DE1933612A1 - Metal oxide acylates and processes for their preparation - Google Patents

Description

Dr. Jacobus Rinse

Bernardsville, N.J. /UNITED STATES

2nd July 1969 SJ / Hu

7059

Metal oxide acylates and "processes for their preparation

The invention relates to metal oxide acylates and a process for preparing the same.

The inventive metal oxide acylates (further with "MOA" abbreviated) are characterized in that

(A) their metal component of at least two, at least bivalent, preferably bivalent to tetravalent, identical or different, with one another via oxygen bridges connected metal atoms and

(B) their acylate component to at least 55 mol%

(A) from residues of at least 7 »preferably 9 to

Non-volatile monocarboxylic acids containing 22 O atoms and

(b) from 0 to 100, preferably from 5 to 100, mol% calculated on (a), from phenol residues, and remaining from oxacyl residues of volatile aliphatic Carboxylic acids exist.

The new MOA products essentially consist of the following compound types, in their formulas means: M - a 2-valent, M ¹ - a 3-valent, M "- a 4-valent, M ¹¹ 'a 2-, 3- or Tetravalent metal, X - an oxacyl radical, η 1, 2 or 3 and m = 2, 3 or 4-:

(1) Linear compounds with 2-, 3- or 4-valent metal atoms in the molecule:

(X-0-) _n M ¹ "-0-M ¹ " (-0-X) _n XMOM ¹ (X) -OMX

(XMOM "(X ₂ ) -OMX (XM-0-) _n M ¹ " -0-M ¹ "(0-MX) _n

M ¹ '' (OEX) _m.

(2) Cyclic trimers with trivalent metal atoms in the molecule (OM ¹ X) ₅ :

M.
i i

(3) Cyclic tetramers with tetravalent metal atoms in the molecule:

Metal component.

The products according to the invention can preferably be used as a metal component contain: the bivalent metals calcium, magnesium,

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Strontium, Barium, Zinc, Cadmium, Nickel, Kotalt, Mercury; the divalent or trivalent metals iron, chromium and manganese; the trivalent metals aluminum, antimony, bismuth and cerium; the 2- or 4-valent metals tin and lead as well as the 4-valent metals Metals titanium, silicon and zircon. If the metal atoms in the MOA molecule are different, they can be of the same or be of different values. If only the metals zinc, lead, aluminum, antimony, titanium, zirconium or mercury are present, so the products are almost or completely colorless; some other metals give colored products (see below).

The ratio between the metal component to the acylate component is at least 1: 1, i.e. preferably with an excess of metal, e.g. in a ratio of 2: 1, 3: 1 or higher. In these cases the excess metal is in the form of metal oxide, in such a finely divided state suggest that it remains dispersed in the MOA and acts as a lightfast pigment. Products containing such a pigment are can be used as paints with a high metal content, which are easy to manufacture and whose pigment is not previously rubbed or needed to be ground. Paints of this type dry with a high gloss and preferably contain the color pigment Ferric (brown MOA) or ferroxide (black MOA), copper (green MOA), chrome (green MOA), nickel (green MOA) or manganese oxides (brown MOA). A good red-brown color pigment is the ferric oxide tallate containing ferric oxide Formula (OFeX) -, which adheres firmly to aluminum surfaces

..Λ

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and mixed with Aluiainiumschüppchen for gold imitation. tionen, while the e'uprooxidhaltige cupric oxide tallate of the formula 0 (GuX) _{2 can be used} as a green anti-rot paint.

Acylate component.

The residues of non-volatile monocarboxylic acids present in the acylate component are essentially Oxacyl residues of the following organic acids:

(1) Aliphatic linear chain acids such as stearic acid; branched chain Acids such as 2-ethylhexanoic acid; saturated acids like palmitic acidj unsaturated acids like oil and Linoleic acid.

(2) Cycloaliphatic acids such as naphthenic acids, e.g., cyclopentyl carboxylic acid.

(3) Aromatic acids such as rosin and abietic acid Tall oil fatty acid and p-toluenesulphonic acid.

The oxacyl residues can also be derived from mixtures of different acids, such as those in coconut and tall oil fatty acids are present.

In individual cases, the acylate component can also contain residues of volatile aliphatic monocarboxylic acids with Λ to 5 carbon atoms, in particular formic and especially acetic acid, ie formate and acetate groups, which originate from the manufacturing process described in more detail below; this is especially true for lead and zinc oxide acylates. As a rule, however, the products should be free of residues of volatile monocarboxylic acids,

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since these increase the viscosity and the melting point of the finished products in a manner which is unfavorable for their use, but decrease their solubility in organic solvents; therefore, the presence of those best is detrimental to the products. In principle, the acylate component should consist of such residues that the products are either liquid or have a relatively low melting point, so that liquid compositions can easily form; Also they should as far as possible in paint and paint solvents, such as naphtha, xylene or turpentine, be readily soluble and the ^Lo-1 solutions in the dry hard, heat stable, give adherent protective coatings on metal and non-metal surfaces.

