DE102015225879A1 - Tris- (alkylalkoxysilyl) amine-rich compositions, their preparation and their use - Google Patents

Abstract

The present invention relates to novel compositions having a high proportion of tris (alkylalkoxysilyl) amines, their preparation and their use.

Description

The present invention relates to compositions containing tris (alkylalkoxysilyl) amines, their preparation and their use.

Aminofunctional silicon compounds are today characterized in many technical applications.

Amino-functional silicon compounds are obtainable, for example, by reacting a chloroalkylalkoxysilane with a significant excess of ammonia (NH 3) or a primary or secondary amine, if appropriate in the presence of a solvent, a mixture of monosilylated or oligosilylated amines and ammonium chloride or amine hydrochlorides generally being formed , At a molar feed ratio of chloroalkylalkoxysilane to NH3 of 1 to 10, both primary, secondary and tertiary amines are formed. Therefore, a recovery ratio of at least 1 to 30 is recommended for the recovery of monosilylated amines. The crude product thus obtained is worked up after the salt removal and the removal of the solvent to obtain the Alkoxysilylalkylamins usually by distillation, leaving a residue of high boilers (including DE-AS 11 58 071 . DE 101 40 563 A1 . DE 103 35 178 A1 . DE 10 2008 002 181 A1 . DE 10 2008 002 182 A1 . DE 10 2008 002 183 A1 . US 2,832,754 . EP 0 849 271 A2 . EP 1 209 162 A2 . EP 1 295 889 A2 . EP 1 476 450 A1 ). Furthermore, so-called cyclic organosilylamines may be present in the product ( EP 1 262 484 A2 ).

Another possibility for the preparation of amino-functional silanes is the hydrosilylation of a primary, secondary or tertiary allylamine in the presence of a catalyst (inter alia EP 0 135 813 A2 . EP 0 196 639 A2 . EP 0 284 447 A2 . US 4,927,949 . EP 0 302 672 A2 . EP 0 321 174 A2 . EP 0382 258 A1 . EP 0 403 706 A2 . EP 0 709 391 A1 ).

Another possibility for the preparation of primary, secondary and tertiary aminofunctional silanes is given by a catalytic hydrogenation of Cyanoalkylalkoxysilanen (et al US 2,930,809 . WO 2003/044027 ).

EP 0 531 948 A1 discloses the preparation of mixtures of mono-, bis- and tris (silylorgano) amines by the treatment of primary aminoorganosilanes with palladium monoxide.

The use of aminoalkoxysilanes or their hydrolysates as water-soluble adhesion promoters has long been known, for example as so-called size or primers in the glass fiber industry.

A number of other application areas for primary, secondary or tertiary aminofunctional silanes or siloxanes are:
The use in coating systems, in the field of corrosion protection, for the biocidal finishing of surfaces, in the treatment of wood, in the production of electrophotographic toner, as an ingredient in aminosilicone fluids ( US 5 077 421 ), as an ingredient in epoxy resins [ Chemical Abstracts (1991) - CA 114: 83579s ], for the production of organically modified glasses ( EP 0 223 987 A2 ), as anticancer agents [ Chemical Abstracts (1983) - CA 99: 133650c ], for modification of glass and glass fiber surfaces, in wastewater treatment, for pigment treatment, as a component in catalysts and for their preparation ( US 4 053 534 ), as flocculants, in adhesives and sealants or cable applications, to name just a few examples.

Aminoalkyltrialkoxysilanes can form on hydrolysis a maximum of one silane triol group per molecule. Silanols and other silanol functions can crosslink with each other or with other OH functions, for example with OH functions of a substrate or of dissolved, emulsified or suspended monomeric or polymeric substances. Such OH functions could z. Example: silanol functions on silica, glass, mineral, glass fiber or mineral fiber surfaces, OH functions on cellulose, leather, paper, wood and the like, but also OH functions on metal surfaces or metal oxide surfaces and OH functions at the Surface of plastics or polymers in preparations, for example natural or plastic emulsions or dispersions.

Also, purely water-based compositions with multifunctional organopolysiloxanes are known as adhesion promoters, cf. among others EP 0 675 128 B1 . EP 0 716 128 B1 . WO 2009/030538 A1 , As a rule, such polysiloxanes no longer carry alkoxy groups, ie they are completely hydrolyzed. In these systems, the cause of the improvement in water solubility is essentially attributed to the salts of the amino-functional groups.

Cationic organosilane polycondensation products in alcoholic solution are for example U.S. 5,591,818 known. In the production here the hydrogen salts are used exclusively monosilylated alkylamines.

In EP 1 031 593 A2 For example, oligosilylated aminoalkyl-functional silicon compounds are referred to as "bis-products" such as bis-AMMO, bis-AMEO, bis-cyclo-AMEO, bis-DAMO, bis-TRIAMO. EP 1 031 593 A2 discloses a substantially alcohol-free composition which consists of a mixture of water-soluble, mono- and oligosilylated amino-functional, alkoxygruppenfreier silicon compounds, water and optionally a content of acid, wherein the proportion of monosilylated amino-functional groups compared to oligosilylated amino-functional groups is significantly higher here. Water is used in excess to produce them, so that the alkoxy groups are virtually completely hydrolyzed, ie, particularly reactive silanol groups are present and the siloxanes correspondingly present in the aqueous composition do not carry any alkoxy groups. Further, in EP 1 031 593 A2 reports that at a weight ratio of monosilylated alkylamines (a) to oligosilylated alkylamines (b) with a / b <1 gelation or very high haze can occur.

In DE 103 35 178 A1 discloses a water-soluble composition comprising a mixture of mono- and oligosilylated aminoalkyl, alkoxy and optionally hydroxy-functional silicon compounds, wherein (A) the aminoalkyl-functional to (B) the bis- or trisaminoalkyl-functional silicon compounds in a weight ratio of the silane feeds of ( A) :( B) ≤ 0.5. Such mixtures are obtained by mixing the respective components.

In new applications, there is an increased demand for compositions containing specific alkylalkoxysilylamines, i. Alkylalkoxysilylamine-containing mixtures which are as rich as possible in tris (alkylalkoxysilyl) amines, i. Tris (alkylalkoxysilyl) amines as the main constituent of the composition and optionally further alkylalkoxysilylamines as minor constituents or in minor proportions. In practice, it is disadvantageous that tris (alkylalkoxysilyl) amines usually occur only in small amounts as a by-product in the synthesis of aminoalkylsilanes and are therefore unfortunately not available in sufficient quantity.

