Method of endowing materials with hydrophilic properties using organosiloxane coating with nitrilotrimethylene phosphonic acid

FIELD: chemistry.

SUBSTANCE: to endow various materials with hydrophilic properties, a modifier is deposited on the surface of said materials. A coating is formed by successively depositing aqueous solution of an oligo(aminopropyl)ethoxysilane of a general formula shown on fig 1, and subsequently depositing aqueous solution of nitrilotrimethylene phosphonic acid of a general formula shown on fig 2. After deposition, each solution is dried on air and heat treated.

EFFECT: invention enables to endow various materials with improved hydrophilic properties.

8 dwg, 6 ex

 

The invention relates to the production of modified materials and can be used to impart hydrophilic properties of the surface materials.

The known method hydrophilicity the treatment of textile material composition containing a mixture of polyorganosiloxane and polydiorganosiloxane (see patent DE No. 3932276 Composition for textile processing and the processing method") [1]. Used polyorganosiloxane has hydrophilic properties, but is water-insoluble compound. To increase its emulsifying ability in the processing of fibrous materials added another polyorganosiloxane that perform the function of surfactants. The disadvantage of this method is the instability of the emulsion, its tendency to coagulation, due to the properties of the used polyorganosiloxane.

The closest according to the features of the claimed method is a method of making textile materials made of fibers of different nature hydrophilic properties (see patent RU No. 2370583 "Method of making fibrous materials hydrophilic properties using oksoalkilzameshchennykh block copolymers") [2]. One of the main disadvantages of this method is that it involves a significant expenditure of copolymers (oxyalkylation used in quantities is 1-5% by weight of fibrous material).

The problem to which the invention is directed, is to develop an improved method for imparting hydrophilic surface properties of various materials at significantly lower costs modifier.

The technical result is achieved due to the application of a surface modifier, formed by molecular Assembly organosiloxane coatings with N,N-bis(1,2-dihydroxypropyl)aminoalkyl groups, and a distinctive feature of the proposed method is that the surface modifier material is formed in two stages, with the first stage using oligo(aminopropyl)amoxicilkin, and the second stage uses nitrilotrimethylphosphonic acid.

Two-stage method of molecular Assembly consists of performing the following operations.

In the first stage performs the immobilization of oligo(aminopropyl)ethoxysilane (I-III, see Figure 1) on the surface of the material. In the second stage are condensation grafted aminopropionitrile organosiloxanes cover with nitriltrimetilenfosfonovaya acid when heated (see Figure 2).

The operation of immobilization on the surface of the material oligo(aminopropyl)ethoxysilane (I-III, see scheme 1) is that the surface of the material moistened with ethanol or aqueous solution of the oligomer is acceptable concentration 0.1; 1%, followed by drying in air and chemical fixing of the modifier on the surface by heat treatment.

In the specified processing modifier (I-III) covalently attached to the surface of the material due to the condensation of taksigrup modifier with the functional groups of the polymer material, forming on the surface of the micro/nano-coating (see Figure 1).

The number organosiloxane coating on the surface of the material after impregnation, drying and heat treatment are judged by the increase in mass of the material, expressed in percent of the initial mass of the material. When a single impregnation, drying and heat treatment of material gain not reached the required values, then the impregnation, drying and heat treatment of the material is held several times up until the weight does not reach the required values.

In the second stage shall wetting modified surface 10%aqueous solution nitriltrimetilenfosfonovaya acid, followed by drying in air and conducting the condensation grafted aminopropionitrile organosiloxanes cover with nitriltrimetilenfosfonovaya acid when heated.

In the specified processing nitrilotrimethylphosphonic acid reacts with the amine groups organosiloxane coating forms on the surface the particular hydrophilic groups (Figure 2).

When the surface layer becomes "brush geometry" (see figure 3).

The presence in the coating of hydrophilic (water-soluble) groups imparts hydrophilic properties to the surface of the material.

The mechanism of formation of hydrophilic organosiloxane coatings on the surface of silicate glass in the first stage is based on the interaction of the reactive hydrophilic amoxicillih groups oligo(aminopropyl)ethoxysilane (I-III) with silanol groups present on the surface of silicate glass (Figure 4), which proceeds with the selection of ethyl alcohol removed by heat treatment of the material.

In the second stage, the mechanism of formation of hydrophilic organosiloxane coatings based on the interaction of grafted aminopropylation organosiloxane coatings with nitriltrimetilenfosfonovaya acid (see Figure 2), resulting in the chemical bonding of hydrophilic nitrilotriethanol groups aminopropylene groups on the surface organosiloxanes coverage.

The mechanism of formation of hydrophilic organosiloxane coatings on the surface of the polyester film in the first stage is based on the interaction of the reactive hydrophilic ethoxyline groups oligo(aminopropyl)ethoxysilane (I-III) with a terminal carboxyl (-COOH) and hydroxyl (-OH) groups will have aximise on the surface of the polyester film (see 5), which proceeds with the selection of ethyl alcohol removed by heat treatment of the material.