If these conditions are observed, up to 50 mol% of the monocarboxylic acids can preferably be formed by phenol radicals be replaced by phenolate groups, specifically by radicals of unsubstituted or substituted phenols, in particular by o-, m- or p-cresol, pentachlorophenol and phenylphenol, if appropriate also of naphthols such as ß-ETaphthol. The total amount of the acylate groups based on non-volatile carboxylic acids (a) and phenols (b) should be at least 70 mol%, calculated on the Total amount of acylate groups. Phenolate-containing iron oxide acylates are advantageous as color pigments and wood preservatives applicable.

The products according to the invention can also be condensation products represent the MOA with metal oxides; the content of this

Component is preferably up to 10% by weight by weight of the MOA component. The metal oxide component consists of titanium or aluminum oxide or a titanium-silicon mixed oxide.

The new MOA products react with organic acids, in particular with mono- and dicarboxylic acids, such as acetic and maleic acid, with the formation of solids, furthermore with inorganic acids such as sulfuric acid, with the formation of soaps and are therefore it can be used as an acid binder. The MOA products also reacted with alcohols to form solutions, with phenols such as pentachlorophenol to form fungicides and with Sulfur with the formation of intermediate products for the production of high-viscosity polymers.

Production of the metal oxide acylates.

Known processes for the production of metal acylates are generally limited to metals, the metal alcoholates (cf. U.S. Patent 3,296,242), alkoxides and aryloxides able, and on lower acyl residues in the finished product.

The process according to the invention for the preparation of the metal oxide acylates described above is characterized in that

(A) at least one metal or its metal oxide compound with the non-volatile monocarboxylic acids, if appropriate in the presence of a volatile one containing up to 5 carbon atoms

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a monocarboxylic acid, preferably form or

Acetic acid sets and

(B) from the SeafeteLons masses at a temperature between 100 and 25O ° Ö the volatile compounds as much as possible in the presence of a means of setting them free abde stlllieirfe.

Oxides, hydroxides, Carbonates and lower acylates, the acyl radicals of which are 1 to Have carbon atoms, preferably acetates dissolved in an alcohol. The fffe-feallaeylate can also be used in situ during the process educated; be, usually a mixture of a metal oxide is preferably used with acetic acid as the starting material. The metals can also be used as metal powder bring. Are two or more different metals as an exit point hemrözi; so the one metal usually lies as Acetate or formoacetate and the other or the other metals as oxides. For example, the following are starting materials:

1) metal oxides such as chromium trioxide and lead oxide;

2) metal hydroxides such as Calcium ™ and aluminum hydroxide;

3) Metal carbonates such as manganese and lead carbonates

4-) Metal acetates such as basic ferric acetate HOFe (OCOGH ^) ₂ and titanium tetracetate Ti (OCOCH,) ^.

The free acid or a phenol is used as the AcylatJEOM component. Sets m & n the metal compounds in relation to the

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If an excess of acylate component is used, then - as described above - MOA products are formed, which form the excess metal

i
contain metal oxide pigments.

by inisitu educated, finely divided and not dismissed as volatile carboxylic acid is preferably acetic acid; Formic acid can also be used, less propionic and butyric acid.

The mixture of starting materials is heated until the metallic starting materials have completely gone into solution. The implementation takes place according to the following formula schemes (in which M - a 2-value, M '- a 3-value, M "- a 4-value Metal, X - the oxacyl residue of a non-volatile aliphati between monocarboxylic acid and R - a hydrogen atom, a lower one Alkyl or acyl radical):

I. MCO-, + 2CH-, C00H- ^ M (OOCCHO ₀ + H ₀ O MO + 2CH ₅ COOH- ^ M (00OCH ₅ ) ₂ + H ₂ O M (OH) ₂ + 2 / CH ₅ COOH- ^ M (OOCCH) ₂ + M + 2CH, C00H-> M (OOCCH ₅ ,) _o + H ₀

1 t> 0 c- egg

M (OOCCH-,) _o + HX-> XTiOOCCH _x + CH ₂ COOH XMOOCCH ₅ + H ₂ O-> XMOH + CH ₅ COOH

^{+ H} 2 °

CO

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II. -M ¹ ^ (OO,), + 4- GH ^ COOH -? - 2Μ '(OH) (OOCGH _x ) _o + 3CO ₀ + H ₀ O

M ' ₂ 0 ₅ + 4'GH ₃ GOOH- ^ 2M' (OH) (0OGGH ₃ ) _g . + M ¹ (OH), + ^ GH ₃ GOOH—> M ¹ (OH) (0OGGH ₃ ) ₂ + 3M ¹ + 4CH ₃ GOOH + 3Η ₂ ° --7 "Φ ^ι ί ^ΟΗ Ή ^οοσΟΗ 3) 2 HOM ¹ (OOGCH ₃ ) ₂ + HX - ^ HOM '(X) OOGGH ₃ + GH ₃ GOOH 3HOM ^ (X) OOCGH ₃ -> (OM ¹ X) _3. + 3 / 3H ₃ GOOH ν