The invention had the object of providing a method which allows a targeted, large-scale production of Alkylalkoxysilylamine containing compositions, such compositions should have as high levels of at least one tris (alkylalkoxysilyl) amine compound, especially with regard to new applications in Form of alkylalkoxysilylamine-containing mixtures rich in tris (alkylalkoxysilyl) amine, d. H. Tris (alkylalkoxysilyl) amine main component of the mixture is.

The stated object is achieved according to the disclosure of the claims.

• (A1) ein monosilyliertes Amin der allgemeinen Formel (I) NH₂[(CH₂CH₂)NH]_x(R¹)-Si(R²)_y(OR)_3-y (I), worin R für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R¹ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt, R² eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, x gleich 0 oder 1 und y gleich 0, 1 oder 2 sind, mit einem Chloralkylalkoxysilan der allgemeinen Formel (II) Cl-(R³)-Si(R⁴)_z(OR⁵)_3-z (II) , worin R⁵ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R⁴ eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, R³ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt und z gleich 0, 1 oder 2 ist, in einem molaren Verhältnis monosilyliertes Amin zu Chloralkylalkoxysilan von 1:≥ 2, vorzugsweise von 1:2,1 bis 1:25, besonders bevorzugt 1:2,5 bis 1:20, ganz besonders bevorzugt 1:2,8 bis 1:15, insbesondere 1:3 bis 1:5, umsetzt, den dabei entstehenden Anteil an festem Salz abtrennt und anschließend nicht umgesetztes Chloralkylalkoxysilan aus der Produktzusammensetzung abdestilliert, oder
• (A2) ein Gemisch aus einem monosilylierten Amin der allgemeinen Formel (I) NH₂[(CH₂CH₂)NH]_x(R¹)-Si(R²)_y(OR)_3-y (I), worin R für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R¹ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt, R² eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, x gleich 0 oder 1 und y gleich 0, 1 oder 2 sind, und einem bissilyliertes Amin der allgemeinen Formel (III) (R⁵O)_3-z(R⁴)_zSi(R³)-NH[(CH₂CH₂)NH]_x(R¹)Si(R²)_y(OR)_3-y (III), worin R und R⁵ unabhängig jeweils für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen stehen, R² und R⁴ unabhängig jeweils eine Alkylgruppe mit 1 oder 2 C-Atomen darstellen, R¹ und R³ unabhängig jeweils einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellen und x gleich 0 oder 1 ist und z und y unabhängig jeweils gleich 0, 1 oder 2 sind, mit einem Chloralkylalkoxysilan der allgemeinen Formel (II) Cl-(R³)-Si(R⁴)_z(OR⁵)_3-z (II), worin R⁵ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R⁴ eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, R³ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt und z gleich 0, 1 oder 2 ist, in einem molaren Verhältnis monosilyliertes Amin zu Chloralkylalkoxysilan von 1:≥ 2, vorzugsweise 1:2,1 bis 1:2, besonders bevorzugt 1:2,5 bis 1:15, ganz besonders bevorzugt 1:2,8 bis 1:10, insbesondere 1:3 bis 1:5, umsetzt, den dabei entstehenden Anteil an festem Salz abtrennt und anschließend nicht umgesetztes Chloralkylalkoxysilan aus der Produktzusammensetzung abdestilliert, oder
• (A3) ein bissilyliertes Amin der allgemeinen Formel (III) (R⁵O)_3-z(R⁴)_zSi(R³)-NH[(CH₂CH₂)NH]_x(R¹)Si(R²)_y(OR)_3-y (III), worin R und R⁵ unabhängig jeweils für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen stehen, R² und R⁴ unabhängig jeweils eine Alkylgruppe mit 1 oder 2 C-Atomen darstellen, R¹ und R³ unabhängig jeweils einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellen und x gleich 0 oder 1 ist und z und y unabhängig jeweils gleich 0, 1 oder 2 sind, mit einem Chloralkylalkoxysilan der allgemeinen Formel (II) Cl-(R³)-Si(R⁴)_z(OR⁵)_3-z (II), worin R⁵ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R⁴ eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, R³ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt und z gleich 0, 1 oder 2 ist, in einem molaren Verhältnis monosilyliertes Amin zu Chloralkylalkoxysilan von 1:≥ 2, vorzugsweise 1:2,1 bis 1:15, besonders bevorzugt 1:2,5 bis 1:12, ganz besonders bevorzugt 1:2,8 bis 1:8, insbesondere 1:3 bis 1:5, umsetzt, den dabei entstehenden Anteil an festem Salz abtrennt und anschließend nicht umgesetztes Chloralkylalkoxysilan aus der Produktzusammensetzung abdestilliert, oder
• (B) Ammoniak mit einem Chloralkylalkoxysilan der allgemeinen Formel (II) Cl-(R³)-Si(R⁴)_z(OR⁵)_3-z (II), worin R⁵ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R⁴ eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, R³ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt und z gleich 0, 1 oder 2 ist, in einem molaren Verhältnis Ammoniak zu Chloralkylalkoxysilan von 1:≥ 3, vorzugsweise 1:3,2 bis 1:9, besonders bevorzugt 1:3,5 bis 1:5, unter einem Druck von 25 bis 100 bar und bei einer Temperatur von 50 bis 110 °C umsetzt, den dabei entstehenden Anteil an festem Salz abtrennt und anschließend nicht umgesetztes Chloralkylalkoxysilan aus der Produktzusammensetzung abdestilliert, oder
• (C) ein Trialkenylamin, vorzugsweise Triallylamin, in Gegenwart eines Edelmetallkatalysators, der als geträgertes oder komplexes Katalysatorsystem vorliegen kann, vorzugsweise ein Pt- , Rh- oder Ru-haltiges Katalysatorsystem, mit einem Hyrogenalkoxysilan, vorzugsweise Hydrogentrimethoxysilan, Hydrogentriethoxysilan, hydrosilyliert, wobei man die Eduktkomponenten in einem molaren Verhältnis Trialkenylamin zu Hydrogenalkoxysilan von 1 zu ≥ 2,2, vorzugsweise 1 zu 2,5 bis 1 zu 50, besonders bevorzugt 1 zu 2,8 bis 1 zu 10, besonders bevorzugt 1 zu 3 bis 1 zu 5, einsetzt, und fakultativ das so erhaltene Produktgemisch aufarbeitet.

