DE1939465A1 - Process for the production of silanes - Google Patents

Description

"Process for the production of silanes

The invention is a process for the production of Silanes of the general formula

- Si - A

- Si

R ¹ η

- Y

where R and R ^{1 can be} identical or different radicals from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl or aryl radical, A the radical of a dihydric phenol, X and Y end groups and η a fractional or integer from 1 to 50. The process is particularly characterized in that N-mono- or disubstituted acid amides are optionally used as catalysts.

It is known to produce such silanes with the addition of condensation auxiliaries. Suitable condensation auxiliaries are compounds which are used in stoichiometric amounts as acid-forming agents, and catalytically active compounds which catalyze the splitting off of the hydrogen halide. As an acid-binding agentL

have been described alkali or alkaline earth carbonates or amines, which the split off hydrogen halide with the formation of ■ Ability to bind alkali or alkaline earth halides or amine hydrochlorides. As catalytically active compounds are the tertiary amines have been described. It has been found, however, that these compounds are not satisfactory for all purposes are effective.

It has now been found that the process for the preparation of silanes of the general formula

R.
Si-A

R '

- Si - Y

R ¹

where R and R ^{1 are} identical or different radicals from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl or aryl radical, A is the radical of a dihydric phenol, X and Y can be end groups and η can be a fractional or whole number from 1 to 50, at temperatures of 50-200 ⁰ O can perform in the presence of catalysts, when the catalysts used are optionally N-mono- or di-substituted acid amides.

Li-substituted acid amides with aliphatic radicals which contain 2-5 carbon atoms and acid amides in the form of quaternary ammonium compounds have proven particularly advantageous as catalysts. Carbodiimides as special forms of acid amides can be used in vorteilhafterweiee.

According to the invention, these catalysts can be used alone or as a mixture. ·

Those dihydric phenols that do not form cyclic silicic acid esters are particularly suitable for the production of the silanes, i.e. the 2 OH groups of the dihydric phenol must not be in the ortho position to one another. Suitable dihydric phenols are: ·

Resorcinol, hydroquinone, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-me ethylphenyl) methane, bis (4-hydroxy-3> 5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, bis (4-hydroxy-3,5-difluorophenyl) methane, 1,1-bis- (4-hydroxyphenyl) -ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) -butane, 2,2-bis- (4-hydroxyphenyl) -4- (methyl) -pentane, 2,2-bis- (4-hydroxy-3-methyl-phenyl) -propane, 2,2-bis- (4-hydroxy-3-chlorophenyl) -propane, 2,2-bis- (4-hydroxy-3,5-dichlorophenyl) -propane, 2,2-bis- (4-hydroxy-3,5-dibromophenyl X-propane, Bis- (4-hydroxyphenyl) -phenylmethane, bis- (4-hydroxyphenyl) -phenylmethylmethane, Bis- (4-hydroxyphenyl) -diphenylmethane, bis- (4-hydroxyphenyl) - (4-methylphenyl) -methane, 1,1-bis (4-hydroxyphenyl) -1- (3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2,2,2-trichloroethane, Bis (4-hydroxyphenyl) - (4-chlorophenyl) methane,

1,1-bis- (4-hydroxyphenyl) -cyclohexane, bis- (4-hydroxyphenyl) -cyclohexylmethane, 4,4'-dihydroxydiphenyl, 3ι3Ί 5i5'-tetramethyl-4,4 * -dihydroxydiphenyl, Dihydroxynaphthalenes, 4,4'-dihydroxydiphenylsulfone, 4,4-Dihydroxydiphenyläther etc. It can also Mixtures of the aforementioned dihydric phenols are used.

009887/2013

The following have proven to be suitable as dihalosilanes according to the present invention: dicyclohexyldichlorosilane, cyclohexylmethyl-. dichlorosilane, dinaphthyldichlorosilane, hydrogenphenyldichlorosilane, Methylphenyldichlorosilane, diphenyldichlorosilane etc. It can mixtures of the aforementioned dihalosilanes can also be used.

The silanes are produced by converting the bivalent ones Phenols with the dihalogen compounds in stoichiometric, under-stoichiometric and over-stoichiometric amounts, i.e. per Moles of dihalosilane are either 1 mole of dihydric phenol or more or less than 1 mole of dihydric phenol. the The amount effectively used depends on the desired degree of condensation. Since η is a whole or fractional number from 1 50 can be, it means for η = 1 that dihydric phenol is used in a molar ratio of 1: 2. For η = 50 the corresponding is 0.98: 1 molar ratio.

Since the condensation reaction slows down with increasing molecule size expires, the resulting condensates have predominantly uniform molecular sizes according to the molar ratio from dihydric phenols to dihalosilanes.

