DE1954001A1 - New organosilicon compounds - Google Patents

Description

PR P .. BOUTTKER
i MÖLL

MÖLLER

iatuiittUiwiUe

8 MU N CHBN 80 MS-P.205 / G

Ludle-Grahn-Slraße 3i

Telelon 4437 56 Dr

Midland Silicones limited,

Reading Bridge House, Reading , Berkshire (UK)

New organosilicon compounds

The invention relates to monomeric and polymeric organo-silicon compounds with one or more amine oxide groups bonded to the silicon via hydrocarbon radicals. The invention also relates to a process for the preparation of such compounds and finally to aqueous solutions of the same.

The organosilicon compounds according to the invention are those with at least one to the Silicon bonded group of the formula

- R-NH ₀

O
where mean:

R is a divalent hydrocarbon bonded to the nitrogen atom via a saturated carbon atom

-2-109809 / 2272

atoffrest with 2 to 21 carbon atoms and

X is in each case an alkyl or cycloalkyl radical; an alkenylate of at least 3 carbon atoms; a Aralkyl or Alkoxyalkylreat or one of the Organosilyl or organosilozy radical bonded to nitrogen atom via a radical "R".

In the group -RNXp the radical R can be any bivalent and a hydrocarbon radical having 2 to 3 bonded to the nitrogen atom via a saturated carbon atom including 21 carbon atoms. The radical R has (consequently) such a meaning that the Nitrogen atom is not bonded directly to an aliphatically or aromatically unsaturated carbon atom contained therein. The nitrogen atom thus hangs not directly on a carbon atom in an aromatic nucleus which may be contained in the radical R. Examples of radicals R are consequently ethylene, n-propylene · * isobutylene, undecylene, octadecylene, cyclobexylene and p-xylylene radicals. 3ind several residues R present, they can consist of the same or different residues.

Specific examples of the radicals X, which can be the same or different, are methyl, ethyl, butyl, Hexyl, octadecyl, cyclohexyl, allyl, cyclohexenyl, Benzyl or trimethylsilylethyl and the remainder

Me

J ₄ Si Me

Me 2 O SiMe, I. O Sl I. Me

-3- 1 09809/2272

The organosilicon compounds according to the invention can be monomeric or polymeric and, for example, made of silanes, low molecular weight siloxanes, higher molecular weight polysiloxanes and silcarbane slloxanes, such as Slläthylenensiloxanen exist. The preferred organosilicon compounds according to the invention are those which contain at least one group of formula

where mean:

R is a divalent aliphatic hydrocarbon radical having 1 to 4 carbon atoms and

X is a methyl, ethyl or alkoxyethyl radical, contain, with the rule that the remaining valences of the Sfliolmatoms by oxygen atoms of siloxane bonds, monovalent hydrocarbon radicals or monovalent hydrocarbonoxy radicals are saturated,

Thus, the organosilicon compounds according to the invention include silanes of the general formula

Q. _n Si Fr H X-, 1 η 4-n L · 2 J η

wherein Q is a monovalent hydrocarbon radical or a monovalent radical consisting of carbon, hydrogen and oxygen, α «1 or 2 and the radicals R and X have the meaning given.

-4-109809 / 2272

The radical Q can thus, for example, be an alkyl and cycloalkyl radical, such as a methyl, ethyl, propyl, Hexyl, nonyl, octadecyl and cyclohexyl radicals; an alkenyl radical such as vinyl, allyl and metballyl; or an aryl radical, such as phenyl, diphenyl and Means naphthyl radical. If Q means a radical with carbon, hydrogen and oxygen, then the oxygen can be in the form of ether bonds or be bonded directly to the silicon atom. Examples of such radicals are alkoxy radicals, such as methoxy, ethoxy, propoxy and butoxy radicals; Aryloxy residues, such as pbenoxy radicals; Alkoxyalkyl radicals, such as Methoxyäthyl- and Äthoxybutylreste and residues of the Formulas

0-CH ₃

-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ and -CH ₂ OCH ₂ CH ₂ OC ₂ H ₅ .

For economic reasons, those silanes (of the formula given) are most preferred, In which each radical Q is a methyl radical and the radical X is each a methyl or ethyl radical and η = 1.