Thus, it has surprisingly been found that in a simple and economical manner substantially tris (alkylalkoxysilyl) amine-containing composition, in particular those containing more than 71 wt .-% tris (alkylalkoxysilyl) amines, can be obtained if

• (A1) a monosilylated amine of the general formula (I) NH ₂ [(CH ₂ CH ₂ ) NH] _x (R ¹ ) -Si (R ² ) _y (OR) _3-y (I), wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms, R ^{1 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{2 is} an alkyl group having 1 or 2 C atoms, x is equal 0 or 1 and y are 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ⁵ represents a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkyl group having 1 or 2 carbon atoms, R ³ represents a divalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio monosilylated amine to chloroalkylalkoxysilane of 1: ≥ 2, preferably from 1: 2.1 to 1:25, more preferably 1: 2.5 to 1:20, most preferably 1: 2.8 to 1:15, in particular 1: 3 to 1: 5, reacted, the resulting proportion of solid salt separated and then distilled unreacted chloroalkylalkoxysilane from the product composition, or
• (A2) a mixture of a monosilylated amine of the general formula (I) NH ₂ [(CH ₂ CH ₂ ) NH] _x (R ¹ ) -Si (R ² ) _y (OR) _3-y (I), wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms, R ^{1 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{2 is} an alkyl group having 1 or 2 C atoms, x is equal 0 or 1 and y are 0, 1 or 2, and a bis-silylated amine of the general formula (III) (R ⁵ O) _3-z (R ⁴ ) _z Si (R ³ ) -NH [(CH ₂ CH ₂ ) NH] _x (R ¹ ) Si (R ² ) _y (OR) _3-y (III), wherein R and R ^{5 are} each independently a linear or branched alkyl group having 1 to 4 C atoms, R ² and R ^{4 are} each independently an alkyl group having 1 or 2 C atoms, R ¹ and R ^{3 are} each independently a bivalent, represent linear or branched alkyl radical having 1 to 4 carbon atoms and x is 0 or 1 and z and y are each independently 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio monosilylated amine to chloroalkylalkoxysilane of 1: ≥ 2, preferably 1: 2.1 to 1: 2, more preferably 1: 2.5 to 1:15, most preferably 1: 2.8 to 1:10, in particular 1: 3 to 1: 5, reacted, the resulting proportion of solid salt separated and then distilled unreacted chloroalkylalkoxysilane from the product composition, or
• (A3) a bis-silylated amine of the general formula (III) (R ⁵ O) _3-z (R ⁴ ) _z Si (R ³ ) -NH [(CH ₂ CH ₂ ) NH] _x (R ¹ ) Si (R ² ) _y (OR) _3-y (III), wherein R and R ^{5 are} each independently a linear or branched alkyl group having 1 to 4 C atoms, R ² and R ^{4 are} each independently an alkyl group having 1 or 2 C atoms, R ¹ and R ^{3 are} each independently a bivalent, represent linear or branched alkyl radical having 1 to 4 carbon atoms and x is 0 or 1 and z and y are each independently 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio monosilylated amine to chloroalkylalkoxysilane of 1: ≥ 2, preferably 1: 2.1 to 1:15, more preferably 1: 2.5 to 1:12, most preferably 1: 2.8 to 1: 8, in particular 1: 3 to 1: 5, reacted, the resulting proportion of solid salt separated and then distilled unreacted chloroalkylalkoxysilane from the product composition, or
• (B) Ammonia with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio of ammonia to chloroalkylalkoxysilane of 1: ≥ 3, preferably 1: 3.2 to 1: 9, more preferably 1: 3.5 to 1: 5, under a pressure of 25 to 100 bar and reacted at a temperature of 50 to 110 ° C, the resulting proportion of solid salt separated and then distilled unreacted chloroalkylalkoxysilane from the product composition, or
• (C) a trialkenylamine, preferably triallylamine, in the presence of a noble metal catalyst, which may be present as a supported or complex catalyst system, preferably a Pt, Rh or Ru containing catalyst system, hydrosilylated with a hyrogenalkoxysilane, preferably hydrogentrimethoxysilane, hydrogentriethoxysilane, using Reactant components in a molar ratio Trialkenylamin to Hydrogenalkoxysilane of 1 to ≥ 2.2, preferably 1 to 2.5 to 1 to 50, more preferably 1 to 2.8 to 1 to 10, particularly preferably 1 to 3 to 1 to 5, is used and optionally working up the product mixture thus obtained.

worin R für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht.In the present invention, monosilylated amines are to be understood as meaning those compounds which contain only one silyl group, as can be seen as the aminoalkylalkoxysilane of the general formula I, in particular but not exclusively. H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (AMMO), H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ (AMEO), H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ (AMEO), H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (DAMO), H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (TRIAMO). as well as corresponding cyclic compounds, in particular cycloaminoalkylalkoxysilanes of the general formula IV

wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms.

Oligosilylated amines in the present invention are in particular to be understood as meaning those which carry two or more than two silyl groups on an amino group or alkylamine, for example according to formula III (bis-silylated) or formula V (tris-silylated) and corresponding compounds which cyclized present.

Thus, for example, the following preferred bis-silylated alkylamines can be taken from formula III: (H ₃ CO) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (Bis-AMMO) (H ₅ C ₂ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ (Bis-AMEO) (H ₃ CO) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (Bis-DAMO) (H ₃ CO) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (Bis-TRIAMO).

The general formula V represents only one of many possibilities for tris-silylated alkylamines N [(CH ₂ ) ₃ Si (OR) ₃ ] ₃ (V),
wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms,
preferably methyl and ethyl,
for example, but not exclusively, it can be seen from formula V N [CH ₂ ) ₃ Si (OCH ₃ ) ₃ ] ₃ (Tris-AMMO) N [CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ ] ₃ (Tris-AMEO).

If water enters the product of the present process or into a corresponding composition, condensation products based on previously described compounds can be formed after hydrolysis.

