DE2137633A1 - PROCESS FOR THE PRODUCTION OF DIORGANO TITANIUM OXIDE COMPOUNDS - Google Patents

Description

TITANGESELLSCHAPT MBH Leverkusen, July 21, 1971

Leverkusen Su / Rüh

2237633

Process for the preparation of diorganotitanium oxide compounds

The invention relates to the preparation of compounds of the general

R ¹ O
Formula _., _Tn ^ Ti = O, in which R 'and R "represent organic radicals which can be the same or different. Compounds of this type have been known for some time.

Dialkoxy titanium oxides, in particular di-n-butoxy and di-n-propoxy titanium oxide, were first discovered by AN Nesmejanov> 0. V. Nogina, R. Ch. Frejdlina (Doklady AkaÜ. Nauk SSSR 95 (195 ² O pages 813-815) The alkoxy compounds of trivalent titanium required for this purpose had to be prepared beforehand by reducing tetraalkoxy titanium compounds with alkali metals. By transesterification with higher alcohols or phenols, the corresponding higher and more complex dialkoxy titanium oxides could be prepared from such accessible lower dialkoxy titanium oxides .

(A. N. Nesmejanov, 0. V. Nogina, V. A. Dubovickij; Izvest. Akad. Nauk SSSR (1961) pages

Bradley D. C., Gaze R., Wardlaw W. (J. Chem. Soc. (1955) pp. 721-726; and (1957) pages 469-478) succeeded somewhat later, by hydrolysis of To produce tetraalkyl titanates with water in a molar ratio of 1: 1 dialkoxy titanium oxides, but only in polymeric form.

Titanium oxides of the type (R ¹ O) -Ti- (R ¹¹ O), in which R ¹ and R ″ are identical or different

11

can be, according to US-PS 3.4l8.3 ^ 7 from lower tetraalkoxytitanium compounds (RO) / Ti by reaction with organic hydroxy compounds of the

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ORIGINAL INSPECTED

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general formula R ¹ OH and / or R "0H and subsequent partial hydrolysis synthesized. The reaction takes place approximately according to the following equation:

(RO) ^ Ti + R * 0H> (RO) ₃ Ti (OR ') j

(RO) ₇ Ti (OR ¹ ) + R "0H 5 (RO) ₂ Ti (OR ¹ J (OR")

(RO) ₂ Ti (OR ¹ ) (OR ") + HOH ^ 2 ROH + (R ¹ O) TiO (OR ¹ )

In this way, however, only those titanium oxide compounds can be produced whose organic radicals cannot be split off hydrolytically, preferably those in which R * and R "are an alkyl radical with 10-20 carbon atoms, an alkylphenyl-alkoxyphenyl or halophenyl radical, or else a -Si (R ) - radical, with R ₁ = benzyl radical. Apart from the fact that the preparation is very expensive, compounds with lower hydrolytically cleavable alkyl radicals cannot be obtained in this way.

According to the known methods, either only polymeric products can be produced represent, or it must be difficult and cumbersome procedural steps be made to ge the monomeric compounds

It has been found that the following procedure offers the possibility of simple way to monomeric diorganotitanium oxides of the general formula

_. "_. ^ iTi = O, in which R ¹ O and R "0 are identical or different alkoxy,

Represent aralkoxy, aroxy, alkaroxy, carboxy or 3-oxo-alkenoxy radicals, to get: "

A compound of the formula TiCl X, in which X is chlorine or an alkoxy, Is aralkoxy, aroxy, alkaroxy, carboxy or 3-oxo-alkenoxy radical, is in an inert solvent g <- "is and by introducing gaseous Ammonia precipitated in the form of the corresponding ammonia addition product. The precipitated addition product is used in stoichiometric amounts compounds containing hydroxyl and / or carboxyl groups and / or enolizable and / or water reacted so that

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a) upon receipt of a connection TiCIJC in which X is chlorine, per mole of releasing piece tem TiCIi, simultaneously or in any order one mole of water and two moles of same or in each case one mole of two different hydroxyl or carboxylgruppenhaltlger or enolizable compounds of the formulas R ₁ -OH, R ₁ -COOH, R ₁ -CO-CH ₂ -CO-R ₂ , in which R _{1 is} an alkyl, aralkyl, aryl, alkylaryl and R _{p is} an alkyl, aralkyl, aryl, Alkylaryl and R_ can be an alkyl, aralkyl, aryl, alkylaryl or alkoxy radical, or that

b) upon presentation of a compound TiClJiCp in which X is an alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or 3-oxo-alkenoxy radical, first one mole of water per mole of the diorganotitanium dichloride used and then optionally two moles of the same or one mole each of two different hydroxyl or carboxyl group-containing or enolizable compounds of the general formulas R ₁ -OH, R ₁ -COOH, R ₁ -CO-CHp-CO-R, in which R is an alkyl, aralkyl, aryl, alkylaryl - and R can be an alkyl, aralkyl, aryl, alkaryl or alkoxy radical which boil at a higher temperature than the organic component released during the reaction, are added,

and that then from the precipitated ammonium chloride and the solvent is separated.

