DE1098502B - Process for the production of hard ester waxes - Google Patents

Description

GERMAN

Suspensions of waxes and paraffins in solvents have recently become more and more important as liquid, anhydrous polishing compounds. Compared to the wax pastes, they have certain advantages due to their larger solvent content for a number of possible applications, such as: B. that of easier and simpler handling. This liquid polishing compositions usually comprised between 10 and 20 ° / ₀ solids and correspondingly from 90 to 80 ° / ₀ wax solvent. The solid content, which is ultimately decisive for the quality of the wax film on the object to be cared for, consists of good polishing compounds, mainly a valuable hard wax and paraffin as a cheaper component. However, since the commercially available ester waxes, such as carnauba, or the partially synthetic ester waxes based on montan wax, alone or together with paraffin and the usual amounts of solvents for liquid flooring compounds, form pastes that are dimensionally stable at room temperature, in order to achieve low-viscosity, deeply stock suspensions, with liquefying additives, such as. B. metal soaps, highly branched esters according to German patent specification 1 011 872 or polymerized vinyl ethers of fatty and wax alcohols can be worked. There are also already known waxes for liquid polishing compounds, which are obtained from hard paraffin by chlorination, dehydrochlorination, oxo reaction, alkali melt, acid splitting and saponification. These contain considerable amounts of metal soaps, in addition to free acids and a lot of unchanged starting paraffin. Their production is very tedious and relatively expensive.

It has now been found that hard ester waxes, which are suitable for the production of low viscosity at room temperature, deep-setting wax suspensions, can be obtained by using wax acids with higher molecular weight waxy alcohol mixtures, such as those produced by the catalytic hydrogenation of oxidation products higher molecular weight paraffin hydrocarbons are obtained, esterified.

Wax acids with acid numbers are suitable as acid components for the ester waxes according to the invention between 70 and 160, as it is preferably achieved by oxidative bleaching, ζ. B. with chromic acid, from montan wax or from mixtures of montan wax and higher molecular weight ones that have been partially oxidized with air and melt above 80 ° C Paraffin hydrocarbons are obtained. Furthermore, by chlorination, dehydrochlorination and Chromic acid oxidation or by air oxidation and chromic acid oxidation from higher molecular weight, above 80 ° C Melting paraffinic hydrocarbons can be used.

Mixtures of aliphatic wax alcohols with a larger or smaller residual process for production serve as the alcohol component
of hard ester waxes

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly master Lucius Sd Brüning,

Frankfurt / M., Brüningstr. 45

Dr. Oswald Metz, Gersthofen via Augsburg,
has been named as the inventor

content of paraffin, as obtained by oxidation of higher molecular weight natural, but preferably synthetic Hydrocarbons with a freezing point above 70 ° C, especially above 80 ° C, and preferably above 90 ° C, and catalytic hydrogenation of the oxidation products. Such hydrocarbons are z. B. well refined petroleum paraffins or hydrocarbon mixtures from the catalytic carbon dioxide hydrogenation or mixtures thereof with a maximum of about 40 percent by weight of a waxy high or low pressure polyolefin, z. B. homopolymers or copolymers of ethylene or propylene or mixtures thereof, with a Average molecular weight below 20,000. The percentage refers to the total to be oxidized Mixture.

The paraffins are oxidized in a manner known per se at a temperature between 120 and 180 ° C. with oxygen or a gas containing elemental oxygen, such as air or air enriched with oxygen. It has proved advantageous to oxidize to such an extent that at least 50 ° / _0/0 of paraffin are converted into oxygen-containing compounds, in particular more than 70 ° / ₀ and preferably 80 to 95 °. Under certain circumstances, especially if very high molecular weight hydrocarbon mixtures are used, all of the material can be reacted with oxygen. It should be noted, however, that the last paraffin residues are attacked only hesitantly, while at the same time an ever increasing breakdown of the oxidation products already present takes place. The resulting reduction in the average molecular weight of the alcohols can then have a detrimental effect on the hardness of the ester waxes.

The conversion of these paraffin oxidates into the wax alcohol mixtures can also be carried out in a manner known per se, e.g. B. by catalytic Hydrogenation with copper chromium oxide as a catalyst

109 508/396

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at a temperature between 200 and 350 ° C and with a paraffin content of 4.8%. The pale yellow

an initial pressure between 150 and 250 atmospheres. Paraffin oxidate had an acid number of 50.5, a

the carbon saponification number of 126, a hydroxyl number of 23, which is present in the oxidation mixture

acids, esters and ketones into the corresponding alcohols carbonyl number of 73 and a pour point of

converted. The white waxy 5 90.5 / 91.0 ° C.