• (A1) ein monosilyliertes Amin der allgemeinen Formel (I) NH₂[(CH₂CH₂)NH]_x(R¹)-Si(R²)_y(OR)_3-y (I), worin R für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R¹ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt, R² eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, x gleich 0 oder 1 und y gleich 0, 1 oder 2 sind, mit einem Chloralkylalkoxysilan der allgemeinen Formel (II) Cl-(R³)-Si(R⁴)z(OR⁵)_3-z (II), worin R⁵ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R⁴ eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, R³ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt und z gleich 0, 1 oder 2 ist, in einem molaren Verhältnis monosilyliertes Amin zu Chloralkylalkoxysilan von 1: ≥ 2, vorzugsweise 1:2,1 bis 1:25, besonders bevorzugt 1:2,5 bis 1:20, ganz besonders bevorzugt 1:2,8 bis 1:15, insbesondere 1:3 bis 1:5, umsetzt, die Umsetzung bei einer Temperatur von 60 bis 220 °C und einem Druck von 0,5 bis 50 bar über 1 bis 10 Stunden durchführt, den dabei entstehenden Anteil an festem Salz abtrennt und anschließend nicht umgesetztes Chloralkylalkoxysilan aus der Produktzusammensetzung abdestilliert, oder
• (A2) ein Gemisch aus einem mono-silylierten Amin der allgemeinen Formel (I) NH₂[(CH₂CH₂)NH]_x(R¹)-Si(R²)_y(OR)_3-y (I), worin R für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R¹ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt, R² eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, x gleich 0 oder 1 und y gleich 0, 1 oder 2 sind, und einem bis-silylierten Amin der allgemeinen Formel (III) (R⁵O)_3-z(R⁴)_zSi(R³)-NH[(CH₂CH₂)NH]_x(R¹)Si(R²)_y(OR)_3-y (III), worin R und R⁵ unabhängig jeweils für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen stehen, R² und R⁴ unabhängig jeweils eine Alkylgruppe mit 1 oder 2 C-Atomen darstellen, R¹ und R³ unabhängig jeweils einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellen und x gleich 0 oder 1 ist und z und y unabhängig jeweils gleich 0, 1 oder 2 sind, mit einem Chloralkylalkoxysilan der allgemeinen Formel (II) Cl-(R³)-Si(R⁴)_z(OR⁵)_3-z (II), worin R⁵ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R⁴ eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, R³ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt und z gleich 0, 1 oder 2 ist, in einem molaren Verhältnis mono-silyliertem Amin zu Chloralkylalkoxysilan von 1: ≥ 2, vorzugsweise 1:2,1 bis 1:25, besonders bevorzugt 1:2,5 bis 1:15, ganz besonders bevorzugt 1:2,8 bis 1:10, insbesondere 1:3 bis 1:5, umsetzt, die Umsetzung bei einer Temperatur von 60 bis 220 °C und einem Druck von 0,5 bis 50 bar über 1 bis 10 Stunden durchführt, den dabei entstehenden Anteil an festem Salz abtrennt und anschließend nicht umgesetztes Chloralkylalkoxysilan aus der Produktzusammensetzung abdestilliert, oder
• (A3) ein bis-silyliertes Amin der allgemeinen Formel (III) (R⁵O)_3-z(R⁴)_zSi(R³)-NH[(CH₂CH₂)NH]_x(R¹)Si(R²)_y(OR)_3-y (III), worin R und R⁵ unabhängig jeweils für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen stehen, R² und R⁴ unabhängig jeweils eine Alkylgruppe mit 1 oder 2 C-Atomen darstellen, R¹ und R³ unabhängig jeweils einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellen und x gleich 0 oder 1 ist und z und y unabhängig jeweils gleich 0, 1 oder 2 sind, mit einem Chloralkylalkoxysilan der allgemeinen Formel (II) Cl-(R³)-Si(R⁴)_z(OR⁵)_3-z (II), worin R⁵ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R⁴ eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, R³ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt und z gleich 0, 1 oder 2 ist, in einem molaren Verhältnis mono-silyliertes Amin zu Chloralkylalkoxysilan von 1: ≥ 2, vorzugsweise 1:2,1 bis 1:15, besonders bevorzugt 1:2,5 bis 1:12, ganz besonders bevorzugt 1:2,8 bis 1:8, insbesondere 1:3 bis 1:5, umsetzt, die Umsetzung bei einer Temperatur von 60 bis 220 °C und einem Druck von 0,5 bis 50 bar über 1 bis 10 Stunden durchführt, den dabei entstehenden Anteil an festem Salz abtrennt und anschließend nicht umgesetztes Chloralkylalkoxysilan aus der Produktzusammensetzung abdestilliert, oder
• (B) Ammoniak mit einem Chloralkylalkoxysilan der allgemeinen Formel (II) Cl-(R³)-Si(R⁴)_z(OR⁵)_3-z (II), worin R⁵ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 4 C-Atomen steht, R⁴ eine Alkylgruppe mit 1 oder 2 C-Atomen darstellt, R³ einen bivalenten, linearen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen darstellt und z gleich 0, 1 oder 2 ist, in einem molaren Verhältnis Ammoniak zu Chloralkylalkoxysilan von 1: ≥ 3, vorzugsweise 1:3,2 bis 1:9, besonders bevorzugt 1:3,5 bis 1:5, unter einem Druck von 25 bis 100 bar und bei einer Temperatur von 50 bis 110 °C umsetzt, den dabei entstehenden Anteil an festem Salz abtrennt und anschließend nicht umgesetztes Chloralkylalkoxysilan aus der Produktzusammensetzung abdestilliert, oder
• (C) ein Trialkenylamin, vorzugsweise Triallylamin, in Gegenwart eines Edelmetallkatalysators, der als geträgertes oder komplexes Katalysatorsystem vorliegen kann, vorzugsweise ein Pt-, Rh- oder Ru-haltiges Katalysatorsystem, mit einem Hyrogenalkoxysilan, vorzugsweise Hydrogentrimethoxysilan, Hydrogentriethoxysilan, hydrosilyliert, wobei man die Eduktkomponenten in einem molaren Verhältnis Trialkenylamin zu Hydrogenalkoxysilan von 1 zu ≥ 2,2, vorzugsweise 1 zu 2,5 bis 1 zu 50, besonders bevorzugt 1 zu 2,8 bis 1 zu 10, besonders bevorzugt 1 zu 3 bis 1 zu 5, einsetzt, und fakultativ das so erhaltene Produktgemisch aufarbeitet.