The reaction taking place here can be shown schematically according to the following equations for X = Cl and χ ^ 4 as well as when using a compound R _{1 -OH:}

TiCl ^ + xNIL -> TiCl _{4 -XNH 5} ;
iCl ₄ -XNH ₅ + H ₂ O - ^ TiOCl ₂ * (x-2) NH, + 2NH ₄ Cl

TiOCl ₂ * (X ^) NH ₃ + 2R ₁ OH - ■> _{R o} J> Ti = O + 2NH ₄ Cl + (x-4) NH

_o J ₄ )

When using two different organic compounds R. ¹ OH and R. "OH, the reaction proceeds according to:

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R ₁ ¹ O TiOCl ₂ ⁴ (x-2) NH + R ₁ ¹ OH + R ₁ ¹¹ OH -> _R " ₀ ^ Ti = O + 2NH ₄ Cl + (x-4) NH,

In the event that X is an alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or 5-oxo-alkenoxy radical and χ = 2, the compounds react according to the scheme

TiCl ₂ (OR) ₂ + xNH _{v 22}

TiCl ₂ (OR) ₂ -XNH + H ₂ O -> TiO (OR) ₂ + 2NH ₄ Cl + (x-2) NH,

or

RO
TiCl ₂ (OR) ₂ -XNH + H ₂ O + 2R ₁ OH - > _RQ > Ti-0 + 2R0H + 2NH ₄ Cl + (x-2) NH

If the conversion is to take place according to the last equation, the boiling point of the compound used must be R.
Reaction formed compound ROH.

point of the compound R, OH used are higher than that of the

Whether the reactions actually expire after these equations ¹ or not is not known in detail. This is irrelevant for the idea of the invention.

An essential part of the invention is the precipitation of the ammonia addition compounds of the titanium compound TiCl _p Xp used. These compounds can be separated and detected after the ammonia has been introduced. These are solid, mostly yellow substances that are insoluble in solvents that are inert _{to TiCl 4.} How many ammonia molecules attach to each of the titanium compounds has not been determined in detail. However, it is known that, depending on the reaction conditions, compounds of the formula TiCl _{4 -XNH 7} with 4, 6 or 8 NHL molecules are formed _{from TiCl 4 and ammonia.} There, as determined in the course of the investigation

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could be the addition of about k moles of ammonia per mole of TiClj. is sufficient for the entire course of the reaction, it can be concluded that addition compounds of TiCl. with 4 moles of NH- arise.

If compounds of the formula TiCl _p X are used in which X is an organic radical as defined above, the amount of NH. The fact that the number of added NH -, - molecules is about 2, can be indirectly concluded from the fact that when the ammonia addition compound is reacted with water according to the equation on page 4, lines 6 and 8, no appreciable amounts of ML, are left in freedom be set.

The precipitated ammonia addition compounds are then reacted with the stoichiometrically required amounts of water and the hydroxyl or carboxyl group-containing or enolizable compounds of the general formulas R ₁ -OH, R ₁ -COOH, R ₁ -CO-CH ₂ -CO-R ₂ . For each mole of titanium compound used, 1 mole of H _p 0 and 2 moles of one of the organic compounds or in each case 1 mole of two different organic compounds are added. When using different organic compounds, these can be distinguished by their radicals R or R _? differ, for example R ₁ ¹ OH and R ₁ ¹¹ OH, and also belong to different classes of compounds, for example R ₁ ¹ OH and R ^ 'COOH.

. ".""" ^ TiCJL · is assumed, whose organic radicals R ¹ O and R ¹¹ are selected O so as to allow the joint to be made - the addition of the organic compound if of a Diorganotitandichlorid of the formula may be omitted, are identical. The addition of water creates the desired diorganotitanium oxide directly from the ammonia addition product.

Should, however, a titanium oxide with other organic residues than those If the titanium compound used is to be produced, the corresponding organic compound or compounds must be added

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, whereby these have to boil higher than those for the implementation in Organic component or components to be set free. The reaction can be represented for R '= R "= R in the form of a transesterification:

(RO) ₀ Ti = O + 2R ₁ OH - - £ - (R ₁ O) ₀ Ti = O + 2R0H.