Hydrogenation products represent mixtures of one and more- In a steel autoclave the oxidate was then in

valuable, primary and secondary alcohols and the presence of 10 percent by weight of copper chromium oxide

Paraffin. A separation of the remaining paraffin can be powdered at 290 ° C and 180 atü initial pressure for as long

are carried out, is - but not necessarily emergency- hydrogenated until no more hydrogen uptake took place,

agile. In order to use these alcohol mixtures with ester waxes. After filtering off the catalyst, a pure

To obtain with sufficient hardness, is already with the white alcohol mixture without acid number, saponification number

Starting paraffins on the largest possible molecular and carbonyl number with a hydroxyl number of 156,

weight to attach particular importance. a pour point of 89.5 / 90.0 ° C and one

The esterification takes place with a known paraffin content of 6.0%.

conditions, so for example in the melt under inert gas 15 1.05 parts by weight of this hydrogenation product atmosphere at a temperature between 100 and 200 ° C with 1 part by weight of a by chromic acid refining with distilling off the water of reaction. The acid wax obtained from ester montan wax with acid formation proceeds relatively easily, so that the number of 151 does not necessarily esterify under a nitrogen atmosphere at 175 to 180 ° C. when esterification catalysts are used. A light-colored, hard ester wax was required with it. The ratio of acid to 20, an acid number of 10, a saponification number of 95.5 alcohol is expediently chosen so that the hydroxyl and a pour point of 87.7 / 88.0 ° C. are obtained, groups for complete Esterification suffice. If 15 parts by weight of this molten Practical are stirred, about 0.8 to 1.3, pre-ester wax with 85 parts by weight of white spirit with preferably 0.9 to 1.2 equivalents of hydroxyl groups to boiling points 140 to 190 ° C and cools below meet another 1 equivalent of carboxyl groups. A larger 25 stirring to room temperature, the result is an excess, as well as a larger undershoot, as the homogeneous, stable, low-viscosity wax suspension with proportions specified corresponds is possible a pour point of O to avoid ⁰ C. Even after several days liehst as As a rule, the standing was shown neither in the liquid nor in the quality of the waxes. The esterification, the edge of which is solid deposits,
is driven so far that at least 50 ° / ₀ and forward 30

preferably 70 to 90% of the acids converted into esters Example 2

are. Optionally, of course weiterverestert I _n the same manner as described in Example 1 was

If, above all, the reaction proceeds so quickly, a mixture of 85 parts by weight of a higher molecular weight

that no stronger discoloration of the wax occurs. A synthetic paraffin with a freezing point around 100 ° C

larger proportion of free acids has a detrimental effect on 35 and 15 parts by weight of a waxy low-pressure

the stability of the suspensions. The non-esterified polyethylene with an average molecular weight of

Carboxyl groups can optionally also partially have a melting point of around 2000 and a melting point of 118 ° C. with air

in a manner known per se in alkali and / or oxidized. The oxidate, which has an acid number of 37.5, a

Alkaline earth metal soaps are transferred. The metal saponification number of 98, a hydroxyl number of 27, a

content of the waxes should not exceed ₄₀ carbonyl of 63 0.5 percent by weight, a pour point of-drip

stride, and preferably having less than 0.3 percent by weight, 97.0 / 97.2 ° C and still at 8 ° / ₀ containing paraffin,

based on the amount of wax, Hegen. was then also catalytic as in Example 1

The ester waxes produced according to the invention are hydrogenated. The resulting colorless wax-alcohol mixture was light-colored, hard and, apart from a hydroxyl number of 135, had neither a medium, such as toluene, white spirit, turpentine oil, an acid number nor a saponification or carbonyl number, heat soluble. They are compatible with natural waxes and paraffins, such as had a pour point of 97.3 / 97.5 ° C and desynthetic waxes. Unlike held about 9.5 ° / ₀ paraffin.

the natural hard waxes or partially synthetic 1.25 parts by weight of this mixture were used in the im

Ester waxes based on montan wax have the manner indicated in Example 1 with 1 part by weight of the method given there

it esterifies the property of the acid wax used, which is by no means foreseeable. The bright-

alone or together with hydrocarbon brown, hard ester wax had an acid number of 15,

grow of synthetic as well as natural origin, e.g. B. a saponification number of 81 and a pour point

Catalytic carbohydrate hydrogenation paraffins, of 92.0 / 92.2 ° C.

microcrystalline petroleum paraffins, table paraffins, Οζο- From 15 parts by weight of this ester wax and 85 parts

Kerites or other waxes with solvents, such as 55 parts by weight white spirit, became a stable, thin-bodied,

White spirit or turpentine oil, thin, deeply stocky, homogeneous wax suspension with a pour point of

to form homogeneous wax suspensions. They allow you to get 5 ° C.