III. 4-M "(OOGGH ₃ ) ₄ + ψβ + ^ O- ^ X ^ '^ Og + 161GH ₃ COOH

IV. 2XM0M '(0R) 0MX-> [(XMO) ₂ M ¹ J ₂ O + ROR.

The conversion and the subsequent distillation take place in the absence of solvents if lead and zinc are present as metal components. Other metals can, however, require the presence of limited amounts of solvents, Zr.B. of ligroin (Ep, 150 to 170 ⁰ G), turpentine or o-, m- and p-xylenes or mixtures thereof in order to keep the reaction product in the liquid state during the distillation. As soon as most of the volatile carboxylic acids are distilled off, the products become liquid (this indicates the absence of hydrogen bonds and most of the low molecular weight acids) or are readily soluble in hydrocarbon solvents. The distillation takes place at temperatures between 100 and 25O ⁰ C.

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The removal of the low molecular weight acid residues from the reaction product should, as explained above, take place as completely as possible, but is often associated with difficulties. Chemically bound water favors the splitting off of these
Sour ste. In order to intensify this process, one of the following substances is added to the reaction mixture during the distillation, which contain the faawoaonaLea volatile, low molecular weight aliphatic compounds (carboxylic acids, alcohols,
fe esters - see below -) set free, and the more, the less chemically bound water is present:

(1). Water or steam, until no lower aliphatic compound can be detected in the distillate. As a rule, distillation is carried out at 100 to 250 ° C .; For some metals such as copper and mercury, 100 to 150 ^° C. are sufficient, whereas, for example, iron and chromium require ^{temperatures above 150 ° C.}

* (2). A volatile alkanol, such as isopropanol or butanol, instead or in addition to the addition of water or steam | this Addition takes place for the purpose of reaction with the lower acylate residue with formation of volatile esters and coupling of the metals by means of oxygen, e.g. according to the equation:

20M0C0R + 2 ^; R'0H OMOM + 2RC00R '+ H ₂ O.

(ßLl-alkyl residue of a volatile acid, R's alkyl residue of

i
lower alcohol).

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(3). -A metal alcoholate, either an aluminum- or titanium alcoholate with a maximum of 4 carbon atoms, such as aluminum or titanium butoxide and isopropoxide, or above all a condensation product of titanium and silicon alkoxides, in which the titanium and silicon atoms via a bridging oxygen atom are connected to each other. The mixed alkoxide of the formula is particularly suitable

that by condensation of titanium acetraisopropoxide and condensed Silicic acid ethyl ester is prepared »As a rule 1 to 10% by weight of this is added to the raw reaction product to. For antimony and bismuth oxide acylates, the non-drying ones Oils are, on the other hand, up to 25% by weight are required.

The procedure according to (1) is preferred. The temperature for the procedures (2) and (5) is at least 150 * is preferably between 170 and 200 ⁰ C. In some cases, such as Ferrioxidtallat, the bath are alternately water and alcohol is added for the prevention of solidification. Procedure (3) leads to a different product than procedures (1) and (2), but the product is similar. The products obtained according to (3) are liquid at tree temperature, whereas the products according to (1) and (2) are usually solid, but easily soluble in ligroin, turpentine and xylene.

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In the examples below, various embodiments are presented of the method according to the invention explained in more detail.

I. Metal oxide acylates with Λ metal (Examples 1 to 14jl

Example 1: titanium oxide stearate.
One mixes

114 g of an isopropanol solution of titanium acetate [£ g = öf 9.6 g of Tijmit "53 grams of stearic acid

at 60 ⁰ O, 10 g of water are slowly added during the distillation at 150 ⁰ C in order to remove the remaining acetate groups and. sets a vacuum of 5 mmHg at 180 C. A wax which is clearly soluble in hexane and is suitable for waterproofing is obtained. 1. 40 ⁰ C.

Example 2: tin oxide ethyl hexanoate.
A mixture of

83 g of a ButamL solution of tin tetraacetate (23.6 g Sn) and JO g ethyl cyclic acid,

is at 130 ⁰ C was slowly added 5 g of water and is applied at 180 ° C vacuum. A viscous liquid which can be used as a catalyst for the production of urethane foam is obtained.

Example 3 Zirconium Oxide Oleate.
The following are heated:

150 g of an isopropanol solution of zirconium acetate (18.2 g Zr) - <~>

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56 g oleic acid and

60 g ligroin (bp.
then added dropwise at 200 ⁰ O in the mass of about 50 ml of water until it starts to become cloudy, is a 5 mm vacuum and continuing the heating, bid a temperature of 260 ° 0 achieved. A brown, solid solid which is soluble in xylene and suitable as a drier for oil paints is obtained.

Example 4; Ferric oxide tallate (OFeX);,. It will

38.2 g of basic ferric acetate with

28 g tall oil fatty acid mixture

heated to 220 ^{0 G.} Then 25 g of water are slowly added dropwise to the mixture and a 5 mm vacuum is applied. A reddish-brown resin-like mass is obtained. When mixed with 30 g of ligroin or turpentine, this gives a light brown color which dries to a glossy, hard coating.

oxide example 5? Iron oxide-containing ice ice precipitate.

