointed, for example, to start the polymerization at 50 ° C and the temperature in the course of Allow the reaction to rise slowly to 120 ° C.

A preferred embodiment of the polymerization is, for example, at 50 to 60 ° C. and atmospheric pressure with stirring and nitrogen blanketing add the catalyst to the monomer dropwise to be added and the reaction mixture to be kept at this temperature by cooling.

The hard waxes produced by the process according to the invention are polymers with degrees of polymerization from 2 to 10, preferably 2 to 5, have a light color and can be used without further Cleaning or removal of catalyst residues can be used in practice.

They are soluble in turpentine oil, gasoline and trichlorethylene and are characterized by their exceptionally low melt viscosity and high flow hardness. In the case of polyoctadecyl glycidyl ether, for example, the melt viscosity is 21 to 23 cSt and the flow hardness is 350 to 400 kg / cm ² . For comparison, the corresponding key figures for the polyoctadecyl vinyl ether with about 400 cSt and 220 to 260 kg / cm ^{2 are given} . The process products are particularly versatile in the cleaning agent sector, for example as floor care products, especially for the care of stone floors, as furniture polishes and as car waxes.

example 1

60 g of colorless hexadecyl glycidyl ether with the following key figures: flow / dropping point 26.3 / 26.5; Epoxy content 11.7% (theoretical 14.4%) and a chlorine content of 1.57% were in a 500 ml three-necked flask submitted. With thorough stirring and at an oil bath temperature of 60 ° C., the mixture was added in the course of 5 minutes 0.3 ml of BFg diethyl etherate was added to the monomer. The temperature of the reaction mixture rose at 97 ° C. The mixture was then stirred for a further 15 minutes.

The flow / drop point of the resulting white hard wax of the polyhexadecyl glycidyl ether is 39.7 / 39.9 ° C.

Example 2

For 300 g of octadecyl glycidyl ether with the key figures: flow / dropping point 35.9 / 36 ° C, epoxy content 10.7 (theoretical 13.25) and a chlorine content of 1.4%, 3 , 5 ml of a 50% solution of BF ₃ etherate in dioxane was added. The reaction mixture was cooled with a water bath from time to time. The mixture was then stirred at 60 ° C. for a further 20 minutes.

Polyoctadecylglycidäther is a white hard wax with a flow / dropping point of 49.7 / 49.8 ° C. The The molecular weight of the polyether, determined by the ebullioscopic method, is about 1400.

Example 3

The Docosanylglycidäther used had the following characteristics: yield / drop point of 49.9 / 50 ⁰ Q epoxide content 9.6% (theoretical 11.2) and chlorine content of 1.1%. To 350 g of this Glycidäthers was added dropwise at an oil bath temperature of 6O ⁰ C over 10 minutes 1.2 ml of BFG-Diäthylätherat. The temperature of the reaction mixture rose to 93 ° C. during this process. After the addition of the catalyst had ended, stirring was continued for a further 10 minutes. The polydocosanyl glycidyl ether is a white hard wax with a flow / drop point of 61.5 / 62.5 ° C. The molecular weight of the polymer obtained was about 1000.

Claims (3)

Patent claims: 1. A process for the production of hard waxes, characterized in that glycidyl ether aliphatic alcohols with 16 to 30 carbon atoms are polymerized. 2. The method according to claim 1, characterized in that the polymerization by Friedel-Crafts type catalysts is initiated. 3. The method according to claim 1 and 2, characterized in that the polymerization at temperatures between 40 ° C and 200 ° C. 709 517/546 2.67 © Bundesdruckerei Berlin