The organic compound ROH released in the process then only needs to be distilled off with the excess solvent.

If compounds of the formula TiCl ₀ X ₀ , in which X is an alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or ^ -oxo-alkenoxy radical, are used as starting substances, it is not necessary to proceed directly from these diorganotitanium di-chlorides. It is possible to use TiCl ^. and a tetraorganotitanium compound, for example Ti (OR) ₁ ,, in a molar ratio of 1: 1 or TiClj, and an organic compound, for example ROH, in a ratio of 1: 2 and to allow the two components to react with one another to form the diorganotitanium dichloride, before ammonia is introduced. If TiClu and a suitable alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or j5-0xo-alkenoxy compound are initially introduced in a molar ratio of 1: 2, it is not necessary that the formation of the diorganotitanium dichloride, which is preferably in the Boiling heat occurs, immediately runs completely. When NH, -Gäs is subsequently introduced into the cooled reaction solution, the unreacted organic component reacts with the TiCl ^ until the formation of the diorganotitanium dichloride is complete. The ammonia addition compound is only formed when NH_ is introduced further.

ψ The organic components of the general formulas R.-OH, R ₁ -COOH and R ₁ -CO-CHp-CO-Rp suitable for reaction with the titanium-ammonia addition products are inst -:, idere aliphatic and aromatic Hydroxy compounds, carboxylic acids and enolizable ketones.

Aliphatic oxides are used to produce dialkoxy and diaroxy titanium oxides and aromatic hydroxy compounds are required. Examples of aliphatic hydroxy compounds are aliphatic and cycloaliphatic and

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polyhydric, primary, secondary and tertiary alcohols. As aromatic Hydroxy compounds are preferably phenols, cresols and naphthols.

To obtain diacylate titanium oxides, carboxylic acids are used, both aliphatic and aromatic, saturated and unsaturated Mono-, poly- and hydroxycarboxylic acids.

Enolizable ketones are used for the production of titanium oxide chelates, such as 1,3-diketones and 1,3-ketoearboxylic acid esters.

Are supposed to synthesize diorganotitanium oxides with various organic residues mixtures of hydroxy and / or carboxy and / or 3-oxo-alkenoxy compounds can be used.

It is necessary to carry out the reaction in an inert organic medium, because otherwise the reaction because of the large amounts of ammonium chloride precipitated would not run completely and separation would be difficult. Suitable solvents for this are aliphatic and chlorinated Hydrocarbons as well as lower aromatics, provided they meet the requirement meet to solve the titanium compound serving as the starting product and the desired end product. The preferred solvent is carbon tetrachloride.

The present procedure is expediently carried out as follows:

Titanium tetrachloride or a diorganodichlorotitanium compound is dissolved in an inert solvent, preferably in carbon tetrachloride. The substances used must be completely dry in order to avoid uncontrolled hydrolysis of the titanium compound. During the entire reaction, care must also be taken that, apart from the calculated amount of water, no further moisture can get into the reaction system. At least 4 moles of ammonia gas are passed into the resulting solution of the titanium compound presented, with stirring and cooling when using TiCIn, and at least 2 moles of ammonia gas when using diorganodichlorotitanium compounds,

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* 2237633

but not until the solution is saturated. One falls yellow ammonia addition compound of the titanium compound used. Then it will take from a few minutes to a few hours per mole of titanium compound initially charged, one mole of water and, if appropriate, 2 moles of a suitable organic compound or 1 mole of two different ones organic compounds added dropwise. For compounds with a low boiling point, especially short-chain aliphatic alcohols, slightly more than 2 moles are added because with these low-boiling compounds there is a risk that evaporation losses will occur. Any excess remaining in the suspension bothers and damages not, it is removed with the solvent in the subsequent distillation. The addition of water and organic compound can be done at the same time take place. However, it can also be used in any order.

When using diorganodichlorotitanium compounds as the starting product, it is advisable to add the required amount of water first and then, if necessary, the transesterification component. At the same time, excess ammonia escapes. A temperature rise of up to 50 ° C. is permitted, otherwise external cooling must be used. To complete the reaction and to improve the filterability of the NHLCl, it is advisable to leave the additions for some time, preferably 50 minutes The precipitated ammonium chloride is then filtered off from the suspension obtained and this is washed out several times with the solvent used to completely remove the diorganotitanium oxides retained the solvent was distilled off under normal or reduced pressure. The isolated product is the desired diorganotitanium oxide.