The mixture is heated by

22.4 g iron powder \

80 g acetic acid and

80 ml of water

under reflux until no more hydrogen escapes, distilled then the water and the excess acid from and slowly gives

... 14

56 g tall oil fatty acid mixture and

40 grams of ligroin

to. The resulting deep black solution is kept at a temperature of 200 ° C., then treated with 100 g of water and 10 g of isopropanol in order to split off the remaining acetate groups and heated in a 5 mm vacuum at 220 ° C.

It becomes 84 g of a black pest and by loosening the same in a mixture of 30 g xylene and 10 g butanol one obtained black paint, in which the suspended iron oxide does not settle on storage and which to ^ one high-gloss, rust-proof coating dries.

Example 6: IPerrioxide tallate cresolate. Heat a mixture of

38.2 g basic ferric acetate HOFe (OCOCH;,),., 28 g tall oil fatty acid mixture and

11 g p- and m-cresol mixture
over the course of 30 mis. suf 220 to 230 0, then slowly drop in 25 nil water at this temperature and apply a 5 mm vacuum.

A dark brown color is obtained in every xylene and butanol Soluble hard resin, the solutions of which dry in thin layers to form high-gloss coatings. The resin is used to preserve wood applicable and, thanks to the built-in cresol, has a greatly reduced evaporation capacity.

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Example 7 · Cuprioxide Tallate.
The mix of

41.2 g cupric hydroxide,

56 g tall oil fatty acid mixture,

40 g ligroin or xylene and

24 g acetic acid

is heated at 140 ^{0 C.} "At this temperature, 100 ml of water are slowly added dropwise.

It is noteworthy that when working below 150 ° G, the product obtained is green and, with slow drying, gives light green films;
green coatings.

Films, but turns brown at around 200 ° C and dries too light-

The above, -versetzte water mixture was heated to 190 ⁰ G, and alternately outputs ligroin and xylene - a total of 30 g to in order to keep the mixture in the liquid state and to reduce the Kuprioxid to Kuprooxid; the color of the mass changes from green to brown. Heating to 23O ⁰ G and distilled in a 5 mm vacuum.

What is obtained is a brown pest, whose xylene solutions air dry to form dichromatic coatings with a good gloss and are applicable as antifouling paints for ship floors.

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Example 8: Cupric oxide-containing cupric oxide tallate (XCuOGuX + CuoO). The procedure is as in Example 4-, but 4-0 g of cupric acetate are used instead of ferric acetate. A cupric oxide tallate is obtained in which euprooxide Gu ₂ O is suspended and, after dissolving in one of the solvents mentioned, a quick-drying, brown, antifouling paint.

Example 9: zinc oxide abietinate.
The mixture is heated at 90 ⁰ G Lösungjvon

120 g rosin (acid number 300) in 4-0 g ligroin and

20 g acetic acid with

32.4 g zinc oxide,

allowing the temperature to rise to 190 ° C and then slowly added dropwise 25 ml of water, whereupon added for the purpose of conservation of mass at 200 to 23O ⁰ C in the liquid state 15 g of butanol and 20 g of ligroin (the smell of butyl acetate is felt). Finally, it is heated at 200 ° C. in a 2.5 cm vacuum.

The product has 16.5 wt.% Zinc and Schmitz at 15O ⁰ G. Its solution in 50 g of xylene are a resinous solution.

Example 10; Lead oxyethylhexanoate.
Mix a mixture of

74.2 g ethylhexyl acid,

70 g of acetic acid and

20 g of ligroin with

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, 5 S lead oxide PbO
and heated at 150 ⁰ G until a clear solution is obtained. To this one sets at a temperature between 160 and

G 50 s butanol and maintains this temperature for 60 min, during which the butyl acetate slowly evaporates. To Heating in a 5 mm vacuum gives 185 S of a clear, colorless, syrupy liquid that can be used as a primer is applicable to coatings.

Examples 11 to 15 below relate to cyclic metal oxides. ■

Example 11: Cyclic aluminum oxide isostearate (OAlX) - ,.
At 180 ⁰ G

7.2 g of aluminum acetate formate with

14 g of isostearic acid and
20 grams of ligroin

heated, then added 15 ml of water at the same temperature and heated ^{at 220 0 G in a 5 mm vacuum.}

Example 12: Cyclic chromium oxide isostearates (OGrX).

(a) The mixture is distilled from
24.7 g ghroma acetate,

15 g butanol and

55 ml of water and first add
28 g of I so stearic acid,
50 g butanol and

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20 g of xylene, and after reaching 160 ⁰ C with 20 g of the hydrocarbon solvent "IsoparM." . The mixture is then subjected to steam distillation, the temperature is then increased to 240 ° C. and the acetic acid which has been liberated is evaporated off in a 5 mm vacuum.

