DE1212971B - Process for the production of metal alcoholates of divalent metals - Google Patents

Description

Process for the production of metal alcoholates of divalent metals. 0 volts and a volatile aliphatic monocarboxylic acid, which contains at least two carbon atoms in the molecule, with an alcohol of the general formula in which R 'is an alkyl, aralkyl, cycloalkyl, alkoxyalkyl, alkoxyaryl, aryloxyalkyl, aryloxyaryl, alkoxycycloalkyl, cycloalkoxyalkyl, hydroxyalkyl, hydroxycycloalkyl or hydroxyalkoxyalkyl radical, X stands for an oxygen or sulfur atom , R "is a hydrogen atom or the radical R 'and n is 1 or 2, or of the general formula in which Y = - (CH2) n-1, -C (CH2OH) 2 or - (CHOH) 4- and R ″ and n have the same meaning as in formula I, at elevated temperature and optionally under reduced pressure with distillation The products available are suitable, for example, as stabilizers for polyolefins.

The present process represents a further development of the process for the preparation of alcoholates of divalent metals according to patent 1196 655 and is characterized in that either a) an imidazoline alcohol of the general formula is used instead of the alcohols used there in which R denotes a saturated or unsaturated alkyl radical having 6 to 20 carbon atoms and n = 1 or 2, or b) a cyclic ether alcohol of the general formula in which n = 1 or 2, or c) an amino alcohol having 4 to 8 carbon atoms and a tertiary amino nitrogen on a carbon atom in the a or β position to the C — OH group is used.

Like the method according to patent 1,196,655, that according to the invention Process compared to the previously known process based on alkali metal alcoholates the advantage that the carboxylic acid component is simple, namely by distillation the reaction mixture can be removed while in the prior art method this as Alkali salts remain in the reaction mixture, and that the for the preparation of the alkali metal alcoholates necessary work with exclusion of moisture and with free alkali metals is avoided.

Preferred alcohols of the formula III are those in which n = 1 and R represents saturated alkyl radicals having 6 to 20 carbon atoms. The connections too of formula III, in which n = 2, d. H. which in place of the ethanol group is the propanol residue can be used. In these connections is the second functional one Group next to the hydroxyl group, namely the tertiary amino group on one to the C-OH group ß-carbon atom. The imidazoline derivative of oleic acid is also suitable, d. H. the compound of the formula III in which R is the CH3 - (CH2) 7 - CH = CM - (CM2) 7 radical is.

Cyclic ether alcohols of the formula are also eminently suitable and in general their use gives good results, albeit in some Cases not as good as with the preferred alcohols mentioned above. Suitable cyclic ether alcohol compounds, which preferably contain 5 to 7 carbon atoms, are tetrahydrofurfuryl alcohol, tetrahydropyran-2-methylol and tetrahydropyran-2-ethylol.

The same as the alcohol component in the invention Amino alcohols which can be used in processes preferably have 4 to 8 carbon atoms and a tertiary amino nitrogen at one to the C-OH group a- or, 5-position Carbon atom. Suitable amino alcohols of this type are diethylaminoethanol, dipropylaminoethanol, Diethylaminopropanol and dimethylaminoethanol.

The process according to the invention is further illustrated by the following examples: Example 1 0.50 mol of a coconut fatty acid (NB-oxyethyl) imidazoline condensation product of the formula where n is an integer from 6 to 12, and 0.25 moles of nickel acetate, Ni (OOC CM3) 2 4 H20, were heated for 11/2 hours to 183: t8 ° C in a vacuum of 49 mm of mercury, the volatile condensables Reaction products were collected.

After this time, the liquid reaction product was tarred into a Poured sample bottle. The product presented a dark green, viscous, hardly pourable Liquid.

Analysis: Ni found: 8.10 / 0.

Analysis of the distillate showed that 70% of the theoretically possible Amount of acetic acid had passed over.

The same product was obtained by taking 0.74 moles of the aforesaid Alcohol, 0.37 mol of nickel acetate tetrahydrate and 205 g of an aromatic fraction of petroleum hydrocarbons with a boiling range from about 161 to 176 "C to 175: t10 ° C were heated, the mixture was kept at this temperature for 2 hours while Solvent, water and acetic acid were distilled off, and then water jet vacuum was applied to drive off the remaining vaporizable products.

Example 2 93.5 g (0.8 mol and 50% excess) diethylaminoethanol were in 250 ml of xylene with 62.5 g of nickel acetate tetrahydrate, Ni (OOC CH3) 2 4 4 H20, heated to 110 "C. The solution was filtered, but no undissolved nickel acetate stayed behind.

The solution was then brought to 155 "C internal temperature and 142" C vapor temperature heated and finally with application of vacuum up to 125 "C internal temperature and Stripped 90 "C steam using a water jet pump.

Finally, the product obtained was poured into a shallow pan Poured to cool. The glassy, brittle, clear, green, solid product was on a Ground particle size of 0.044 mm mesh size.

Analysis: Ni calculated: 20.2ovo; found: 21.47%.

Example 3 204.2 g of tetrahydrofurfuryl alcohol and 125 g of nickel acetate tetrahydrate were heated to 127 ° -10 ° C. for 11/2 hours. During the heating were noticeable Phase change recognizable: At 100 "C a clear green solution resulted, at 1300C it turned the reaction product is a fine-pored, whipped cream-like mass, after which to Liquefaction 102 g of tetrahydrofurfuryl alcohol were added and at 165 "C again a clear, dark green solution was obtained.