Thus in a simple way the structure of high quality, By melting together 7.5 parts by weight of the

anhydrous, liquid polishing compounds. Ester wax, 6.5 parts by weight table paraffin with a

The following examples are intended to illustrate the process in more detail. 60 solidification point of 50 ° C, 1 part by weight of ozokerite with

explain. The flow-drop points were after Ubbe- a freezing point of 68 ° C and stirring with

lohde and the pour points according to the regulation in 85 parts by weight of a mixture of 90 parts by weight

Lunge-Berl, »Chemical-technical analysis percentage of white spirit and 10 percent by weight of turpentine oil

thoden ", 8th edition, vol. 4 (1933), p. 657 and following, a wax suspension with a pour point of

certainly. 65 10 ° C obtained. This remained even after a long period of storage

Example 1 low viscosity and without crystalline deposits.

A higher molecular weight hard paraffin from catalytic example 3

Carbohydrate hydrogenation with a freezing point around a higher molecular weight hard paraffin of the catalytic

100 ° C was at 140 to 145 ° C with air to a 70 ° C carbohydrate hydrogenation with a freezing point of

5 6

98 ° C at 160 to 165 ° C with air to a wax obtained from montan wax with chromic acid

Paraffin content of 12 ° / ₀ oxidized. The white oxidate with an acid number of 90.5 in the described in Example 3

possessed an acid number of 29 and a saponification number esterified manner. The received light brown, very

of 83.5, a hydroxyl number of 30, a carbonyl hard ester wax had an acid number of 18, a

number of 76 and a flow drop point of 92.7 / 93.0 ° C. 5 Saponification number of 70 and a flow drop point

The hydrogenation of the oxidate at 260 ° C and at 180 atü of 88.5 / 89.0 ⁰ C.

Initial pressure in the presence of 10 ° / ₀ Kupferchrom- 15 parts by weight of this Esterwachses revealed to-

Oxide as a catalyst resulted in a white reaction with 85 parts by weight of white spirit at 0 ° C

product without acid number, saponification number and carbonyl clogging thin liquid homogeneous wax suspension.

number with a hydroxyl number of 145 and a flowing io

Drop point of 91.5 / 92.0 ⁰ C. Example 6

1.05 parts by weight of these wax alcohols were with A higher molecular weight hard paraffin of the catalytic 1 part by weight of the acid wax from Example 1 at 150 to carbon dioxide hydrogenation with a solidification point of 160 ⁰ C with phosphoric acid as a catalyst under nitrogen-98 ° C was as in Example 1 up to a paraffin content esterified up to an acid number of 14.5. The case 15 of 10.6 ° / ₀ oxidized. The white oxidate had an acid-obtained yellow, hard ester wax had a saponification number of 40.5, a saponification number of 92, a hydroxyl number of 97.0 and a Feet dropping point of 87.5 / number of 26, a carbonyl number of 81 and a flow-88, O ⁰ C. Drop point of 92.0 / 92.5 ° C. The hydrogenation at 24O ⁰ C from 15 parts by weight of this Esterwachses and 85 Ge and 180 atm initial pressure yielded a white waxy wichtsteüen test fuel was a stable, low viscosity, 20 alcohol mixture without acid number, saponification and homogeneous Wachsusspension with a pour point of carbonyl with a hydroxyl number of 145 , an O ⁰ C obtained. Flow drop point of 92.5 / 92.8 ° C and a content

By melting together 7.5 parts by weight of the 12 ° / ₀ paraffin.

Esterwachses, 6.5 parts by weight of a higher molecular weight 1 part by weight of this hydrogenation product was mixed with synthetic paraffin having a solidification point of 98 ° C, 25 1.3 parts by weight of a by Chromsäureoxydation 1 part by weight ozokerite with a solidification point of a mixture of 50 percent by weight of montan wax and 75 ⁰ C and stirring with 85 parts by weight White spirit 50 weight percent of air up to an acid number of a wax suspension was anoxydierten having a pour point of 23, high molecular weight, obtained by 100 ⁰ C 3 ⁰ C. This remained stable even after prolonged standing of the melting synthetic paraffin obtained from the acid and without crystalline deposits. 30 wax with the acid number 111 as in Example 3 ver _,. . estert. The light, hard ester wax obtained had an acid number of 12.5, a saponification number of 95 and, as described in Example 1, a flow point of 89.5 / 90.0 ° C. became hard molecular paraffin from a higher flow point of the catalytic carbon dioxide - 15 parts by weight of the ester wax together with hydrogenation with a solidification point of 98 ° C resulted in a stable, homogeneous oxidation with air with 85 parts by weight of white spirit, a mixture with an acid number wax suspension with a pour point of -5 ° C. of 31, a saponification number of 71, a hydroxyl melt, 10 parts by weight of the ester wax with a number of 19, a carbonyl number of 76, a flowable 4 parts by weight table paraffin with a solidification dropping point of 97.5 / 98.0 ° C and 20.3 ° / ₀ paraffin point of 6O ⁰ C and 1 part by weight of ozokerite made with one. The hydrogenation of this mixture at 260 ⁰ C 40 freezing point of 68 ⁰ C together and stirred the and 180 atm initial pressure gave a white wax without a mixture with 85 parts by weight of white spirit, the acid number, saponification number and carbonyl number, with a thin, homogeneous wax suspension with a hydroxyl number of 108, a pour point of-drip pour point of 6 ⁰ C. 96.8 / 97.0 ° C and 21.3 * / ₀ paraffin. Example 7