The solid obtained of formula (OCRX) wherein η predominately 3, 4 or 5, preferably 3, melting above 150 ⁰ C; its xylene solutions are clear, glossy, deep green in color.

(b) The one obtained by stirring

20 g chromium trioxide CrO ^,

25 g acetic acid and

10 ml of water

obtained clear solution are for the purpose of Eeduktion the CrO ^ to Chromoxide

^ O,

10 g butanol and

56 g of isostearic acid

added, whereupon the temperature is gradually increased to 250 ° C. (water and acetic acid evaporate) and one after the other 20 g each of water, butanol and again water are added. After applying a 5 cm vacuum, at least one distillation is carried out 10 min.

A green solid is obtained, which is predominantly or entirely · composed of cyclic! (OCrX) _n and its solutions in butanol, xylene or ligroin become smooth, high-gloss, saturated

ÖÖ9I4Ö / 2IÖS

dry green, translucent coatings; mixed with Linseed oil and alkyd resin can be used, for example, to form protective coatings.

Example 13 ?; Cyclic ferric oxide neoheptanoate. .

One heats up

38 g of ferric acetate with

26 g weoheptyl acid and

30 g hydrocarbon solvent "Isopar M" to 240 ° C., then 15 ml of water are added at this temperature and distilled in a 2 cm vacuum. The dark brown liquid obtained hardens to a black solid on cooling, which is soluble in equal parts of a 2: 1 xylene-butanol mixture.

Example 1A-: Cyclic ferric oxide linoleate ^ The mixture of

19.1 g basic iron diacetate,

29.5 g of methyl linoleate and

10 g of ligroih

the mixture is heated at 240 ° G for about 60 minutes until foaming has ended then add 10 ml of water and apply a 5 mm vacuum. A clear brown liquid is inherited, which after addition from 0.1 wt.% cobalt naphthenate to a non-tacky, clear coating hardened.

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II. Metal oxide acylates with 2 metals (Examples 15 to 26) ..

Example 15: Iron (III) lead (II) oxide isostearate (XiPbO), Fe. The mixture is heated by

9.5 S basic iron acetate and

33.5 S lead oxide with

35 ml of water
5 min at 100 ⁰ G, then add 42 g of isostearic acid with further heating, then gradually 40 g of ligroin

and after increasing the temperature to 200 ^° C., 10 ml of water are added and the distillation is completed in a 5 mm vacuum. A dark brown liquid is obtained, which solidifies on cooling.

Example 16; Aluminum manganese oxide stearate (XMnO) pAlX. It is heated at 130 ° 0

24.5 g of crystalline manganese acetate with

3.9 g freshly prepared aluminum hydroxide and 60 g ligroin, then with '

28 g of stearic acid, then at 175 ° C

14 g stearic acid and
50 g "Isopar M" hydrocarbon solvent.

The mass is defined at 200 G and liquefied slowly at 230 ⁰ C. After addition of 10 ml of water is to a 5-mni vacuum on. A dark brown solid wax which is soluble in butanol and ligroin is obtained.

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Example 17: aluminum magnesium oxide stearate RxMgO) pAl7pO. One heats up

14.8 g of aluminum acetate formate HGOOAi (OH) OCOCH ^ with '11, 6 g magnesium hydroxide and

50 ml of water, sets after 5 ml of water has evaporated 53 g of stearic acid and

30 grams of ligroin

closed and heated further up to 180 ° G. As soon as the mass clears, 10 ml of water are slowly added, then ^{heated to 20O 0} C "and distilled in a 5 mm vacuum.

Example 18: aluminum zinc oxide stearate (XZnO) ₀ Al Lo.

The procedure is exactly as in Example 17 ₅ , but instead of 11.6 g of magnesium hydroxide, 16.2 g of zinc oxide are used.

Example 19: Zinc aluminum oxide tallate (XZnO) ₂ AlX. To be heated

22 g of crystalline zinc acetate with 3.9 S aluminum hydroxide and
5 ml of water, then at 130 ⁰ C with

28 g tall oil fatty acid mixture and 14 g of the latter at 180 ^° C.

After applying the 5 mm vacuum, 10 ml of water are slowly added. The mass is then heated to 200 ^° C. and distilled in a 5 mm vacuum. The clear oil obtained dries to a clear film according to Zueatz of 0.5 g of a cobalt dryer.t- ¹ - es

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■ - 22 -

Example 20: Zinc aluminum oxide tallate [(XZnO) ₂ AlJ ₂ O. A dispersion of

16.2 g zinc oxide and
2.7 S aluminum powder in

30 g of ligroin with a mixture of -56 g tall oil fatty acid mixture and 12 g acetic acid.

The (to stiffening at 40 ⁰ C, but again, melting at 60 ⁰ G) mass is then 60 min at 160 ⁰ C heated; the volatile constituents are then evaporated off at 260 ^° C., then 15 ml of water are added and the mixture is distilled in a 5 mm vacuum.