The present invention thus provides a process for the preparation of a composition rich in tris (alkylalkoxysilyl) amines by reacting

• (A1) a monosilylated amine of the general formula (I) NH ₂ [(CH ₂ CH ₂ ) NH] _x (R ¹ ) -Si (R ² ) _y (OR) _3-y (I), wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms, R ^{1 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{2 is} an alkyl group having 1 or 2 C atoms, x is equal 0 or 1 and y are 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio monosilylated amine to chloroalkylalkoxysilane of 1: ≥ 2, preferably 1: 2.1 to 1:25, more preferably 1: 2.5 to 1:20, most preferably 1: 2.8 to 1:15, in particular 1: 3 to 1: 5, reacted, the reaction is carried out at a temperature of 60 to 220 ° C and a pressure of 0.5 to 50 bar for 1 to 10 hours, the resulting proportion of solid salt separated and then not distilled off reacted chloroalkylalkoxysilane from the product composition, or
• (A2) a mixture of a mono-silylated amine of the general formula (I) NH ₂ [(CH ₂ CH ₂₎ NH] _x (R ¹⁾ -Si (R ²⁾ _y (OR) _3-y (I), wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms, R ^{1 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{2 is} an alkyl group having 1 or 2 C atoms, x is equal 0 or 1 and y are 0, 1 or 2, and a bis-silylated amine of the general formula (III) (R ⁵ O) _3-z (R ⁴ ) _z Si (R ³ ) -NH [(CH ₂ CH ₂ ) NH] _x (R ¹ ) Si (R ² ) _y (OR) _3-y (III), wherein R and R ^{5 are} each independently a linear or branched alkyl group having 1 to 4 C atoms, R ² and R ^{4 are} each independently an alkyl group having 1 or 2 C atoms, R ¹ and R ^{3 are} each independently a bivalent, represent linear or branched alkyl radical having 1 to 4 carbon atoms and x is 0 or 1 and z and y are each independently 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio of mono-silylated amine to chloroalkylalkoxysilane of 1: ≥ 2, preferably 1: 2.1 to 1:25, more preferably 1: 2.5 to 1:15, most preferably 1: 2.8 to 1:10, in particular 1: 3 to 1: 5, reacted, the reaction is carried out at a temperature of 60 to 220 ° C and a pressure of 0.5 to 50 bar for 1 to 10 hours, the separating off the resulting proportion of solid salt and then distilling off unreacted chloroalkylalkoxysilane from the product composition, or
• (A3) a bis-silylated amine of the general formula (III) (R ⁵ O) _3-z (R ⁴ ) _z Si (R ³ ) -NH [(CH ₂ CH ₂ ) NH] _x (R ¹ ) Si (R ² ) _y (OR) _3-y (III), wherein R and R ^{5 are} each independently a linear or branched alkyl group having 1 to 4 C atoms, R ² and R ^{4 are} each independently an alkyl group having 1 or 2 C atoms, R ¹ and R ^{3 are} each independently a bivalent, represent linear or branched alkyl radical having 1 to 4 carbon atoms and x is 0 or 1 and z and y are each independently 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio of mono-silylated amine to chloroalkylalkoxysilane of 1: ≥ 2, preferably 1: 2.1 to 1:15, more preferably 1: 2.5 to 1:12, most preferably 1: 2.8 to 1: 8, in particular 1: 3 to 1: 5, reacted, the reaction is carried out at a temperature of 60 to 220 ° C and a pressure of 0.5 to 50 bar for 1 to 10 hours, the separating off the resulting proportion of solid salt and then distilling off unreacted chloroalkylalkoxysilane from the product composition, or
• (B) Ammonia with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio of ammonia to chloroalkylalkoxysilane of 1: ≥ 3, preferably 1: 3.2 to 1: 9, more preferably 1: 3.5 to 1: 5, under a pressure of 25 to 100 bar and reacted at a temperature of 50 to 110 ° C, the resulting proportion of solid salt separated and then distilled unreacted chloroalkylalkoxysilane from the product composition, or
• (C) a trialkenylamine, preferably triallylamine, in the presence of a noble metal catalyst, which may be present as a supported or complex catalyst system, preferably a Pt, Rh or Ru containing catalyst system, hydrosilylated with a hyrogenalkoxysilane, preferably hydrogentrimethoxysilane, hydrogentriethoxysilane, using Reactant components in a molar ratio Trialkenylamin to Hydrogenalkoxysilane of 1 to ≥ 2.2, preferably 1 to 2.5 to 1 to 50, more preferably 1 to 2.8 to 1 to 10, particularly preferably 1 to 3 to 1 to 5, is used and optionally working up the product mixture thus obtained.

In the process according to the invention according to the synthesis routes A1, A2 and A3, the preferred component of the formula I is an aminoalkylalkoxysilane from the series 3-aminopropyltriethoxysilane 1-aminomethyltrimethoxysilane, 1-aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane (AMMO), 3-aminopropyltriethoxysilane (AMEO), 3-amino-2-methylpropyltrimethoxysilane, 3-amino-2-methylpropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-butyl 3-aminopropyltriethoxysilane, N- [2-aminoethyl] -3-aminopropyltrimethoxysilane (DAMO), N- [2-aminoethyl] -3-aminopropyltriethoxysilane, N- [2-aminoethyl] -3-aminopropylmethyldimethoxysilane, N- [2 -Aminoethyl] -3-aminopropylmethyldiethoxysilane and / or according to formula III preferably bis-AMMO, bis-AMEO, bis-DAMO, bis-TRIAMO.

Furthermore, in the process according to the invention according to the synthetic routes A1, A2, A3 and B, preference is given to using a chloroalkylalkoxysilane of the formula II from the series 1-chloromethyltrimethoxysilane, 1-chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane (CPTMO), 3 Chloropropyltriethoxysilane (CPTEO), 3-chloro-2-methylpropyltrimethoxysilane, 3-chloro-2-methylpropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylethyldimethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloropropyldimethylethoxysilane.

The reaction according to the synthetic routes A1, A2 or A3 is advantageously carried out in the process according to the invention at a temperature of 60 to 220 ° C. and a pressure of 0.5 to 50 bar for 1 to 10 hours, particularly preferably at a temperature of 80 to 190 ° C and a pressure of 0.8 to 10 bar for 2 to 8 hours, more preferably a temperature of 100 to 180 ° C and a pressure of 0.8 to 10 bar, in particular for 3 to 6 hours at a temperature from 120 to 160 ° C and at a pressure of 1 to 6 bar, and can then remove thereby resulting solid salt from the product composition.