In the second stage, the mechanism of formation of hydrophilic organosiloxane coatings based on the interaction of grafted aminopropylation organosiloxane coatings with nitriltrimetilenfosfonovaya acid (see Figure 2), leading to the binding of hydrophilic nitrilotriacetate groups on the surface organosiloxanes coverage.

These IR spectra, taken with modified samples of materials that contain bands of stretching vibrations of P=0 in the field 2700-2600 cm-1R-HE is in the field 1040-1180 cm-1Si-O-Si linkages in the field 1080-1020 cm-1Si-OC connections in the field 880-810 cm-1and the deformation vibration of Si-C linkages in the area of 1260 and 800 cm-1that confirms the formation of the desired organosiloxanes coverage.

A General method of surface treatment of materials is as follows.

The first stage.

- Carrying out of wetting the surface of the material ethanolic or aqueous solutions of oligo(aminopropyl)ethoxysilane (I-III) of a given concentration of 0.1 - 1%and air drying.

- Chemical fixation of the modifier on the surface when heated.

The second phase.

- Conducting wetting modified surface 10%aqueous solution nitrilotriacetate acid and drying in air.

- Carrying out chemical grouting nitriltrimetilenfosfonovaya acid to aminopropylene groups organosiloxane coating when heated.

Example 1. Processing the surface of a silicate glass of 0.1-1%solution of oligomer (I). The treatment was carried out according to the above-mentioned method.

Processing the modified surface of the silicate glass, 10%aqueous solution nitriltrimetilenfosfonovaya acid. The treatment was carried out according to the above-mentioned method.

Increasing hydrophilicity glass surface was evaluated by the regional corner wetting (see Fig.6).

Example 2. Processing the surface of a silicate glass of 0.1-1%solution of oligomer (II). The treatment was carried out according to the above-mentioned method.

Processing the modified surface of the silicate glass, 10%aqueous solution nitriltrimetilenfosfonovaya acid. The treatment was carried out according to the above-mentioned method.

The increase in hydrophilicity of the surface of the glass was measured at boundary corner wetting (see Fig.6).

Example 3. Processing the surface of a silicate glass of 0.1-1%solution of oligomer (III). The treatment was carried out according to the above-mentioned method.

Processing the modified surface of the silicate glass, 10%aqueous solution nitriltrimetilenfosfonovaya acid. The treatment was carried out as described IU is the odik.

The increase in hydrophilicity of the surface of the glass was measured at boundary corner wetting (see Fig.6).

Example 4. Surface treatment of polyester film of 0.1 to 1%solution of oligomer (I). The treatment was carried out according to the above-mentioned method.

Processing the modified surface of the polyester film 10%aqueous solution nitriltrimetilenfosfonovaya acid. The treatment was carried out according to the above-mentioned method.

The increase in hydrophilicity of the surface of the polyester film was evaluated by the regional corner wetting (see Fig.6).

Example 5. Surface treatment of polyester film of 0.1 to 1%solution of oligomer (II). The treatment was carried out according to the above-mentioned method.

Processing the modified surface of the polyester film 10%aqueous solution nitriltrimetilenfosfonovaya acid. The treatment was carried out according to the above-mentioned method.

The increase in hydrophilicity of the surface of the polyester film was evaluated by the regional corner wetting (see Fig.6).

Example 6. Surface treatment of polyester film of 0.1 to 1%solution of oligomer (III). The treatment was carried out according to the above-mentioned method.

Processing the modified surface of the polyester film 10%aqueous solution nitriltrimetilenfosfonovaya acid. The treatment was carried out according to the above-mentioned method.

The rise of the Hydra is filenote the surface of the polyester film was evaluated by the regional corner wetting (see 6).

Analysis of the results of processing the surface of the materials described in examples 1-6 showed that the proposed method of imparting hydrophilic materials properties allows for various materials of high hydrophilic properties. Wetting angle of the surface of the material decreases 3.6-15.3 times at an expense of oligo(aminopropyl)ethoxysilane (I-III) from 0.1 to 1% of the mass.

Thus, the proposed method of imparting hydrophilic materials properties can improve the hydrophilicity of the surface materials (silicate glass, polyester film) in 3.6-15.3 times, and gidrogenizirovanii ability organosiloxane coating chemically bound to the hydrophilic nitriltrimetilenfosfonovaya groups exceed prototype properties and require a minimum number of initial products for the formation of the surface modifier.

The inventive method can be used to impart hydrophilic properties to the surfaces of various materials such as glass, ceramics, wood, leather, metals and products from them, such as films, fibers, profiles of the product.

Way to make materials of different nature hydrophilic properties by sequential coating on the surface of materials aqueous solution of oligo(aminopropyl)ethoxysilane General formula

where n=5(I)10(II)15(III)
with a concentration of from 0.1 to 1 wt.% and an aqueous solution nitriltrimetilenfosfonovaya acid formula

with air drying and heat treatment after the application of each solution.



 

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