The modification of the aqueous cationic dispersions polyetherurethanes

 

(57) Abstract:

Usage: used for impregnation of fabrics, fibrous bases, carpet materials, for finishing of fiberglass, as sealants, decorative coatings. The inventive aqueous cationic polyetherurethanes dispersion obtained by reacting isocyanate of prepolymer with oxopropylidene Diethylenetriamine with subsequent dispersion obtained in an aqueous solution of acid, is treated with a Hydrosol of silicon dioxide in an amount of 0.1 to 3.0% by weight of the dispersion. table 1.

The invention relates to a method of modifying aqueous cationic dispersions of polyetherurethane (PES) used for impregnation of fabrics, fibrous bases, carpet materials, for finishing of fiberglass, as sealants, decorative coatings, etc.

A method of obtaining a PES dispersions by reacting isocyanate of prepolymer with extension chain amine type, followed by dispersing the resulting product in an aqueous solution of acids [1] the Disadvantage of this method is the low stability of the dispersion, poor sealing capability due to large particle size (1-25 μm), as well as the texts PES dispersion by reacting isocyanate of prepolymer with extension chain amine type, followed by dispersing the resulting product in an aqueous solution of acids, at the same time as chain extension amine of the type used oxopropylidene Diethylenetriamine, and the isocyanate prepolymer is obtained on the basis of polyoxypropyleneglycol and 4,4'-diphenylmethanediisocyanate at a molar ratio of NCO:OH = 2:1 [2] PES variance method [2] are the best in comparison with the method [1] properties. Particle size on 1-2 order of magnitude smaller (tenths-hundredths of microns), the glass transition temperature of the polyester portion of the polymer is lower than in the PES according to the method of [1] and is -15about(For PES based on polyester mol.m. 1000) and -40about(For PES based on polyester mol.m. 2000). PES variance method [2] provides improved performance characteristics of the products obtained at low temperatures. The disadvantage of this method reduced the hydrophobicity of the coatings produced from such dispersions, and not sufficiently high adhesion to a range of materials (polyethylene, polyester, glass and others).

The purpose of the invention increase the hydrophobicity obtained on the basis of PES variance films and coatings, as well as improving the adhesion of such coatings to the substrates while maintaining the operational characteristics of the films and coatings at low temperatures, i.e., the glass transition temperature of the polymer. Okazawa 0.1 to 3.0 mass. with respect to the polymer.

P R I m e R 1. A 30% aqueous dispersion of a PES-based prepolymer obtained by the reaction of polyoxypropyleneglycol mol.m. 1000 and 4,4'-diphenylmethanediisocyanate when the ratio of NCO groups:OH a 2:1 chain extension of oxypropylene Diethylenetriamine (the ratio of NCO groups:OH prepolymer and chain extension 1:0,4) enter 0,05 wt. Hydrosol SiO2under stirring. The percentage of SiO2specified in relation to the polymer. From the obtained modified dispersion is formed at room temperature, the film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, hygroscopicity films 18% adhesion (bond strength when delamination) to polyethylene 1.6 g/cm adhesion to polyester 28,0 g/cm Adhesion to glass when the particle diameter of SiO26 nm equal to 300 g/cm, when the particle diameter of 12.8 nm it is also equal to 300 g/see

P R I m m e R 2. In the dispersion of example 1 is injected 0.1 wt. Hydrosol SiO2under stirring. From the obtained modified dispersion is formed at room temperature, the film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, hygroscopicity films 14% adhesion to polyethylene (strength at delamination) of 3.0 g/cm, edge is it equal to 340 g/see

P R I m e R 3. In the dispersion of example 1 is injected 0.2 wt. Hydrosol SiO2(relative to the polymer). From the obtained modified dispersion is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, hygroscopicity films 14% adhesion to polyethylene and 3.3 g/cm, Dacron 38.0 g/cm, to the glass when the particle diameter of SiO26 nm adhesion equal to 380 g/cm, when the particle diameter of 12.8 nm 360 g/see

P R I m e R 4. In the dispersion of example 1 is administered to 0.3 wt. Hydrosol SiO2(relative to the polymer). From the obtained modified dispersion is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film 14,0% adhesion to polyethylene 3.5 g/cm, the adhesion to the polyester of 38.7 g/cm adhesion to glass when the particle diameter of SiO26 nm is equal to 380 g/cm, when the particle diameter of 12.8 nm is equal to 360 g/see

P R I m e R 5. In the dispersion of example 1 is injected 0.5. Hydrosol SiO2(relative to the polymer). From the obtained modified dispersion is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith the absorption of the films of 13.6%, the adhesion to polyethylene 3.5 g/cm adhesion to polyester 39,0 g/cm adhesion to glass when the particle diameter of SiO2ERU 1 enter 0.7 wt. Hydrosol SiO2(relative to the polymer). From the obtained modified dispersion is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film 13,5% adhesion to polyethylene 3.5 g/cm adhesion to polyester to 39.3 g/cm adhesion to glass when the particle diameter of SiO26 nm is equal to 385 g/cm, while the diameter of 12.8 nm equal to 370 g/see