The organosilicon compounds according to the invention also include Slloxant alt at least one unit of the formula _Rl

X ₂ VR Si

-5-109809 / 2272

in which the radicals X and R have the meaning given; R 'is a monovalent hydrocarbon radical or a monovalent radical consisting of carbon, hydrogen and oxygen for the radical Q represents given meaning and a = 0, 1 or

The siloxane units defined above are in the relevant Siloxane preferably contained in combination with customary siloxane units. The siloxanes according to the invention thus comprise copolymers with at least one of the specified siloxanes and at least a unit of the general formula:

^R "b ^Si

where R "represents a monovalent hydrocarbon or a monovalent radical consisting of carbon, hydrogen and oxygen as defined for the radical Q and b = O, 1, 2 or 3. These siloxane homo- and copolymers can have high or low molecular weights and cyclic, linear or branched chain. Both radicals R ¹ and R "are preferably methyl radicals.

The preparation of the organosilicon compounds according to of the invention can be obtained by oxidation of the corresponding tertiary, amino-substituted organosilicon compound take place. For this reason, the invention also relates to a method for producing Organosilicon compounds with at least one connected to the

-6-

109809/2272

Sllbium-bonded group of the formula;

RN
O

when it is carried out, an organosilicate compound with at least one group of the formula RNX ₂ bonded to the silicon is oxidized with conversion of the tertiary amino group into an amine oxide group.

When performing the method of the invention Organo-organic compound used as the starting material can be made from any organic compound, for example a Sllan or Slloxan, with the required tertiary amino group or such Groups exist. Such starting materials are, for example, silanes of the general formula:

[ ^R

in which the radicals Q, R, X and η have the meaning given own.

Specific examples of such silanes are compounds of the following formulas:

(C ₂ H ₅ O) ₃ SiCH ₂ N (GH ₃ ) (C ₂ H ₅ ) and CgH ₅ (OCH ₃ ) Si - [CH ₂ CH ₂ Sf (CH ₃ ) J ₂ and (CH ₃ ) ₃ Si / "^ CH ₂ N (GH ₃ ) ₂ .

-7-

1Ö98ÖS / 227!

195400t

As starting materials for the preparation of the siloxanes according to the invention, all suitable ones can be used tertiary amino substituents containing slloxane polymers or copolymers can be used. Specific examples of such siloxanes are compounds made from

? CH ₃ Si (CH ₂ ) ₃ If (CH ₃ ) ₂ units

exist; Copolymers with such units and dimethylsiloxane, Fbenylmethylsiloxane or trimethylsiloxane units, copolymers of

O O

C ₆ H ₅ Si CH ₂ N (C ₂ H ₅ ) ₂ or CH ₃ Si (CH ₂ ) ₆ N (CH ₃ ) ₂ units

and dimethylsiloxane units and copolymers of dimethylsiloxane units and

CH ₂ CH ₂ N (CH ₃ ) ₂ units

Process for the preparation of suitable, substituted with a tertiary amino group and in the process Organosilicon compounds * which can be used according to the invention are, for example, the appropriate Chloroalkyl-substituted organosilicon compound with to react a secondary amine or to add an aliphatically unsaturated tertiary amine to an organosilicon compound having at least one hydrogen atom bonded to the silicon, as described, for example, in British patent application 51339/63 is described.

-8-109809 / 2272

* I

-8th-

When carrying out the process of the invention, ie when preparing the organosilicon compounds according to the invention, all oxidizing agents suitable for converting the tertiary amino group into amine oxide groups can be used. Suitable oxidizing agents are, for example, hydrogen peroxide; cheater "organic hydroperoxides, such as n-Propylhydroperoxyd, t-Butylbydroperoxyd, t-Amylhydroperoxyd and p-Methylbenzylhydroperoxyd, and organic peracids, such as peracetic acid, perbenzoic acid and m-chloroperoxybenzoic acid. Preferably, the hydroperoxides are used in conjunction organiechen old known activators such. B. Salts of transition metals »used.

The oxidation of the tertiary amino groups to Aminoxydgruppen sieve can in most cases, at room temperature or gerlngfttglg elevated temperatures, for example at temperatures of about 20 to 35 ⁰ C, to perform. Although it is usually not necessary, higher temperatures can be used in those cases where it is desirable to speed up the reaction. If appropriate, solvents can also be used in the reaction mixture to promote the reaction or to homogenize the reaction mixture. Suitable solvents are, for example, methanol, ethanol, ither, hydrocarbons and chloroform.

