CS256456B1 - Silane reagents containing chemically bound complexone moieties - Google Patents

Abstract

The solution concerns silane agents containing a complexone group in the molecule. The subject of the solution are silane agents containing chemically bonded polydonor complexone groups of the general formula II, III, where R = methyl, ethyl, n = 0 or 1. These agents are prepared by treating the compound (R0)3SiCH2CH2CH2 NHR1, where R = methyl, or ethyl, R1 = H, methyl or ethyl, with a complexone dianhydride of the general formula IV, where n = 0 or 1. The products can be used to introduce complexone groups onto siliceous and other inorganic materials, such as silica gel, diatomaceous earth, glass, alumina, titanium dioxide, or as agents improving adhesion in composite materials of the glass-metal, titanium dioxide-metal type, etc.

Description

The invention relates to silane reagents containing complexone moiety in the molecule.

The silane reagents are used to prepare composite materials and to introduce or immobilize suitable functional groups on silica or other inorganic materials. Silane agents with chelating functional groups, such as the 8-hydroxyquinoline or ethylenediamine type, are known and described in the literature (Plueddemann E.P .: Silane coupling agents, Plenum Press, New York 1980). Some of them are already produced for commercial purposes.

However, silane reagents containing complexone type moieties have not been described in the scientific literature. They are closest to the type of chelating function silane reagents containing an iminodiacetic acid moiety (Chromatographia 17, 200 (1983)).

In the patent literature (US patent 4 071 5 ^ -6) discloses agents of formula I (R ¹ 0 R ¹ = methyl, n = 0 or 1, m) _q Si (CH _{2) 3} (l} CH ₉ CH ₉ ) "NH.

2'n 2-methyl, R = H, CH ₂ COOM, = 1 or 2.

R m

M = .H, (I) an alkali metal,

These reagents are prepared by carboxymethylation of the appropriate amine with sodium chloroacetate in aqueous medium.

The main drawback of the known silane complexone agents is their low chelating ability due to the small number of donor sites in this group for the iminodiacetic acid derivative and the incomplete carboxymethylation for the ethylenediamine derivative.

256 456

However, neither preparation of the two reagents is satisfactory. The synthesis of the iminodiacetic acid derivative involves several steps, and the second reagent is - as already mentioned - chemically highly non-uniform. In both cases, the carboxymethylation of the amino groups is carried out in an aqueous medium, resulting in uncontrolled hydrolysis of the alkoxy groups to form silanols, which then spontaneously condense to the siloxane oligomers.

The present invention provides silane reagents comprising a chemically bonded polydonor complexone moiety of formula II, III ch ₂ cooh (RO) SiCH CH CH NHCOCH 2. / ² \ ^J N (CH CH _O N _O -) - CH CH _{O O} N 0 (Li) / ^{n 2 2} * ² \ / *

HOCOCH ₂ CH ₂ Cl ₂ (RO) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCH 2 CH ₂ cooh

N (CH ₂ CH ₂ N -) - _n CH ₂ CH ₂ N

H ₂ CO ₂ CH ₂ CH ₂ Si (OR ₃ ) (III)

HOCOCH

CHgCOOH where R = methyl, ethyl, n = 0 or 1.

A process for the preparation of these reagents consists in treating compound (RO) ₃ SiCH ₂ CH ₂ CH ₂ NHR ¹ , where R = methyl or ethyl, R ¹ = H, methyl or ethyl, with a complexone dianhydride of formula IV> coch ₂ o ^z n (ch ₂ ch ₂ n

CHoCOOH l ^a> _n CH ₂ CH ₂ N

CDCH, / CHpCOx \ ..... /

CHg CO (iv) _t where n = 0 or 1.

The complexone silane reagents of the invention exhibit some advantages over the prior art. Their chelating ability for metal ions is considerable and the stability of the formed metal chelates approximates that of the EDTA chelates. The novel complexone silane reagents are functionally uniform; in addition to structures II and III, they do not contain other chelating groups. They are synthesized in an anhydrous environment and therefore do not contain silanols - hydrolysis products II and III or products

256,456 condensation of these silanols. Thus, the reagents prepared by the process of the present invention retain unhydrolylated alkoxy groups, allowing controlled hydrolysis of these groups in the next step in the reaction of the reagents with the siliceous materials. Thus, the surface concentration of the complexone moieties can be easily controlled in the products obtained. Last but not least, their preparation is simple and based on easily available and cheap raw materials.

The products of the invention can be used to introduce complexone moieties onto silica and other inorganic materials such as silica gel, diatomaceous earth, glass, alumina, titanium dioxide, or as coupling agents in glass-metal, titanium-metal composite materials .apod.

Example

To a suspension of 5.1 g of ethylenediaminetetraacetic acid dianhydride and 30 ml of anhydrous pyridine was added dropwise 2.3 g of 3-aminopropyltethoxy-silane dropwise with stirring, and the reaction mixture was stirred at room temperature for 12 hours. Unreacted dianhydride is then aspirated and washed with anhydrous pyridine. Pyridine is distilled off from the combined filtrates in vacuo. The residue (3 → 7 g) is a mixture of II and III in an approximate 1: 1 molar ratio, as indicated by mass balance and NMR spectra.

The product is a light brown oil soluble in pyridine, the dimethylsulfoxide form, Ή-NMR spectral data (in C 1 H δ, 84 and 6.37-ethyl, T7.56 and 6.5-CH 6, respectively).

The chlorine air humidity is slowly hydrolyzed and converted to polymeric products that are insoluble in conventional organic solvents.

Claims (2)

i. Silane reagents, characterized in that they contain a chemically bonded coaplexone moiety having structures II and III CHgCOOH (RO) 3 SiCH ₂ CH ₂ CH ₂ NHCOCH-hococh / ^ n (CH ₂ CH ₂ N / CHgCO \> _n CH ₂ CH ₂ n-q (II) _CH2 what '(RO) ₃ sich ₂ CH ₂ CH ₂ NHCOCH2 CH ₂ COOH, CH ₂ CONHCH ₂ CH ₂ CH ₂ Si (or • HOCOCH, n (CH ₂ CH ₂ N 4 _n CH ₂ CH ₂ → CH COOH (III) where R = methyl, ethyl, n = O or 1. 2. A process for producing agents according to claim 1 * characterized in that the compound (RO) ₃ SiCH2CH2CH NHRl _2, where R = methyl or ethyl, R * · · = H, methyl or ethyl, acts complexone dianhydride of the formula IV COCH / \ COCH ^ / CH _o C00H _Z CH _P CO. ₍ ¹ Ϊ \ (CHoCHpN-4 CH ₉ CHpN 0 * * ⁿ * * \. / CH CO ^Z (IV) wherein n = 0 or 1.