The reaction of the invention according to synthesis route B is suitably carried out at a pressure of 25 to 100 bar and a temperature of 50 to 100 ° C. Suitably, the starting materials are allowed to react with thorough mixing and can subsequently remove any resulting solid salt from the product composition.

In carrying out the present process according to A1, A2, A3 or B, solid ammonium chloride or amine hydrochloride is preferably separated from the liquid phase by means of a filter or centrifuge.

In addition, in the process according to the invention of the product composition thus obtained, at least one hydrocarbon, an alcohol, preferably methanol and also ethanol, and / or water can be added as further component.

In general, the present process can be carried out as follows:
The starting materials can be introduced into a reaction flask or pressure reactor. The educts can also be dosed in portions in different order. In the presence of a low-boiling base, the reaction is preferably carried out in a pressure reactor.

The reaction mixture is suitably heated to 60-220 ° C and the reaction followed by determining the CPTEO content in the reaction mixture. After completion of the reaction, the reaction product mixture thus obtained is cooled and the pressure reactor is depressurized. The resulting salt can be separated, for example, by means of centrifuge or pressure filtration. The low boilers are advantageously used under reduced pressure, i. in a vacuum, z. Example by means of thin-film evaporator or other distillation apparatus known to the chemist, at a temperature of max. 180 ° C removed from the product mixture. The work-up of the reaction product mixture can moreover be carried out by means of "Na-methylate" or "Na-ethylate", wherein the reaction product mixture is suitably cooled first, an alcoholic alkali metal alkoxide solution is added, preferably sodium methoxide, potassium methanolate or magnesium methanolate respectively in methanol or sodium ethanolate, potassium ethanolate or magnesium ethanolate respectively Ethanol, in particular in a molar ratio to the component (II) used, react and the resulting proportion of solid salt, ie essentially alkali or magnesium chloride, preferably separated by means of a filter or centrifuge from the organic liquid phase. Subsequent volatile constituents, such as solvents or diluents, and optionally monosilylated amine can be distilled off proportionally or completely from the thus desalted, now low-chloride reaction product. The distillative workup, i. the distillation of the desalted reaction product is preferably carried out under reduced pressure and at a temperature in the range of 60 to 180 ° C, preferably from 80 to 160 ° C. In addition, the filtrate thus obtained can optionally be filtered again and thus freed of residual solid. The work-up of the reaction product mixture can also be carried out aqueous, wherein the reaction product mixture is suitably first cooled, preferably to a temperature of 5 to 70 ° C, particularly preferably 10 to 50 ° C, in particular 15 to 30 ° C, toluene is added and then, preferably below Stirring and after further cooling, for example to 15 to 30 ° C, an aqueous liquor, preferably aqueous potassium or sodium hydroxide solution with pH 12 to 14 admits. It is preferably used per part by weight of the present reaction product 0.2 to 0.8, more preferably 0.4 to 0.6 parts by weight of toluene. Further, it is preferable to use 5 to 50 parts by weight, more preferably 20 to 40 parts by weight, of aqueous alkali per 100 parts by weight of the toluene-containing reaction product. Now it is allowed to react, preferably over 10 seconds to 30 minutes, usually forming two phases quickly, and separates the organic product phase of the salt-containing aqueous phase. Subsequent volatile constituents, such as solvents or diluents, as well as optionally monosilylated amine may be proportionally or completely removed from the thus desalted, now chloride-poor organic phase, ie. H. be distilled off the thus desalted reaction product mixture. The distillative workup, i. the distillation of the desalted reaction product is preferably carried out under reduced pressure and at a temperature in the range of 60 to 180 ° C, preferably from 80 to 160 ° C. In addition, the filtrate thus obtained can optionally be filtered again and thus freed of residual solid. In addition, it is expressly pointed out that all of the preferred ranges mentioned above can each be combined with one another and thus disclosed extensively.

The present invention advantageously compositions with a content of tris (alkylalkoxysilyl) amines of more than 71 wt .-%, based on the composition, which are obtainable by the process according to the invention, wherein all components in a composition according to the invention in total 100 wt .-% result ..

In particular, inventive compositions are characterized by a content of tris (alkylalkoxysilyl) amines of more than 71 wt .-%, preferably from 72 to 98 wt .-%, particularly preferably from 72.5 to 96 wt .-%, based on the composition of, wherein all components in a composition according to the invention add up to 100% by weight.

In addition, compositions according to the invention may advantageously have a content of monosilylated amine of from 0.05 to <29% by weight, preferably from 0.1 to 25% by weight, especially preferably from 0.2 to 15% by weight, all components in a composition according to the invention resulting in a total of 100% by weight

As a further constituent, compositions according to the invention may advantageously have a bis-silylated amine content of from 0.1 to <29% by weight, preferably from 0.2 to 26% by weight, particularly preferably from 0.5 to 15% by weight. %, based on the composition, wherein all components in a composition according to the invention add up to 100% by weight.

Also, compositions of the invention may advantageously have a content of acid chloride of 1 to 1000 mg / kg, preferably 5 to 500 mg / kg, particularly preferably 8 to 400 mg / kg.

Furthermore, compositions according to the invention may contain, as further components, a content of a nonpolar solvent or diluents, such as alcohol or preferably aliphatic or aromatic hydrocarbons, in particular kerosene, diesel, octane, n-hexane, c-hexane, heptane, toluene, xylene, preferably in one respective amount of <27 wt .-%, based on the composition, advantageously, all components in a composition according to the invention add up to 100 wt .-%.

Thus, by means of targeted syntheses, even on an industrial scale, compositions which have a comparatively high proportion of tris-silylated amines can now also be obtained in a simple and economical manner.

Furthermore, compositions according to the invention are generally distinguished by a viscosity of from 1 to 100 mPas, preferably from 2 to 50 mPas, more preferably from 4 to 25 mPas, the viscosity being in accordance with, for example, DIN 53 015 can be determined.