1.1 parts by weight of this hydrogenation product were '45

with 1 part by weight of an acid wax obtained by chromic acid refining of 1 part by weight of the hydrogenation product from Example 6 montan wax with an acid was added in the same way as there with 1.9 parts by weight of 122 in the manner described in Example 3 of an acid wax of acid number 73, which by Chromium esterified. The light brown, hard esterification product acid oxidation of the one also mentioned in Example 6 had an acid number of 16, a saponification number of 50 Luftoxydates with an acid number 23 obtained 80.5 and a flow point of 90.5 / 91.0 ° C. was, esterified and saponified at 140 ° C with 0.2 percent by weight from 10 parts by weight of this ester wax and 90 Ge magnesium hydroxide. The very hard light yellow weight share of white spirit, a stable low-viscosity Esterwachs had received an acid number of 15, a Verseifungshomogene wax suspension with a pour point of number of 60 and a flow-drip point of 95.5 / -1O ⁰ C. 15 parts by weight of ester wax and 85 parts by weight 55 96.0 ° C.

parts by weight of white spirit resulted in a ^{stagnant at 0 0} C by melting together of 7.5 parts by weight of the

Wax suspension of the same appearance. Both suspensions of ester wax, 6.5 parts by weight table paraffin with one

solidification point of 50 ° C. and 1 part by weight of ozokerite remained stable even over a longer storage period

and without crystalline deposits. with a freezing point of 68 ⁰ C and stirring

By melting together 7.5 parts by weight of the 60 with 85 parts by weight of white spirit, a homogeneous,

Ester wax, 6.5 parts by weight table paraffin with a stable wax suspension with a pour point of 7 ° C

Freezing point around 60 ° C, 1 part by weight of ozokerite with received.

A freezing point of 68 ⁰ C and stirring with example 8 85 parts by weight of white spirit became a stagnant ^{at 8 0 C}

Receive wax suspension. This remained even with 65 1 parts by weight of the hydrogenation product from Example 6 for a longer period of time

Storage fluid and without solid deposits. was in the same way as there with 1.2 parts by weight

. · Ι ς of a wax acid with the acid number 118 esterified, the

.Example ο _{aug e} j _formers of higher molecular weight paraffin with a synthesis

0.9 parts by weight of the hydrogenation product from the solidification point of 98 ° C by chlorination up to

Game 4 were with 1 part by weight of a by bleaching 70 a chlorine content of 8.0 ° / ₀ , dehydrochlorination and

Oxidation with chromic acid had been obtained. The resulting light yellow Esterwachs had an acid value of 17.5, a saponification value of 77.5 and a flow-drip Sparks of 89.0 / 89.5 ⁰ C.

By melting together 10 parts by weight of the ester wax and 5 parts by weight of table paraffin a freezing point of 60 ° C and stirring with 85 parts by weight of white spirit was a homogeneous, Thin wax suspension with a pour point of 4 ° C was obtained.

Claims (4)

Patent claims: 1. A process for the production of hard ester waxes, characterized in that wax acids with higher molecular weight waxy alcohol mixtures obtained by oxidation of higher molecular weight paraffin hydrocarbons with a solidification point above 70 ° C and preferably above 90 ° C with oxygen or a gas containing elemental oxygen up to a paraffin conversion of at least 50 ° / ₀ and before preferably between 80 and 95 ° / ₀ and were obtained by subsequent catalytic hydrogenation of the oxidation product, reacted in such a quantitative ratio that 0.8 to 1.3 equivalents of hydroxyl groups meet 1 equivalent of carboxyl groups and the esterification leads so far that at least 50 ° / p of the wax acids are esterified. 2. The method according to claim 1, characterized in that one oxidation products of higher molecular weight Paraffinic hydrocarbons from catalytic carbohydrate hydrogenation are used for hydrogenation. 3. The method according to claim 1, characterized in that higher molecular weight is used for the oxidation Paraffinic hydrocarbons with a maximum content of about 40% of waxy polyolefins are used. 4. The method according to claim 1, characterized ge ^ indicates that the unesterified carboxyl groups of the ester waxes are partly in alkali and or or alkaline earth soaps. © 109 508/396 1.61