Example 21: Lead alumino oxide tallate acetate T (XPbO) ₀ Al] ₀ O and (XPbO) ₂ AlX ¹ . ^U ^ Jd-

To a mixture of

14.8 g aluminum formoacetate,

56 g tall oil fatty acids and 6 g of acetic acid will be

44.6 g lead monoxide and
• 15 g of ligroin

added. After heating to 200 ⁰ C, the mass which is then treated with 30 g of butanol and then heated to 235 ° C and [includes] a 5 mm vacuum to clarify [-] j) as gray product is at 50 ⁰ C determined and, according to the formulas given above, consists of a mixture of tallat (X) and tallat acetate (Χ, Χ ¹ )

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Example 22: Zinc-chromium-oxide-tallate (XZnO) ₂ GrX. There will be a solution of
10 g chromium trioxide in

12 g acetic acid and

5 ml of water with heating

13 g zinc dust

added. The change in the color of the mass from orange-yellow to light green indicates the ongoing implementation. Man then sets

84 g tallol fatty acids mixture, after heating to 220 ° C 15 ml of water and then

5 g butanol

and distilled in a 5 mm vacuum. The product dissolved in ligroin can be used as a wood preservative stain.

Example 23: Zinc-Ehrom-Oxide-Tallate. One gives a mixture of

32.4 g zinc oxide (after reduction with 10 g butanol), 20 g chromium trioxide,

25 g acetic acid and

10 ml of water

119 g tallol fatty acid mixture

and to increase the temperature slowly to 270 ° C, wherein water and acetic acid evaporate heated further at least 60 min, added with 20 ml of water and distilled in a 5 cm vacuum least 10 min. at 270 ⁰ C.

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The light green product consists mainly of (XZnO) ₂ CrI ₂ O, • but can also contain (XZnO) pCrX. His xylene solutions dry to form clear coatings that are suitable as wood protection and rust protection.

Example 24; Zinc-chromium-oxide-tallat KXZnO) ₂ GrLo for a mixture of

24.7 g of crystalline chromium triacetate and 16.2 g of zinc oxide will be

80 ml of water

added; then the mass is heated for 30 min at 100 ° C, whereby the color turns into deep green. Then you give

56 g tall oil fatty acid mixture and 45 grams of ligroin

to, heated to 220 ° C, mixed with 20 ml of water and distilled in a 5 mm vacuum. Solutions of the light green product in Ligroin dry in the presence of 0.5% by weight of a cobalt dryer to high-gloss, crystal-clear coatings that are available as wood and Can serve as a rust inhibitor.

The following Examples 25 and 26 relate to cyclic metal oxide acylates.

Example 25; Cyclic manganese chromium oxide isostearate. Heat a slurry of

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5 g of Cr (X in 10 ml of water as well as

36.8 g of manganese acetate and

56 g of isostearic acid

gradually to 250 ⁰ G and at least 60 min at this temperature, with water and acetic acid evaporating. After adding 20 ml of water, the mixture is distilled in a 5 cm vacuum at 250 G for at least 10 minutes. The deep brown, non-drying liquid product has the! Formula

JQ- Mn-X
X— Gt ⁿ 0

^X 0- -Pli-X.

When mixed with alkyd resin, it can be used to produce high-gloss, translucent coatings.

Example 26; Cyclic cobalt-chromium-oxide-tallate. Work exactly as in Example 25, replacing the 36.8 g of manganese acetate with 37.3 g of cobalt acetate, and a product of the formula is obtained

0 Go X

X - Gr ^X 0

^ O Co X.

III. Metal oxide acylates with at least 3 metals (examples 27 to .34).

Example 27: Aluminum-zinc-cadmium-oxide-isostearate XZnOAl (X) -

■ -OCdX.

A heated to 50 ⁰ C mixture of

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84 g of I so stearic acid and

12 g of acetic acid is added

12.8 g of gadmium oxide and

8.1 g zinc oxide

added and the mass ^{heated to 140 0} G, whereby a clarification occurs. Then you put them with

14.8 g aluminum formoacetate,

that goes into solution at the above temperature, and then
increasing the temperature to 200 ^° C. with 20 ml. water,
which is then distilled in a 5 mm vacuum. The clear liquid obtained hardens below 100 ° C. The solid can be used as a stabilizer of plastic compounds.

In the following Examples 28 to 34, the condensation products of titanium and silicon alkoxides described at the beginning are incorporated into them for the purpose of splitting off the volatile, low molecular weight constituents of the starting mixtures, whereby the end products can contain 3 or 4 different metals. The aforementioned condensation products are obtained, for example, in one of the following ways:

(a) The reaction mixture of

284 g of tetraisopropyl titanate Ti (OIC ₅ H ₇ ) ^ (TPT) and

3OO g condensed ethyl silicate (40% SiO.,)
results in a clear, colorless, stable liquid that has no insoluble skin or crust in the neck of the reaction vessel

forms. The product has the formula (1-G _x H _n O) ₀ Ti 10Si (OG ₀ H ₁ ^) _x | ₂ .