It has been found that the normally insoluble organosilicon molecule by the invention

—9—

BATH ORIGINAL 109809/2272

Incorporation of amine oxide groups (in organosilicon compounds) receives a water-soluble portion. As soon as a sufficient amount of Aminoxyclgruppen is present, will the organosilicon compounds are water-soluble.

It was also found that, according to in which the radical R contains on heating of at least some of the silanes of the invention, two or more carbon atoms, at temperatures above about 75 ⁰ O, bonded to the silicon Aminoxydgruppe of the formula RN (O) X ₂ is converted into an aliphatically unsaturated hydrocarbon group. This conversion takes place, for example, according to the following reaction equation:

SSi CH ₂ -GH ₂ CH ₂ NX ₂ ^ 2 Si CH ₂ .CH =

The amine oxide-substituted siloxanes according to the invention change into cyclic compounds and cross-linked siloxane polymers when heated. the The invention thus makes it possible to provide the person skilled in the art with water-soluble siloxane polymers, which can be converted into an insoluble state when heated. Polymers with such Properties are found in particular in the production of water-soluble treatment agents for Water-repellent finishing of textiles and other materials. Application.

Both the organosilanes and siloxanes slowly decompose in water as a result of hydrolysis of the SiC bond

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109809/2272

with the formation of cross-linked products. This decomposition is accelerated by the presence of a base and by a buffer solution at pH 7 delayed.

The compounds according to the invention are useful as Emulsifiers, anticoagulants, water-soluble antifoams for aqueous systems and for treating glass fibers.

The following examples are intended to further illustrate the invention illustrate.

example 1

A mixture of 3 g of Dlmetbylamlnopropylpentamethyldisiloxan and 2.2g of one diluted with 1 tablespoon of water 30 giw .-, own, neutral hydrogen peroxide solution was stirred for about 30 hours until it became transparent, homogeneous, and neutral to phenol phalanx. The amine oxide solution obtained in this way could easily be diluted with water.

Example 2

A solution of 20 ml (0.18 m) of 30 g of hydrogen peroxide in 100 ml of methanol was added dropwise to a solution of 20 g (0.125 the resulting mixture was heated for 3 hours at reflux temperature. After this time, an aliquot against Pbenolphthalein was neutral and fully miscible with water. After removal of the solvent at reduced pressure, the viscous amine oxide (CH _{3) 2} f! (O) (CH ₂ ) ₃ Sl (CH ₃ ) ₃ obtained.

-11- I 0 9009/2272

10 g of the amine oxide obtained in this way were pyrolyzed at a pressure of τοη 11 cm and the resulting pyrolysis was collected in an ice trap. Decomposition occurred at about 150 °. After the pyrolysis had ended, the fyrolyzate was taken up with ether, washed with water and dried over magnesium sulphate (MgSO.). The ether solution contained (as gas / liquid chromatography studies showed) only one compound which, after evaporation and distillation, was obtained in an amount of 5 g as a colorless liquid . This liquid corresponded to a real sample of allyltrimethyleilane (boiling point 85 °, ga8- / flÜ88igk «itBohrom & tographieohe analysis and infrared analysis)

Example 3

2.0 R (N, N-dimethylajnino) -n-pentylpentamethyldisiloxane were dissolved in 50 ml of chloroform pa, whereupon ozone was durohgeleltet through the resulting solution at a temperature of -50 C until 1 equivalent had been adsorbed . The resulting solution was then evaporated under reduced pressure to give the viscous amine oxide. In analytical and spectral investigations, the amine oxide gave results which were in agreement with the proposed structure. *

Example 4

20.0 ρ pentamethyldisiloxane and 7.0 g diallylmethyl aein were heated with 50 μl of a 10 μl chloroplatinic acid solution in isopropanol. After one hour, the product H _f N-di / 3- (Feirtamethyldisilc: ry) -npropyl ^ -nethylanine was distilled off as a colorless liquid with a boiling point of 102 to 105 ° at a pressure of 0.4 mm in 58% yield.