An isolation of the produced diorganotitanium oxide is only then not possible if the compound is not or not sufficiently soluble in the solvent used and thus completely or partially the precipitated

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Ammonium chloride is added. If it does not succeed, for such a connection, To find a suitable solvent especially for titanium oxides with a higher organic residue, this compound can only be found via the detour of a transesterification or an implementation analogous to the transesterification be won. In such a case, starting from titanium tetra chloride or a dialkoxytitanium dichloride with a short alkyl radical, in the way according to the invention a dialkoxytitanium oxide, preferably dipropoxy or dibutoxy titanium oxide, synthesized and from the precipitated ammonium chloride filtered off. The titanium oxide compound dissolved in the piltrate is then reacted with the higher organic component, whereupon the reaction product precipitates and solvent and lower alcohol can be distilled off.

To prove that actually diorganotitanium oxides in the implementation according to the invention are formed and not about, as equally possible and conceivable, condensed titanates, the reaction behavior of the compounds prepared was investigated and prepared using other methods Polytitanates compared.

For these investigations, reactions with higher alcohols, such as Octyl alcohol and reactions with tetraethyl silicate are suitable.

In the former case, for example, one synthesized according to the invention was synthesized Dibutoxytitanium oxide and a commercially available polybutyl titanate reacted with n-octyl alcohol under identical conditions. In the event of of the dibutoxytitanium oxide should be the transesterification according to the equation:

i = O + 2 C

₈ H ₁₇ OH> (C ₈ H ₁₇ O) ₂ Ti = O + 2 C ₄ H ₉ OH

run completely, while a quantitative one with polybutyl titanate Replacing the butoxy against octoxy radicals is likely to be difficult.

A product with 14.8 % Ti was obtained from the butoxy titanium oxide with 23.3 % Ti, which corresponds almost exactly to the theoretical titanium content (14.9 % Ti) of dioctoxy titanium oxide.

With polybutyl titanate as the starting product with a content of 22.8 % Ti, on the other hand, a substance with 17 * 3 % Ti was obtained, which is a conclusion

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lets that a titanate has formed which contains butoxy and octoxy radicals at the same time; because a pure polyoctyl titanate obtained by transesterification would have a Ti content of only 13 * 8 %.

Considerations have been given for the reaction with tetraethyl silicate and results from A. K. Nesmejanov and O. V. Hogina (Doklady Akad. Nauk SSSR 117 (1957) pages 249-251). You had at Studies of addition reactions with the ^ Ti ^ bond found that for example dibutoxytitanium oxide with tetraethyl silicate in the following form reacts:

OC ₂ H ₅ (C ₄ H ₉ O) ₂ Ti = O + Si (OC ₂ E ^) ₄ -> (C ₄ H ₉ 0) ₂ -Ti-0-Si- (OC ₂ H ₅ ) ₃

The resulting Ti-O-Si "" ^T sr-bbidung theoretically contains 11.5% Ti and 6.7% Si. This reaction was carried out with according to the invention produced Dibutoxytitanoxid, so obtaining a product with 11.2% Ti and 7, 0 % Si.

When using \ ^r on polybutyl with 22.8% Ti, however, a matter was recovered whose titanium content 22.5 $ and the silicon content was. $ 0.7.

These numbers clearly show that what is produced according to the invention Dibutoxytitanium oxide reacts in the manner described by A. N. Nesmejanov, while in the case of polybutyl titanate both components do not or only have reacted to one another to a small extent.

The reaction with Kieselsäuretetraathylester was also used to demonstrate that 3- ^ 18.3 ^ 7 and that of the present invention, identical products are hold by the method -t dor US-PS.

With these results the proof should have been provided that from the ammonia addition products of titanium tetrahalide or diorganotitanium dichloride the corresponding organic titanium oxides are formed by simple reaction with water and suitable organic compounds.

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The synthesis process according to the invention thus opens up a simple one Way to get to this interesting class of compounds, their possible uses lie in the most varied of areas. So compounds of this type are not only used as coating agents, for example for glass and paper, usable; they can also be used as polymerization catalysts use and because of the ability of the Ti = O group to add, they can be used in many applications, for example for the modification of binders and plastics, as an adhesion promoter and for thixotroping emulsion paints.

The method according to the invention is intended by the following examples are explained in more detail without restricting its application. The majority of the following examples produced substances reacted with silica tetraethyl ester and analyzed again.

example 1

Production of dimethcocytitanium oxide (CILO) Ti = O

A solution of 55 ml of TiCli (0.5 mol) in 2 1 of CCl ₁ ^ was placed in a 4 l flask, into which ML gas was introduced with external cooling until saturation. TiCl ^ precipitated out as a yellow ammonia addition compound. _{First 9 g of H 3} O (0.5 mol) and then 55 g of CH, OH (1.1 mol) were added dropwise to the suspension obtained with stirring at room temperature, the yellow precipitate changing its color to white and the temperature by about 10 ° C rose. Boiling under reflux for two hours completed the reaction and improved the filterability of the precipitated NHLCl during the subsequent separation of the precipitate from the cooled suspension. After the CCIj had been distilled off from the filtrate, a light white, almost chloride-free powder of dimethoxytitanium oxide was obtained. The analytically determined Ti content of the product was 37 * 5 $ (theoretical value: 38.1 %).