The conversion of the dihydric phenols with the dihalosilanes can take place either in the melt or in the solution. at When using solvents, it is expedient to use solvents which are inert to the reactants.

The condensates are preferably produced at normal pressure. However, the use of an overpressure of up to approx

009887/2013

1933465

12 atü can be advantageous. However, the use of overpressure does not mean a significant amount compared to the pressureless method Advantage.

The procedure can be single and mixed, if necessary N-mono- or disubstituted acid amides or imides are carried out, substituted imides in the sense of present invention understood as a kind of cyclic amide should be.

Suitable, optionally N-mono- or disubstituted acid amides are the carboxamides of monobasic aliphatic, aromatic and araliphatic carboxylic acids having 1 to 18 carbon atoms. The monobasic acids mentioned, such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, lauric acid, palmitic acid, stearic acid, benzoic acid, phenylacetic acid and phenylbutyric acid, can be straight-chain or branched in the alkyl chain, such as a keto group in pyruvic acid, acetoacetic acid, or levulinic acid. Suitable bases on which the acid amides in question are based are ammonia or mono- or diamines. Primary or secondary mono- or diamines of the saturated, aliphatic, araliphatic, cycloaliphatic or series are preferred. Derive aromatic series with only one aromatic ring. Examples of the amines are methylamine, dimethylamines, di-η- or -i-propylamine, di-η- or -iso-butylamine, di-2-methylhexylamine, di-laurylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, cyclohexylamine,

009887/2013

Dicyclohexylamine, benzylamine, dibenzylamine, aniline, N-methylaniline, Called toluidine, phenylenediamine and hexahydrophenylenediamine. One or both alkyl groups of the amines can also be substituted by the phenyl or toluyl radical or by cycloalkyl groups with 5 up to 6 ring atoms, which are optionally also substituted by alkyl groups, in particular one or two methyl groups can be replaced or substituted. Of those as amino components Particularly suitable diamines for the preparation of the acid amides are those in which the two Amino groups are separated by one to 8 methylene groups. In the diamines, too, those bound to the nitrogen atom can still be found Hydrogen atoms except for at least one, e.g. through alkyl groups be substituted by 1 to 4 carbon atoms, the phenyl or toluyl radical or a 5- to 6-membered cycloalkyl radical. As representative Particularly suitable carboxamides which are used as catalysts according to the invention can be listed by name are: Ν, Η-di-n-butylformamide, methyiformamide, Ν, ΐί-dimethyl-

-la

acetamide, Ν, Ν-diethylacetamide, ΪΓ, Ν-di-n- or. -i-propylbutyramide, N, F-di-n- or -isobutylbutyramide, N-benzyl-butyric acid amide, N, N-dipropyl-2-ethylhexanoic acid amide, acetoacetic acid-N, lT-di ~ n-butylamide, acetoacetic anilide, benzoic acid benzylamide, Ν , Ν-Dipropylbenzoic acid amide, NjF'-Diformylhexamethylenediamine. Furthermore, cyclic acid amides or. -Imides such as succinimide can also be used. Also suitable are barbituric acids as catalysts in embossing, which by hydrocarbon radicals, especially by C ₁ - C - may be substituted alkyl or phenyl groups such dimethylbarbituric, Diäthylbarbitursäure, di-ipropylbarbitürsäure, diallylbarbituric acid, di-n-butylbarbituric acid and Phenyläthylbarbitursäure.

009887/2013

1939A65

But also carbonic acid amides or carbonic acid imides, preferably the N-substituted ones Derivatives such as IT-phenyl urethane, diphenylcarbodiimide, Diphenylguanidine can be used.

Sulfonamides are also suitable catalysts, such as 4-sulfomoylacetaniline, F'-amidino-sulfonanilamide, N'-2-pyridyl-sulfanilamide. Phosphorous acid amides, such as ΪΓ, Ν, Ν ¹ , N ¹ , N " ¹ ', N ^f ' -hexamethylphosphoric acid triamide, IT, N, N ¹ , N ¹ , N ¹ ', N ¹ ' -hexamethylphosphoric acid triamide, IT, M", N ', N ¹ , N ¹ ', N ¹ '-hexa-n- or isobutylphosphorous acid triamide, phosphorous acid trimorpholide can be used as catalysts. The phosphoric acid triamides, which can also be used as catalysts, are, however, inferior to phosphoric acid et \ ^ as in their catalytic effect.