P R I m e R 7. In the dispersion of example 1 is injected with 0.9 wt. Hydrosol SiO2(relative to the polymer). From the obtained modified dispersion is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film 13,2% adhesion to polyethylene 3,55 g/cm adhesion to polyester 39,0 g/cm adhesion to glass when the particle diameter of SiO26 nm is equal to 380 g/cm, while the diameter of the particles of SiO2of 12.8 nm equal to 380 g/see

P R I m e R 8. In the dispersion of example 1 is administered to 1.1 wt. Hydrosol SiO2(relative to the polymer). From the obtained modified dispersion is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film 12,3% adhesion to polyethylene 3.5 g/cm adhesion to polyester 41,0 g/cm adhesion to glass when the particle diameter of SiO26 nm is equal to 390 g/cm, and the diameter of cha 2 (relative to the polymer). From the obtained modified dispersion is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film 11,7% adhesion to polyethylene of 3.45 g/cm adhesion to polyester 42,0 g/cm adhesion to glass when the particle diameter of SiO26 nm is equal to 390 g/cm, while the diameter of the particles of SiO2of 12.8 nm equal to 420 g/see

P R I m e R 10. In the dispersion of example 1 injected 1.5 wt. Hydrosol SiO2(relative to the polymer). From the obtained modified dispersion is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film 11,5% adhesion to polyethylene 3.6 g/cm adhesion to glass when the particle diameter of SiO26 nm equal to 400 g/cm, when the particle diameter of 12.8 nm is equal to 410 g/see

P R I m e R 11. In the dispersion of example 1 is injected 2.0 wt. Hydrosol SiO2(relative to the polymer). From the obtained modified latex is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film 9,5% adhesion to polyethylene 3.75 g/cm adhesion to polyester 42,0 g/cm adhesion to glass when the particle diameter of 6 nm is equal to 390 g/cm, when the particle diameter of 12.8 nm equal to 420 g/see

P R I m e R 12.consistent latex is formed into film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film is 5.0%, the adhesion of the film to the polyethylene 3.8 g/cm adhesion to polyester 43,0 g/cm adhesion to glass when the particle diameter of SiO26 nm is equal to 410 g/cm, when the particle diameter of 12.8 nm equal to 420 g/see

P R I m e p 13. In the dispersion of example 1 is injected 5.0 wt. Hydrosol SiO2(relative to the polymer). From the obtained modified latex is formed into film. The film properties were not evaluated, because the structure of their heterogeneous, there is a network of cracks.

P R I m e R 14 (comparative). From the dispersion of example 1 without SiO2molded film. The film properties: glass transition temperature of the polyester part of the PES 15aboutWith, the hygroscopicity of the film 18,0% adhesion to polyethylene 1.5 g/cm, the adhesion to polyester 26,0 g/cm, the adhesion to glass is equal to 300 g/see

Properties of films obtained from PES dispersion with additives Hydrosol SiO2without it, shown in the table. As can be seen the introduction of SiO2in an amount of 0.1 to 3.0 wt. with respect to the polymer can increase the hydrophobicity of the films, namely the absorption of the films decreased by 72.2% (when the content of SiO23.0 wt.).

With the introduction of Hydrosol SiO2in PES variance dramatically increased the diametre particles of SiO26 nm) and 40% (when the particle diameter of SiO2of 12.8 nm).

Deformation-strength properties of the films of PES-dispersion with the introduction of SiO2(in the optimal range of concentrations) is not particularly limited. Measurement of the average particle radius of PES variance before and after the introduction of the Hydrosol SiO2method of turbidity spectrum showed that abrupt changes of the size of the particles does not occur. Operational properties of the films of PES variance low temperatures does not deteriorate with the introduction of Hydrosol SiO2as the glass transition temperature of the polyester part of the PES with the introduction of SiO2is not changed. It should also be noted additional positive effects achieved by the introduction of Hydrosol SiO2in PES variance: improving the structure of the surface layer of the films obtained on glass and polyethylene and Mylar substrates, namely SiO2provide films with a uniform homogeneous defect-free surface, whereas without SiO2the surface has folds, wrinkles, uneven. Obtaining films and coatings with a thickness of > 1 mm of the PES variance is impossible without prior introduction of SiO2in the dispersion, as without the modifier in this case, Rai, the introduction of SiO2helps reduce the stickiness of the films of PES variance. Special experiments on determination of water vapor permeability of the films showed that the introduction of the Hydrosol SiO2in PES variance does not impair the breathability of the films.

The modification of CATIONIC WATER POLYETHERURETHANES DISPERSIONS by reacting isocyanate of prepolymer with oxopropylidene Diethylenetriamine with further dispersing the resulting product in an aqueous solution of acids, characterized in that, in order to increase the hydrophobicity obtained based on the dispersions of films and coatings, improve the adhesion to the substrate while maintaining the performance characteristics at low temperatures, after dispersion with stirring enter the Hydrosol of silicon dioxide in an amount of 0.1 to 3.0% by weight dispersion calculated on the dry matter.

 

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