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(b) The mixture, heated to 120 ° C., of 284 g of TPT with 250 g of tetrameric silicon oxide bu1> oxide (CLHqO) ₂ , Si.O ^ results in a clear, colorless, liquid product of the cyclic structure

, 0 Si-OXC ₂ H _n

\ ^{3 7}

Ci-G ₅ -H ^ O-) ~ = Ti. 0

0 Si-0-i-0, H ₇ ,

OC ₄ H ₉

The product has a higher stability in terms of temperature and hydrolysis than the starting materials. It dries in the air to give a smooth coating and can be used as a primer for protective coatings or as an adhesive for solid substrates. A condensation at 50 ⁰ C gives a similar product.

(c) The mixture of 568 g TPT and 150 g heated to 100 ° C Condensed ethyl silicate is a liquid oligomer that has a lower hydrolyzing rate than TPT and than Catalyst in the manufacture of silica alkoxide oligomers is applicable.

(d) The heated with slow dropwise addition of water to a temperature of 100 to 120 ⁰ C mixture of 568 g of TPT and 150 g of regular Orthoäthylsilikat gives a similar oligomer.

... 28

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(e) From the ^{mixture, heated at 100 to 120 0} G, of 182 g of condensed TPT and 208 g of orthoethylsilicate, a condensate with alternating -Si-O- and -Ti-O groups is obtained. The condensed TPT is obtained by heating TPT with water at 100 to 120 ⁰ C according to the equation: (n + 1) Ti (OR) ₄ + nH ₂ 0-> (EO) ₃ Ti-O- [Ti (OR) 2-Oj _n-1 -Ti (OR) ₅ + 2nR0H, where R is -isopropyl.

(f) By heating a mixture of 145 S cLes according to the US patent 3,087 94-9 of the prepared titania butoxide and 206 g Sxliciumtetraathoxid (bp 165 ° 0) at 50 ° C is a colorless one Liquid that can be heated up to 200 G without decomposition or evaporation. It consists of silicon titanium oxide ester; it is dominated by cyclic, primarily tetrameric oligomers, although some linear oligomer is also present.

Example 28:

A mixture of

30 g antimony triacetate,

56 g tall oil fatty acid mixture and

10 grams of ligroin

to 200 ⁰ G, sets a 5 mm vacuum, brings the temperature to 1JO ⁰ G, then adds 12 g of the Ti-Si condensation product described above under (a) and increases the temperature to 170 ⁰ G. After distilling off the Ethyl and isopropyl acetate is distilled in a 5 mm vacuum. A clear, light brown liquid is obtained, which is used as a catalyst for production

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... 29

of urethane resins can serve.

Example 29:.

A mixture of

30 g of antimony triacetate and

56 g tall oil fatty acid mixture.

to 210 ^° C. A 5 mm vacuum is then applied, the ^{mixture is cooled to 100 °} C. and a mixture of
6 g titanium isopropoxide and

6 g condensed ethyl silicate
and heated to 190 ^° C. An oil is obtained.

The Ti-Si condensation product added in Example 28 is left here (a) arise in situ in the reaction mass.

Example $ 0;

One heats up

25.5 g bismuth carbonate BIoO ₂ CO, and

40 g acetic anhydride
under reflux, there

36 g of ethylhexyl acid

to, increases the temperature to 210 ^° C., a 5 mm vacuum is applied and cools down to 100 ^° C. Then 20 g of the Ti-Si condensation product (a) are added; the temperature is now ^{increased to 130 °} C. for 10 min and the mixture of ethanol and isopropanol is distilled off in a 5 mm vacuum. A clear brown liquid is obtained.

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Example 31 '- A mixture of

40.6 g bismuth triacetate and 56 g tall oil fatty acid mixture

is heated to 21O ⁰ C, then a 5 mm vacuum applied and cooled to 10O ⁰ C. Then, as in the. Example 29,

6 _H g of titanium isopropoxide and

6 g condensed ethyl silicate,

the in situ condensation product (a) form, and heated to 190 ⁰ G. obtaining a dark-colored liquid.

Example 32:

A solution of 20 g of zinc oxide in a mixture of 43 g ethylhexyl acid and 6 g acetic acid

to 220 ^° C., a 5 mm vacuum is applied and the temperature is brought to 150 ^° C. The Ti-Si condensation product (a) is then introduced, ^{heated for 40 min at 10 ° to 180 °} C. and in the 5 mm -Vacuum distilled. A viscous liquid is obtained.

Example 33 ' A mixture of

28.6 g basic ferric acetate, 24.3 g zinc oxide and 84 g tall oil fatty acid mixture

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we heated to 200 0. After applying a 5 mm vacuum, it sets man

10 g of the Ti-Si condensation product (a)

and distilled in vacuo. A clear, dark brown color is obtained Liquid that can be used as a protective stain for timber.

If the condensation product (a) is exchanged for each of the products (b) to (f), similar results are obtained.