BATH ORIGINAL 109809/2272 """ ² "

2.0 g of the amine prepared in the manner described above were dissolved iji 50 ml of chloroform was cooled whereupon the resulting solution to a temperature of -50 ⁰ C. Ozone was passed through the cooled solution until 1 equivalent had been adsorbed. The chloroform was then removed under reduced pressure to give the N-oxide of the amine reactant. The structure of this compound was confirmed by analysis.

The alkoxide was soluble in water and suffered slow decomposition in aqueous solution, with the formation of decamethyl tetra-loxane and di-n-propylmethylamine-N-oxide became.

When heated to 150 ° the amine oxide decomposed to H-methyl-N- ^ ¹ - (pentaaethyldisiloxy) -n-propyl7-bydroxylaain, cyclopropane and a folysiloxane residue.

Example 5

After the procedure described in Example 4 was used the Η-oxide of Ν, Ν-diethylaainopropylpentamethyläisiloxan produced. Has been resolving this Oxyds prepared in water with a 50% strength by weight solution, Spectral examinations of the solution obtained showed that the oxide formed within 4 weeks Decamethyltetraslloxane and Ν, Ν-diethyl-l-propylamine oxide decomposed.

Oils decomposition was catalyzed by traces of NaOH.

-13- ORIGINAL BATHROOM

109809/2272

Eelsplel 6

25 g of a copolymer consisting of 75 mol, 2 dimethylsiloxane and 25 mol- # Ν, Ν-dimethylamino-n-propyl- (methyl) -siloxane units, with a molecular weight of about 5000 were dissolved in 500 ml of chloroform . The solution obtained was cooled to a temperature of -5O ⁰ G, whereupon dry ozone was passed into the solution until it reacted neutrally to phenolphthalein.

After chloroform was removed from the reaction mixture under reduced pressure, a obtained viscous, water-soluble liquid. A 1% strength by weight aqueous solution gave a surface tension value of 23.5 of a dyn cm ~.

- patent claims -

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109809/2272

Claims (5)

Patent applications 1./New organosilicon compounds with at least one Arainosubstituted on the silicon-bonded Hydrocarbon group, characterized in that the amino-substituted hydrocarbon group the general formula - R - NX ₀
i ² corresponds to, where mean: R is a divalent hydrocarbon radical bonded to the nitrogen atom via a saturated carbon atom, from 2 to 21 carbon atoms and X is in each case an alkyl or cycloalkyl radical; a Alkenyl radical with at least 3 carbon atoms; an aralkyl or alkoxyalkyl radical or a Organoslyl or organosiloxy radical bonded to the nitrogen atom via a radical "R". 2. Organosilicidmverbindangen according to claim 1, characterized characterized in that they are the general silanes formula: ⁸¹ [Bf ₂ ] «j 109809/2272 19S4001 consist, which mean: Q is a monovalent hydrocarbon radical or a monovalent radical consisting of carbon, hydrogen and oxygen; R is a divalent, connected to the nitrogen atom via a saturated carbon atom-bonded hydrocarbon radical with 2 to 21 carbon atoms; X, 'in each case an alkyl or cycloalkyl radical; a Alkenyl radical with at least 3 carbon atoms; an aralkyl or alkoxyalkyl radical or an organosilyl or organosiloxy radical bonded to the material atom via a radical "R" and the like η = 1 or 2. 3. Organosilicate compounds according to claim 1, characterized in that characterized in that they are made from slloxanes with at least one unit of the formula: ^R 'a beetehen, wherein the radicals R and X in claim have given meaning, R 'a monovalent Hydrocarbon radical or one made of carbon. • Invalid «n Hydrogen and oxygen / represents a radical and · = 0, 1 or 2. -16- BATH ORIGINAL 109809/2272 - 1 Ο - 4. Process for the preparation of Organoslllclumverblndungen, characterized in that one Organoell clum compound with at least one the silicon bonded group of the formula: -RNX ₂ where mean: K is a bivalent, connected to the nitrogen atom via a saturated carbon atom bonded Konlenwasserstoffrest from 2 to 21 carbon atoms and X iewells an alkyl or cycloalkyl radical; an alkenyl radical with at least 3 carbon atoms; an aralkyl or alkoxyalkyl radical or an organoellyl or organoslloxy radical bonded to the nitrogen atom via a radical ^W R ^N old an Oxadationsmttel implemented. 5. Organosilicate compounds according to claim 1, characterized characterized in that they are in the form of an aqueous solution: are present. 6ad original 103809/22/2