The liquid product was then poured into a shallow pan and dried in a vacuum oven at 115 "C to remove excess tetrahydrofurfuryl alcohol to abort. The resulting glassy product was reduced to a particle size of 0.044 milled mm mesh size.

Analysis: Ni calculated: 220/0; found: 26.520 / 0.

The product is a pale blue-green, free-flowing powder. It is a mixture of nickel alcoholates as specified in Example 6 for cadmium Art.

Example 4 1.33 mol of tetrahydrofurfuryl alcohol and 0.1 mol of cobalt acetate tetrahydrate, Co (OOCCH3) 2 4 M2O, were put together in a 500 ml three-necked flask, each with a Thermometer for measuring the temperature in the reaction mixture and in the vapor phase, a stirrer, a distillation column, a condenser and a collecting vessel was equipped for the distillate, heated to 180i5 ° C for 21/2 hours. The hot reaction product was filtered and the filter cake sucked as dry as possible.

The filter cake was made twice by slurrying in 15 ml of isopropanol washed and filtered.

The wet cake, which weighed 21 g, was air dried overnight.

Yield: 18.0 g. The product obtained was grainy and light in color purple color.

Analysis: Co found: 26.90 / o.

The filtrate (39.5 g) still contained 3.50/0 cobalt.

The cobalt content in the end product and in the filtrate was 1000 / o of the amount used Cobalts.

Example 5 2.5 moles of tetrahydrofurfuryl alcohol and 0.5 moles of lead acetate trihydrate were heated in xylene to about 110 "C. After 21/2 hours of heating at 180: t5 ° C water jet vacuum was applied, and the residue obtained as a residue that had not passed over The reaction product was a clear, dark-red to red-brown liquid, which is easily soluble in xylene. Analysis of the solid, in an amount of 44.30 / 0 resulting product was 56.8% lead.

Calculated: 50.6 per cent lead.

The further heating of the reaction product to remove excess, unreacted tetrahydrofurfuryl alcohol or by reaction with acetic acid Tetrahydrofurfuryl acetate formed at 180: t5 ° C led to cloudiness Precipitation of metallic lead. The product is basic tetrahydrofurfurylate lead with a lead content of 65 to 700/0.

Keep the dark red or red-brown liquid for 5 days At room temperature, an almost white, granular precipitate gradually separates out of it which can be easily separated by filtration. After washing with isopropanol and drying at 110 "C for 2 hours, the analysis showed that the product was 71% lead contained.

By adding a phenolic antioxidant to the lead acetate-tetrahydrofurfuryl alcohol mixture before the reaction, the color of the final product is not improved.

Example 6 204 g (2.0 moles) tetrahydrofurfuryl alcohol and 47.4 g (0.176 moles) cadmium acetate trihydrate, Cd (OOC CH3) 2. 3 H2O were heated together as described in Example 5, whereby a basic product, which is a mixture of compounds of the formulas A and B, was obtained.

Analysis: Cd calculated for A: 35.70 / 0; Cd calculated for B: 50.80 / 0; Cd found: 46.90 / 0.

The product turns out to be firm, dark brown, shiny like a mother-of-pearl Mixture of compounds A and B.

EXAMPLE 7 1.5 mol of lead acetate trihydrate and 3.0 mol of 2-oleyl-N- (β-oxyethyl) -imidazolidine of the formula were stirred together with heating until a solution of the lead salt had occurred. The reaction mixture was then heated more strongly and finally to 180 + 8 "C until it was soluble in mineral spirits and in petroleum ether, which was reached after about 11/2 hours. The product is a clear, honey-colored liquid with a Gardner viscosity of about 320 cP The analysis showed a lead content of 19.40%.

1.0 mol of copper acetate monohydrate and 2.0 mol of that used in Example 7 Alcohols were together as described there to 150 to 160C and then one heated to 165 to 175 "C for another half hour. The dark green, pasty, semi-solid product showed a copper content of 5.80 / 0.

In the above examples you can also use the following, earlier described other carboxylic acids for the preparation of the starting materials for the production of the metal alcoholates according to the invention are used: propionic acid, Butyric acid, isooctanoic acid, 2-ethylbutanoic acid, cyclohexanecarboxylic acid, acrylic acid, 3- (2-ethylbutoxy) propionic acid; these acids preferably have about 2 to 8 carbon atoms. Less volatile carboxylic acids that have a larger number of carbon atoms (e.g., naphthenic acids having an acid number of about 300) can also be used but more extreme conditions, especially vacuum, must be carried out the reaction can be applied.

As mentioned earlier, using the examples above can come in handy other alcohols, e.g. B. tetrahydropyran-2-methylol or Triethanolamine, are used, some or all of which the examples can replace according to alcohols used.

The products that can be prepared according to the invention can be used as stabilizers, especially for olefin polymers. When stabilizing polypropylene The nickel alcoholates that can be prepared are especially mixed with the known o, o'-bis (p-alkylphenyl) thioethers suitable. Other olefin polymers, such as polyethylene, can also be obtained by adding the new nickel alcoholates are improved.

Claims (1)

Claim: Further development of the process for the preparation of alcoholates of divalent metals according to Patent 1196655, characterized in that instead of the alcohols used there, either a) an imidazoline alcohol of the general formula is used in which R denotes a saturated or unsaturated alkyl radical having 6 to 20 carbon atoms and n = 1 or 2, or b) a cyclic ether alcohol of the general formula in which n = 1 or 2. or c) an amino alcohol having 4 to 8 carbon atoms and a tertiary amino nitrogen on a carbon atom in the α or β position to the C-OH group is used. Documents considered: German Patent No. 955 321.