A further subject of the present invention is the advantageous use of a composition according to the invention or a composition prepared or obtainable by the process according to the invention as adhesion promoter, e.g. in the form of a primer, as an ingredient in coating systems, as an ingredient in paints and varnishes, as a drilling aid, as an agent or as an additive in the extraction and production of petroleum and / or natural gas, as an agent or in a means for solidification or crosslinking in particular sand rich Soil layers, as an agent or in a rock-hardening agent, preferably for steam or liquid-permeable rocks or sands, for example sandstone, consolidated sands, as an agent or in a means for landfill sealing, as an agent or in a foundry sands agent, as an ingredient in epoxy as well as phenolic resins, as a component in plastics, as a component in organically modified glasses, for the modification of glass and mineral fiber surfaces, for glass fiber reinforcement of plastics, as an ingredient in sizing and for the treatment of fillers and pigments, and as an additive in adhesives and sealants ,

Thus, according to the teaching of the invention advantageously compositions having a content of tris (alkylalkoxysilyl) amines of more than 71 wt .-%, in particular those containing tris (alkylalkoxysilyl) amines to 98 wt .-%, in a simpler and more economical Be prepared and provided in an advantageous manner for various applications.

All the preferred ranges listed above within the scope of the present application subject matter can be combined with one another and thus disclosed in their entirety.

Moreover, in the numerical preferred ranges of the present invention listed above, all numerical intermediate values or numbers are to be read in full as a disclosure.

The present invention will be further illustrated by the following examples without limiting the subject matter.

Examples

pH Determination

The determination of the pH can be carried out by means of pH indicator paper or pH indicator strips (Merck KGaA). In the case of aminosilanes, the sample is first mixed 1: 1 with deionized water prior to measurement.

Determination of water contents in amines

The determination of water in amines is carried out according to Karl-Fischer, in addition to the product information of Messrs. Merck KGaA, "Karl Fischer application - product group alcohols, amines" of 13.12.2011 ,

Gas chromatographic determination of aminoalkylalkoxysilanes and alcohol

Principle of the method -

The determination of the individual components is carried out by gas chromatography.

Analysis conditions -

All information is intended as a guide. Columns of similar polarity e.g. from other manufacturers are allowed. If the separation can demonstrably also be achieved with a packed column device, this is also permitted.

When handling the samples, their sensitivity to moisture must be taken into account. Device: Capillary gas chromatograph with WLD and integrator eg HP 5890 with integrator HP 3396 Column: capillary column Length: 25 m inner diameter: 0.20 mm Film Thickness: 0.33 mm stationary phase: HP Ultra 1 temperatures: Column oven: 120 ° C-2 min-10 ° / min-275 ° C-8 min injector: 250 ° C Detector: 280 ° C Carrier gas: helium Flow: about 1 ml / min Split ratio: about 1: 100 Injected sample: 0.4 ml

3. Evaluation

• a) normalization to 100 area%, the calibration factors are all set equal to 1 (e.g., AMEO)
• b) If the product contains high boiler components, it will be calibrated with AMEO and internal standard (Dodecan).

Determination of total chloride in organosilanes

Method:

A maximum of 800 mg of the sample is weighed into a quartz dish. The ignition wire is wrapped in cigarette paper and hung in the quartz bowl. The quartz bowl is suspended in a calorimeter bomb, in which 5 ml of water are presented, and the ignition wire connected to the ignition device. The bomb is closed and filled with oxygen up to a pressure of 35 bar. Considering appropriate security measures, the bomb is detonated in a water-filled calorimeter. After cooling, the excess oxygen is released. The bomb contents are rinsed with acetic acid in ethanol (25%) in a 150 ml plastic cup. The residue in the quartz bowl is also transferred to the plastic cup. After addition of 10 ml of hydrofluoric acid (conc.) Is stirred for 30 minutes. The resulting solution is titrated potentiographically with silver nitrate solution [c (AgNO ₃ ) = 0.1 or 0.01 mol / l]. A blank value created in the same way is deducted.

Evaluation:

• Total chloride [mg / kg] = 1000 (A-B) c 35.45 / E

  A

  = Consumption for the sample in ml

  B

  = Consumption for the blank value in ml

  c

  = Concentration of AgNO ₃ solution in mol / l

  e

  = Weight in g

Example 1:

240.8 g (1.0 mol) of CPTEO and 55.0 g (0.25 mol) of AMEO and 134.2 g (1.33 mol) were added under N ₂ in a dry 1 l Büchi glass autoclave with stirrer and distillation apparatus. Submitted triethylamine. The reactor was closed and the mixture heated to 175 ° C. This resulted in an overpressure of 3-4 bar. After 8 h, the reaction was stopped. The reaction product mixture thus obtained was filtered through a Seitz-K-900 filter plate and washed twice with a little toluene. Subsequently, the toluene and the excess CPTEO was removed in vacuo at a maximum of 120 ° C. A slightly yellow liquid is obtained. GC analysis gave the following result in area% WLD: 0.9% CPTEO, 12.3% bis-AMEO, 79.9% Tris-AMEO chloride: 350 mg / kg

Example 2:

Were placed in a dry 1 liter Buchi glass autoclave equipped with a stirrer and distillation apparatus, and N ₂ 198.14 g (0.82 mol) CPTEO and 175.18 g (0.41 mol) of bis-AMEO, and 124.53 g (1.23 mol) triethylamine submitted. The reactor was closed and the mixture heated to 175 ° C. This resulted in an overpressure of 3-4 bar. After 8 h, the reaction was stopped. The reaction product mixture was filtered through a Seitz-K-900 filter plate and washed 2 times with a little toluene. Subsequently, the toluene and other volatile constituents were removed from the desalted reaction product mixture in vacuo to a maximum of 180 ° C over 13 h. The distillation residue (product) was analyzed by GC, cf. Table 1. Table 1: Result of GC analysis of the product GC-WLD-FL% product Reaction time [h] Mass [g] ETOH toluene Triethylamine CPTEO Cyclo-bis-AMEO Bis AMEO Tris AMEO rest Dest. 13.2 243.30 - - - 0.15 0.41 7.36 89.24 2.84

Calculated yields based on 0.41 mol bis-AMEO and weight = 243.3 g yield Tris-AMEO = 85%

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (11)