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The experiment was repeated with the difference that in the suspension of the TiClh-ammonia addition product first methanol and then water / water were added dropwise. The substance isolated in this way differed neither in appearance nor in composition from that used in the Addition of water and methanol was obtained in reverse order.

■ Example 2

Production of dipropoxy titanium oxide (CJLO) Ti = O

a) from titanium tetrachloride by adding water and propanol separately.

27.5 ml TiCl ₁ . (0.25 mol) in 1 1 CCl ₂ . were dissolved, were precipitated as a yellow ammonia addition compound by introducing ΝΗ, gas. First 4.5 g of HO (0.25 mol) and then JO g of n-propanol (0.5 mol) were added dropwise to the suspension obtained at room temperature with stirring. The mixture was then stirred for a further hour at about 20 ° C. before the precipitated NH ₂₁ Cl was filtered off and the solvent was distilled off. The product obtained was almost free of chloride and was a highly viscous yellow substance with an analytically determined titanium content of 26.0 % (theoretical value: 26.4 %)

The experiment was repeated, with the addition of propanol before the of the water, the same product was obtained as above with the reverse addition.

b) from dipropoxytitanium dichloride and water.

aa) when producing the half-ester from equimolecular amounts of tetranopropyl titanate and TiCl ₁ ..

To this end, 142 g of tetra-n-propyl titanate (0.5 mol) were dissolved in 2.5 1 CCl ₂ , and 55 ml of TiCl ₂ (0.5 mol) were added. The half-ester Ti (OC-Ji _7. ) "Cl _p formed in this way was precipitated as an ammonia addition compound by introducing NH -, - gas. Then 18 g of HpO (1.0 mol) were added at room temperature,

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Stirred for a further 2 hours and separated from the NH.Cl formed. The substance obtained, freed from the solvent, was a yellow, highly viscous mass with a titanium content of 25.8 %.

bb) when producing the half-ester from n-propanol and TiCl _2,.

In a solution of 55 ^m l TiCl _2, (0.5 mol) in CCl 2 1 _2, was added dropwise at the boil in the course of one hour 65 g n-propanol (1.08 moles), the HCl evolved. After boiling under reflux for one hour, NH, gas was passed into the cooled solution to precipitate the ammonia addition compound. _{9 g of H p} 0 (0.5 mol) were then added to the suspension, the mixture was stirred for a further 2 hours and worked up in the manner described above. The product obtained differed neither from the substance isolated under a) nor from the substance isolated under aa).

Example 3

Production of dibutoxy titanium oxide (ChHgO) ₂ Ti = O

a) from TiCl ₂ , by adding water and butanol separately.

In a solution of 110 ml of TiCl ₂ ^ (1.0 mol) in 4 1 CCl ₂ , NH ~ gas was introduced with external cooling until saturation, the yellow TiCl ₂ , ammonia addition compound precipitated. In the course of 60 minutes, 18 g of H ₃ O (1.0 mol) and 148 g of n-butanol (2.0 mol) were then added and the mixture was stirred at 20 ° C. for a further hour. The suspension was worked up as indicated in the above examples. A yellowish, viscous, almost chloride-free liquid with a titanium content of 23 * 3 ^c / ° (theoretical value: 22.8 %) was isolated.

b) from TiCl ₂ , by simultaneous addition of water and butanol.

In this variant, as described above, the procedure was followed The difference is that the required amounts of water and butanol are not

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one after the other, but together as a slogan. That isolated product was identical to that obtained under a).

c) from dibutoxytitanium dichloride and water.

aa) when producing the half-ester from equimolar amounts of tetran-butyl titanate and TiCl ^.