Titanic acid amides and stannic acid amides, such as di-n-propoytitanium diamide and di-η- or -iso-butyltin diamide, can also be used as catalysts be used. Also amides of silica and their derivatives, which are known as silylainins and silazanes, can be used, such as diphenyl-di- (dimethylamine) -silane, diphenyl-di- (di-n-propylamino) -silane, diphenyl-di- (di-n-butylamino) -silane, Diphenyl-di- (U, n-butylamino) -silane, methyl phenyl-di- (di-n-pentylanino) -silane, diphenyl-di- (methylphenylamino) -silane, Diphenyl-di- (n-butylphenylamino) -silane, methylphenyl-di- (i-propylphenylamino) -silane, Phenyl-tri- (di-n-butylamino) -silane et al.

It is not necessary to use the finished amides directly as catalysts; the components can also be used from which they are built up, e.g. a mixture of a primary or secondary mono- or diamine of the above

009887/2013

named type and an anhydride or acid chloride of the monocarboxylic acids mentioned use, as under the reaction conditions also form the acid amides to form the silanes. Also mixtures with tertiary amines according to the German patent application (file number P 15 18 733.4) or their quaternary ammonium salts, such as trimethylbenzylammonium chloride, triethylbenzylammonium hydroxide or acetate or triethylaramonium hydrochloride can be used in the present invention.

In the presence of these catalysts, the condensation takes place quickly with the separation of almost stoichiometric amounts of gaseous HCL instead.

The fact that N-substituted acid amides cause the reaction without Accelerating side effects is surprising, since acid amides such as benzoic acid amide, formamide and acetamide probably accelerate the rate of reaction, but they only give products of lower molecular weight than the N-dialkyl-substituted ones Acid amides. In the case of the N-dialkyl-substituted acid amides, it increases the effectiveness with the length of the alkyl radical.

When using the catalysts of the invention the reaction temperature is zv / isehen 50 and 200 ⁰ O, preferably between 80 and 160 ⁰ C.

The reaction can also be carried out in inert solvents, the inert solvent both having the function of a real solvent as well as that of a dispersant. Suitable solvents are: If necessary, aliphatic as also aromatic hydrocarbons, possibly chlorinated as well as simple and cyclic ethers.

Ü09887 / 201 3

Suitable aliphatic hydrocarbons, both single compounds as well as mixtures such as isooctane and gasoline fraction and those having a boiling range of 120 - 180 ⁰ C to call.

Suitable chlorinated, aliphatic hydrocarbons are for example tetrachloroethane, tetrachlorethylene, pentaehloroethylene i.a., benzene, toluene, xylene, cyclohexanyltoluene, cyclohexylethylbenzene, Isopropylethylbenzene, hexylcumene and the isomeric mixtures, dihexylbenzene, di-para-to.lylmethane, nitrobenzene, Diphenyl, etc., as well as the chlorinated trichlorobenzene and dichloroethylbenzenes are, for example, suitable hydrocarbons. Ethers that can be used to carry out the reaction are, for example, diisopropyl ether and 1,4-dioxane The above list of suitable ethers shows that both aliphatic and aromatic, open-chain and cyclic ethers can be used.

The acid amides or their derivatives used as catalysts are used in amounts of 0.1-20 moles, preferably 0.1-2 moles, based on moles of halosilanes. They can be added to the batches at once or in several small portions.

The following examples illustrate the subject matter of the invention.

Example 1:

In a 2 l flask equipped with a stirrer and reflux condenser, 0.5 mol of 2,2-bis (4-hydroxyphenyl) propane was dissolved in 1500 ml of o-dichlorobenzene. Thereafter, 1 ml of di-n-butylbenzosäureamid added as the catalyst and 0.53 mole of di-t dazugetropf methyldichlorosilane.

After 11 hours of refluxing, the elimination of HCl was practically complete (the same reaction was carried out without a catalyst, after 1 hours the elimination of HCl was not complete). The batch was filtered heroically. Evaporation Io vacuum a pour point were isolated from about 55 ⁰ C old from the 711trat 118 g Polydimethyldianylester. The reduced viscosity of a 0.5 percent strength by weight solution in chloroform at 25 ^° C. was 1.22.

Example 2t

As in Example 1, 73 * 2 g (0.20 mol) of 2.2 ~ Bie (?, 5-dichlGr-4-hydroxyphenyl) propane in 500 ml of o-dichlorobenzene and 1 * ml of M _$ $ - Di-n- · implemented butylbenzoesäureamid Then, 53.1 g _(O9 21 mol) diphenyldichlorosilane added slowly, about 24 times-ETO "- DIGEM refluxing was det virtually completed the HOl elimination. The solvent was evaporated. It remained yellow. solid product with a? p.270-290 ⁰ O and a * · * .Ti * (determined as in Example 1) τοη 0.49 furüok.