Example 34-s

A 100 0 hot solution of ■

25.5 g barium acetate in

40 ml of water are mixed with '■

74 g ethylhexyl acid
and heated to 100 ° C, then gives

12.6 g bismuth carbonate

and heated for another 30 minutes until the mass clears. Thereafter, a 5 mm vacuum is set, cooled to 110 ⁰ G, and 9 of the Ti-Si-condensation product (a) g was added. The mixture is then heated to 130 ° C. and a 5 nua vacuum is applied again to remove the alcohols. 117 g of a viscous, clear oil which is suitable as a heat stabilizer, for example for vinyl plastics, are obtained.

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Claims (1)

2nd July 1969
SJ / Hu <jrb 7059 Claims / 1. \ Metal oxide acylates, characterized by ^ - η e t that (A) the metal components of which are at least two, at least divalent, preferably divalent to tetravalent, identical or different metal atoms linked to one another via oxygen bridges and (B) their acylate component to at least 55 mol% (A) from residues of at least 7 »preferably 9 to
Non-volatile monocarboxylic acids containing 22 carbon atoms, (b) from 0 to 100, preferably from 5 to 100 KoI ⁰ Zo _1, calculated on (a), from phenol residues and the remainder from oxacyl residues from volatile aliphatic Carboxylic acids exist. 009840/2305 2. Metal oxide acylates according to claim 1, consisting of at least two metals of different valence and in the Acylate component to at least 70 mol% from acylates (a) and (b). 3. Metal oxide acylates according to claim 1 and 2, the acylate component thereof is phenolate-free and / or consists exclusively of residues of non-volatile monocarboxylic acids. 4. Metal oxide acylates according to claim 1 to 3 of the formula (XMQ) ₂ M ¹ OM ¹ COMX) ₂ , where M - 2-valent, Ή * - 3- ^ valent metal atoms and X - are the acylate groups consisting of (a) and (b). 5 «metal oxide acylates according to claim Λ to 4 with a molar ratio of metal to acylate, in particular to the acylate of non-volatile carboxylic acids, higher than 1: 1, preferably 2: 1, 3: 1 or even higher, the excess metal in the form of finely divided, stable dispersed metal oxides is present and the reaction product is a pigmented color. 6. MetallQxidacylate according to claim 1 to 5, containing as Metal oxides representing color pigments Ferro, ferric, copper, chromium, nickel or manganese oxides. 7. metal oxide acylates according to claim 1 to 6, characterized in that that it condenses a titanium-silicon-misehoxide contain. 8. Metal oxide acylates according to claim 1 to 7 »consisting of Ferric oxide tallates im. Mixture with aluminum flakes. 9. Process for the preparation of metal oxide acylates according to claim. 1 to 8, characterized in that one (A) at least one metal or its metal oxide compound with the non-volatile monocarboxylic acids, if appropriate in the presence of a volatile aliphatic monocarboxylic acid containing up to 5 carbon atoms, preferably Formic or acetic acid, converts and (B) the volatile compounds are distilled off as largely as possible from the reaction masses at a temperature between 100 and 250 ⁰ O in the presence of an agent for releasing them. 10.Verfahren according to claim 9 »characterized in that one or the metal oxide compound used is oxides, hydroxides, carbonates / acylates with 1 to 5 carbon atoms in the acylate, preferably acetates, in particular of iron (II), iron _w (III), copper, chromium, nickel and manganese. 11. The method according to claim 9 and 10, characterized in that that the metal acylates of lower acids in the reaction mixture can arise in situ. 12 .. The method according to claim 9 to 11, characterized in that · that the volatile compounds are set free Water or steam and / or a lower volatile alcohol such as butanol or isopropanol is also used. 13 · The method according to claim 9 to 12, characterized in that that one has to set free the volatile compounds at most 10% by weight (of the weight of the metal oxide acylate formed) Aluminum or titanium alkoxides, preferably liquid condensation products of the latter with silicon alkoxides, where the alkyl radicals contain a maximum of 4 carbon atoms, mi tve rwende t. 14. The method according to claims 9 to 13, characterized in that that you set free the volatile compounds ι a liquid condensation product of the formula used. 15. For releasing volatile compounds according to claim 13 and 14 serve-) liquid condensation products of titanium and silicon alkoxides, their alkyl radicals at most Contains 4 carbon atoms. 009840/2305 '" ³ 16. Liquid acyclic condensation product according to spoke 15 of the formula 1-C ₅ H ₇ -O-) ₂ Ti £ -OS.i (OG ₂ H ₅ 17. Liquid cyclic condensation product according to claim 15 of the formula S (iC, H _l7 O-.) PTi ^N 0 0 Si-OIC ₅ H ₇ i ^N 0 Ί8. Process for the production of the liquid condensation products according to claim 15 to 1 ?, characterized in that man (a) condensed or uncondensed titanium isopropoxide with (b) Silicium-tetraethoxide (orthoethylsilicate) / Stebssf or condensed ethyl silicate or tetrameric silicon but- . oxide of the formula (C ₄ H ₉ O) ₄ Si ₄ O ₆ condensed. 009840/2305