A solution of 170 g of n-butyl titanate (0.5 mol) in 2.5 liters of CCl ₂ was admixed with 55 ml of TiCl 2 (0.5 mol); KEL gas was passed into the resulting half-ester solution with cooling, the corresponding ammonia addition compound being precipitated. 18 g of HO (.1.0 mol) were then added to the suspension at about 20 ° C. , the mixture was stirred for a further 2 hours and, as described above, freed from N% C1 and solvent. Siei: nioh * distinguished the isolated dibutoxytitanium oxide from the products obtained under a) and b).

bb) when producing the half-ester from n-butanol and TiCl ^. In a boiling solution of 55 ml TxGij. (0.5 mol) in 2 1, 80 g of n-butanol (1.08 mol) were added dropwise, releasing HCl. The solution was then refluxed at boiling temperature for a further hour before the anionic acid addition compound of the half ester was precipitated _{after cooling by saturation with NE 7 gas.} 9 g of HpO (0.5 mol) were added to the batch, the mixture was stirred at 20 ° C. for a further 2 hours and worked up in the customary manner. In this batch, too, the isolated substance could not be distinguished from the products obtained under a) and b).

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Example 4

Production of diphenoxy titanium oxide ((L-HLO) JTi = O

a) from TiCl ₂ . by adding water and phenol separately.

A solution of 110 ml of TiCl ^ (I ₅ O mol) in 4 1 CCl ^ was saturated with cooling 'with ΝΗ, gas. _{18 g of H p} 0 (1.0 mol) and 188 g of phenol (2.0 mol), dissolved in 800 ml of CCl ₂ ^, were added in succession to the resulting suspension of the TiCl _{2 ammonia addition product.} After stirring for one hour, the diphenoxytitanium oxide was isolated in the manner described. It was a solid, red-brown product with a titanium content of 19.1 % (theoretical value: 19.2 %) .

b) from diphenoxytitanium dichloride and water in the production of the half-ester from phenol and TiCl ^.

A solution of 9 h g of phenol (1.0 mol) in 400 ml of CCl _{2 was added} dropwise to a boiling solution of 55 ml of TiCl ^ (0.5 mol) in 1 liter of CCl ₂ . In order to achieve the most complete possible elimination of HCl, the reaction mixture was kept at the boiling point under reflux for one hour. After the solution had cooled, the ammonia addition compound of the half-ester was precipitated by introducing NH, gas. Then 9 SH _p 0 (0.5 mol) were added, the mixture was stirred at 20 ° C. for a further hour and worked up in the usual way. The isolated, solid, red-brown diphenoxytitanium oxide had a titanium content of 19.0 % ; it did not differ from the product obtained under a).

Example 5

Production of dipropionate titanium oxide (CH ^ -CH -CO) ₀ Ti = O

By introducing NH -.- gas into a solution of 55 ml of TiCl ₂ (0.5 mol) in 1 1 of CCl ₂ . became the ammonia addition compound of TiCl ₂ . failed. A solution of 9 g of H _p 0 (0.5 mol) in X> \ g of propionic acid (1.0 mol) was slowly added to this suspension. After stirring for two hours at 50 ° C., NH ₂₁ Cl and CCl ₂ . separated in the usual way. Solid, yellowish dipropionate titanium oxide remained with a titanium content of 22.6 % (theoretical value: 22.8 %).

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Example 6

Production of distearattite anoxide (C, _, H _.- CO) Ti = O

■ * - -L / X> \\ Ί

from dibutoxytitanium dichloride.

First of all, dibutoxytitanium oxide was produced using dibutoxytitanium dichloride as described in example j5c). After separation of the NHhCl from the reaction solution containing the Dibutoxytitanoxid Piltrat with the required amount of stearic acid - 568 g of stearic acid (2. ₅ 0 mole) to 47.9 g Ti (1.0 mol) - added. The mixture was then heated to boiling temperature under reflux for 2 hours before the solvent and released n-butanol were distilled off. The synthesized waxy distearate titanium oxide was light brown and contained 7 »5 % Ti (ttEcpetical value: 7 * 6 fs) ·

Example 7 _CH _

Production of bis (ethylaeetoacetate ) titanium oxide (C Ht-OOC-CH = CO) -Ti = O a) from TiClj ,, water and ethyl acetate.

A solution of 55 ml TiCl ^ ₁ (O ₅ 5 mol) in 1 1 CCl ^ was treated in the manner described with NH_ gas. Then, within 10 minutes, first 9 S HpO (0.5 mol), then 130 g of ethyl acetate (IjO mol) were added in each case. The mixture was stirred under reflux for 30 minutes at room temperature between the two additions and for 2 hours at boiling temperature after the two additions. The bis- (äthylaeetoacetat) titanium oxide obtained after separation of üiHj.Cl and CCIh was a red viscous liquid with 14.7 % Ti (theoretical value: 14.9 %).

b) from dibutoxytitanium dichloride ^ water and ethyl acetate.