Compositions containing more than 71 to 98% by weight of tris- (alkylalkoxysilyl) amines, based on the composition, wherein the respective components in the composition add up to 100% by weight. A composition according to claim 1 containing from 72.5 to 96% by weight of tris (alkylalkoxysilyl) amines, based on the composition, wherein the respective components in the composition add up to 100% by weight. Compositions according to claim 1 or 2, containing from 1 to 1000 mg / kg of acidic chloride Compositions according to claim 3 containing 5 to 500 mg / kg of acid chloride, more preferably 8 to 400 mg / kg. Compositions according to claim 4 containing 8 to 400 mg / kg of acidic chloride. Process for the preparation of a tris (alkylalkoxysilyl) amine-rich composition according to one of claims 1 to 5, by reacting (A1) a monosilylated amine of the general formula (I) NH ₂ [(CH ₂ CH ₂ ) NH] _x (R ¹ ) -Si (R ² ) _y (OR) _3-y (I), wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms, R ^{1 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{2 is} an alkyl group having 1 or 2 C atoms, x is equal 0 or 1 and y are 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio of monosilylated amine to chloroalkylalkoxysilane of 1: ≥ 2 to 1:25, the reaction at a temperature of 60 to 220 ° C and a pressure of 0.5 to 50 bar above 1 to 10 hours, separating off the resulting proportion of solid salt and then distilling off unreacted chloroalkylalkoxysilane from the product composition, or (A2) a mixture of a monosilylated amine of the general formula (I) NH ₂ [(CH ₂ CH ₂ ) NH] _x (R ¹ ) -Si (R ² ) _y (OR) _3-y (I), wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms, R ^{1 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{2 is} an alkyl group having 1 or 2 C atoms, x is equal 0 or 1 and y are 0, 1 or 2, and a bis-silylated amine of the general formula (III) (R ⁵ O) _3-z (R ⁴ ) _z Si (R ³ ) -NH [(CH ₂ CH ₂ ) NH] _x (R ¹ ) Si (R ² ) _y (OR) _3-y (III), wherein R and R ^{5 are} each independently a linear or branched alkyl group with 1 to 4 C atoms, R ² and R ^{4 are} each independently an alkyl group having 1 or 2 C atoms, R ¹ and R ^{3 are} each independently a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and x is the same Is 0 or 1 and z and y are each independently 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ⁵ represents a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkyl group having 1 or 2 carbon atoms, R ³ represents a divalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio of monosilylated amine to chloroalkylalkoxysilane of 1: ≥ 2 to 1:25, the reaction at a temperature of 60 to 220 ° C and a pressure of 0.5 to 50 bar above 1 to 10 hours, separates the resulting proportion of solid salt and then distilled unreacted chloroalkylalkoxysilane from the product composition, or (A3) a bis-silylated amine of the general formula (III) (R ⁵ O) _3-z (R ⁴ ) _z Si (R ³ ) -NH [(CH ₂ CH ₂ ) NH] _x (R ¹ ) Si (R ² ) _y (OR) _3-y (III), wherein R and R ^{5 are} each independently a linear or branched alkyl group having 1 to 4 C atoms, R ² and R ^{4 are} each independently an alkyl group having 1 or 2 C atoms, R ¹ and R ^{3 are} each independently a bivalent, represent linear or branched alkyl radical having 1 to 4 carbon atoms and x is 0 or 1 and z and y are each independently 0, 1 or 2, with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio of monosilylated amine to chloroalkylalkoxysilane of 1: ≥ 2 to 1:15, the reaction at a temperature of 60 to 220 ° C and a pressure of 0.5 to 50 bar above 1 Performs to 10 hours, separates the resulting proportion of solid salt and then distilled off unreacted chloroalkylalkoxysilane from the product composition, or (B) ammonia with a chloroalkylalkoxysilane of the general formula (II) Cl- (R ³ ) -Si (R ⁴ ) _z (OR ⁵ ) _3-z (II), wherein R ^{5 is} a linear or branched alkyl group having 1 to 4 C atoms, R ^{4 is} an alkyl group having 1 or 2 C atoms, R ^{3 is} a bivalent, linear or branched alkyl radical having 1 to 4 carbon atoms and z is 0, 1 or 2, in a molar ratio of ammonia to chloroalkylalkoxysilane of 1: ≥ 3 to 1: 9 under a pressure of 25 to 100 bar and reacted at a temperature of 50 to 110 ° C, the resulting proportion of solid salt separated and then unreacted chloroalkylalkoxysilane distilled off from the product composition, or (C) a trialkenylamine, preferably triallylamine, in the presence of a noble metal catalyst which may be present as a supported or complex catalyst system, preferably a Pt, Rh or Ru containing catalyst system, with a hyrogenalkoxysilane, preferably hydrogentrimethoxysilane, hydrogentriethoxysilane , hydrosilylated, wherein the reactant components in a molar ratio Trialkenylamin to Hydrogenalkoxysilane of 1 to ≥ 2.2 to 1 to 50, and optionally works up the product mixture thus obtained. A method according to claim 6, characterized in that the product composition thus obtained is added at least one further component at least one hydrocarbon, an alcohol, preferably from series methanol and ethanol, and / or water. Compositions containing more than 71 to 98% by weight of tris- (alkylalkoxysilyl) amines, based on the composition, wherein the respective components in the composition add up to 100% by weight, obtainable according to Claim 6 or 7.  A composition according to any one of claims 1 to 8, characterized by a content of mono-silylated amine of 0.05 to <29 wt .-%, preferably from 0.1 to 25 wt .-%, particularly preferably from 0.2 to 15 Wt .-%, based on the composition, wherein the respective components in the composition add up to 100 wt .-%. A composition according to any one of claims 1 to 9, characterized by a content of bis-silylated amine of 0.1 to <29 wt .-%, preferably from 0.2 to 26 wt .-%, particularly preferably from 0.5 to 15 Wt .-%, based on the composition, wherein the respective components in the composition add up to 100 wt .-%. Use of a composition according to any one of claims 1 to 10 as an adhesion promoter, as a primer, as an ingredient in coating systems, as an ingredient in paints and coatings, as a drilling aid, as an agent or as an additive in the extraction and production of oil and / or natural gas, as an agent or in a means for solidifying or crosslinking in particular sand-rich earth layers, as an agent or in an agent for rock consolidation, preferably for steam or liquid permeable rocks or sands, such as sandstone, solidified sands, as an agent or in a means for landfill, as a means or in a foundry sands agent, as an ingredient in epoxy and phenolic resins, as a component in plastics, as an ingredient in organically modified glasses, for the modification of glass and mineral fiber surfaces, for the glass fiber reinforcement of plastics, as an ingredient in sizing and for the treatment of F llstoffen and pigments and as an additive in adhesives and sealants.