BelspiA 3s

Analogously to Example 2, 1 g of diphtnyl-dl ^ n-propylaainoJ-silane was carried out instead of o-dichlorobeniol. The H01 treatment was over after about 24 hours. R «d.Viscosity (beetle * νί · In '

INSPECTED

Example 3:

Analogously to Example 2, 1 g of diphenyl-di- (n-propylamino) -silane was used used as a catalyst instead of N, N-di-n-butylbenzoic acid amide. The same product as Example 2 was obtained with a reduced viscosity of 0.51 (determined as in Example 1)

Example 4:

Analogously to Example 2, the experiments were carried out in trichlorobenzene instead of o-dichlorobenzene. The HCl elimination was after finished approx. 24 hours. Red. Viscosity (determined as in Example 1) 0.44.

Example 5:

Analogously to Example 1, 1 ml of N, N-di-n-butylbutyramide was used as the catalyst used instead of Ν, Ιί-din-butylbenzoic acid amide. It Polydimethy] dianvlester was obtained with a pour point of 57 ° C * The reduced viscosity (determined as in Example 1) was ί ', 22.

Example 6:

Analogously to Example 1, 2 g of diphenyl-di-Cdi-n-butylamino ^ silane were used as a catalyst instead of N, N-di-n-butylbenzoic acid amide. It was polydimethyldianyl ester with a pour point of 10? ^p G isolated. The reduced viscosity was 1.25.

Example 7:

Analogously to Example 1, ι ml Ν, Κ, Ν ¹ , N ¹ , N ¹ ', N ¹ ' -Hexamethylphosphorigsäureamxcl instead of Ν, Ν-di-n-butylbenzoic acid amide was used as a catalyst. It was also a polymer with a

009887/20 13

- 12 -. Isolated at a pour point of 55 ° C. The reduced viscosity was 1.25.

Example 8:

In a 2 l flask equipped with a stirrer and reflux condenser 0.8 mol of ρ, ρ'-diphenol were dissolved in 150 ml of toluene. Thereafter 1.2 mol of dimethyldichlorosilane and 2 g of diphenyldi (di-ipropylamine) silane were added as a catalyst.

After 10 hours of refluxing, the splitting off of HCl was practically complete. 205 g of poly-n-methyldimethyl-p, p ^T -diphenyl ester with a pour point of 58 ° C. and a reduced viscosity of 1.2 were obtained.

Example 9:

Analogously to Example 8, 1 g of N-benzylbutyramide was used instead of diphenyl-di- (di-i-propylamino) -silane used as a catalyst. There were 200 g of poly-n-methyldimethyl-p, p'-diphenyl ester with a pour point of 57 ° C. and a reduced viscosity of 1.2.

Example 10:

In a 1 l flask equipped with a stirrer and reflux condenser, 0.5 mol of ρ, ρ'-diphenol was dissolved in 500 ml of o-dichlorobenzene. Thereafter, 1.5 g of acetoacetic acid-NjN-di-n-butylamide were used as a catalyst added and within 1 hour 0.75 g of diphenyldichiοrsilane added dropwise with stirring into the hot solution.

The split off HCl was taken up in NaOH and titrated. The elimination of HCl was complete after about 3 hours. (The same reaction was carried out without a catalyst. The elimination of HCl was not complete after 9 hours). The solution was at about 60 ^° C

009887/2013

filtered. After evaporation in vacuo, 225 g of diphenyl-p, ρ 'remained Diphenyl ester obtained with a pour point of 118 ° C. The elemental analysis showed values that corresponded to the structure

Cl - Si (C ₆ H _{5) 2} - 0 (O ₆ H _{4) 2} O ₂ Si (C ₆ H _{5) 2} Cl

Example 11;

Analogously to Example 10, 2 g of diphenyl-di- (di-i-propylamine) -silane were used as catalyst instead of acetoacetic acid-NjF-di-n-butylamide. 220 g of diphenyl-p, ρ'-diphenyl ester with a
Melting point of 115 ⁰ C were obtained. The elemental analysis gave values consistent with the structure of the compound described in Example 10

The end groups X and Y can be identical or different. They can mean halogen atom and -A-H.

009887/2013

Claims (4)

Claims in which R and R ^{f are} identical or different radicals from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl or aryl radical, A is the radical of a dihydric phenol, X and Y are end groups and η is a fractional or whole number from 1 to 50, from dihydric phenols and dihalosilanes at temperatures of 50 x - 200 ⁰ O in the presence of catalysts, characterized in that optionally used as catalysts N-mono- or disubstituted acid amides. 2. The method according to claim 1, characterized in that the acid amides in the form of their quaternary ammonium compounds begins. 3. The method according to claim 1, characterized in that one uses as an acid amide carbodiimide. 4. The method according to claim 1-3, characterized in that N-substituted acid amides with aliphatic radicals containing 2 to 5 carbon atoms are used. Dr Kni / Wi. 009 8 87/2013