Ia a suspension of the ammonia addition product prepared according to Example 3c) of the dibutoxytitanium dichloride xv was per mole of half-ester 1 mole of HpO 'is added, stirred and rubbed as under jjc) filtered off from the NHlCl. The dibutoxytitanium oxide contained in the Piltrat

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the required amount of ethyl acetoacetate - 260 g of acetoacetate (2.0 mol) per 47.9 S Ti (1.0 mol) - was added and the mixture was stirred under reflux at the boiling point for hours. Released n-butanol and CCl ₂ . were then distilled off. The isolated substance was identical to that obtained under 7a).

Example 8 _n “ CH ₃

Production of bis (acetylacetonate) titanium oxide (CH ^ -CO-CH = CO) ₂ Ti = O

a) from TiCIu, water and acetylacetone.

One as produced in the previous examples. Suspension of TiCl _2.-Ammoniate was mixed with 200 g of acetylacetone (2 _# 3Mole) per mole of titanium compound and then with 18 g of HgO (] 0Mol). The mixture was stirred under reflux for JO minutes at about 20 ° C. between the additions, and for 2 hours at the boiling point after the additions. Then NH ₁ ^ Cl was filtered off and CCl _{1 was} distilled off from the filtrate. The bis (acetylacetonate) titanium oxide obtained was a dark red, highly viscous substance with a titanium content of 17.9 % (theoretical value: 18.3 %).

b) from dibutoxytitanium dichloride, water and acetylacetone.

As stated under Example 7b), dibutoxytitanium oxide was initially in CCl ₂ . produced as a solvent. After the NH ₂₁ Cl had been separated off, 2 moles of acetylacetone were added per mole of titanium compound, the mixture was stirred under reflux for 2 hours and CCl ₂ . as well as released n-butanol distilled off. The product obtained did not differ from that obtained under 8a).

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20988B / 1388

2237633

Production of butoxypropionate titanium oxide _y Ti = O

C ₂ H ₅ CO 0

In a solution of 55 ml TiCl ^ (0.5 mol) in 1 1 CCIu was with cooling ΝΗ -, - Gas introduced, whereby the ammonia addition compound of TiCl ^ failed.

Then J> 7 g of n-butanol (0.5 mol) and 57 g of propionic acid (0.5 mol) were added over the course of about 10 minutes and the mixture was stirred for a few more minutes before 9 g of HpO (0.5 mol) were added over the course of 10 minutes Mol) were dropped into the suspension. The mixture was then stirred for a further hour. The suspension was worked up as indicated in the previous examples; the butoxypropionate titanium oxide obtained contained 22.5 % Ti (theoretical value: 22.85 %) .

Some examples were repeated, using as a solvent instead of carbon tetrachloride cyclohexane was used. The products obtained with different solvents differed not from each other.

TG 71 - 19 -

2 0 9 B 8 b / 1 3 8 8

Claims (10)

2237633 Claims ί, -L / experienced for the production of diorganotitanium oxides of the general ^ - ^ Formula: R ¹¹ O ^ in which R ^! 0 and R ¹¹ O represent identical or different alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or 3-oxo-alkenoxy radicals, characterized in that one-a compound of the formula TiCl ₂ Xp, in which X is chlorine or denotes an alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or 3-oxo-alkenoxy radical, dissolved in an inert solvent and precipitated by introducing gaseous ammonia in the form of the corresponding ammonia addition product and the precipitated addition product with stoichiometric amounts of hydroxyl - and / or carboxyl-containing and / or enolizableX "compounds and / or water so that a) when a = compound TiCl X, in which X is chlorine, one mole of water and two moles of the same or one mole of two different hydroxyl or carboxyl group-containing or enolizable compounds of the formulas R per mole of TiCl u used simultaneously or in any order ₁ -OH, R ₁ -COOH, R ₁ -CO-CH -CO-R, in which R _{1 is} an alkyl, ₁ -OH, R ₁ -COOH, R ₁ -CO-CH -CO-R,
ralkyl, aryl, alkylaryl and
Alkylaryl or alkoxy radical can be added, or that Aralkyl, aryl, alkylaryl and R an alkyl, aralkyl, aryl, b) upon presentation of a compound TiCl_Xp in which X is an alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or 3-oxo-alkenoxy radical, first one mole of water per mole of the diorganotitanium dichloride used and then optionally two moles of the same or one mole in each case of two different hydroxyl or carboxyl group-containing or enolizable compounds of the general formulas R ₁ OH, R ₁ -COOH, R ₁ -CO-CH ₂ -CO-R ₂ , in which R ₁ TG 71 - 20 - 2 0 8 8 8 H / 1 3 S 8 2237633 an alkyl, aralkyl, aryl, alkylaryl and Rp an alkyl, Aralkyl, aryl, alkylaryl or alkoxy radicals that boil at a higher temperature than that released during the reaction organic component, are added, and that one of the precipitated ammonium chloride and the solvent separates. 2. The method according to claim 1, characterized in that the compound of the formula TiCl_X _{p is} preferably titanium tetrachloride or a dialkoxytitanium dichloride, the alkoxy groups of which each contain up to 4 carbon atoms. 3. Process according to Claims 1-2, characterized in that the hydroxyl-containing compounds of the formula R, -OH are aliphatic and cycloaliphatic monovalent and polyvalent, primary, secondary . and tertiary alcohols and aromatic hydroxy compounds, preferably Phenols, cresols and naphthols. 4. Process according to claims 1-2, characterized in that the carboxyl group-containing compounds of the formula R ₁ -COOH are aliphatic and aromatic, saturated and unsaturated mono-, poly- and hydroxycarboxylic acids. 5- Process according to claims 1-2, characterized in that enolizable ketones, such as 1,3-diketones or!, ^ - ketocarboxylic acid esters, are used as enolizable compounds of the formula R ₁ -CO-CHp-CO-R _2. 6. Process according to claims 1-5, characterized in that one for the preparation of diorganotitanium oxides of the formula ^ .Ti = O,
TG 71 - 21 - 2 0 9 H 8 Η / 13 8 8 2237633 in which R * O and R ¹¹ O are the same, from TiCl ^ the precipitated TiCln-ammonia addition product per mole of TiCl ₂ , simultaneously or in any order with one mole of water and 2 moles of a compound of the general formulas R ₁ -OH, R -COOH, R ₁ -CO-CH ₂ -CO-R, in which R can be an alkyl, aralkyl, aryl, alkylaryl and R can be an alkyl, aralkyl, aryl, alkylaryl or alkoxy radical, s implements. 7 · Process according to claims 1-5, characterized in that for the preparation of diorganotitanium oxides of the formula in which R ¹ O and R "0 are different, from TiCl ₂ , the precipitated TiCl ^ ammonia addition product per mole of TiCl _2. Simultaneously or in any order with one mole of water and one mole each of two different compounds of the general formulas R ₁ -OH, R ₁ -COOH, R ₁ -CO-CH -CO-R, in which R _{1 is} an alkyl, aralkyl, aryl, alkylaryl and Rp is an alkyl, aralkyl, aryl, alkylaryl or can be alkoxy. 8. The method according to claims 1-5, characterized g e indicates that for the preparation of the formula Diorganotitanoxiden Ti = O in which R ¹ O and R ¹¹ O are the same, from diorganotitanium dichlorides of the formula TiClpX, in which X is an alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or a j5-0xo-alkenoxy radical, the precipitated ammonia addition product per mole of titanium compound used with one mole of water and two moles of a compound of the general formulas R ₁ -OH, R ₁ -COOH, R ₁ -CO-CH ₂ -CO-R ₂ , in TG 71 - 22 - 20988 H / 1388 ' ll "> / 633 which R. can be an alkyl, aralkyl, aryl, alkylaryl and R _{p can be} an alkyl, aralkyl, aryl, alkylaryl or alkoxy radical which boils at a higher temperature than the compound released during the reaction . 9 · Process according to claims 1-5 *, characterized in that for the preparation of diorganotitanium oxides of the formula R ¹ CK in which R ¹ O and R ¹¹ O are different, from diorganotitanium dichlorides of the formula TiCl _p X _p , in which X is an alkoxy, aralkoxy, aroxy, alkaroxy, carboxy or a 3-oxo-alkenoxy radical, the precipitated Ammonia addition product per mole of titanium compound used with one mole of water and one mole of two different compounds of the general formulas R ₁ -OH, R ₁ -COOH, R ₁ -C in which R _{1 is} an alkyl, aralkyl, aryl, alkylaryl - and R "can be an alkyl, aralkyl, aryl, alkylaryl or alkoxy radical which boil at a higher temperature than the compound released during the reaction, 10. Process according to claims 1-5, characterized in that one for the preparation of diorganotitanium oxides of the formula Ti = O in which R Ό and R ¹¹ O represent identical or different alkoxy, aralkoxy, aroxy, alkaroxy, carboxy and / or j} oxo-alkenoxy radicals, from diorganotitanium dichlorides of the formula ^x R "0 TG 71 - 2j5 - 209HRK / 1388 ORIGINAL INSPECTED 2237633 whose organic radicals R ¹ O and R ¹ O are identical to those of the compound to be prepared., which converts the ammonia addition product precipitated by the introduction of gaseous ammonia with one mole of water per mole of titanium compound used. 20 988R / 1388