RU2767054C1 - Method of producing a polyurethane composition for making a vapor-permeable membrane - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing a polyurethane composition for making a vapor-permeable membrane. Method is carried out by reacting polyoxyethylene glycol with molecular weight of 400, ortho-phosphoric acid and triethanolamine while stirring at temperature of 80±2 °C and a residual pressure of 0.7 kPa for 2 hours, further, copper (II) chloride is added and dissolved in the reaction mass at a temperature in range of 85–90 °C, after copper (II) chloride dissolution, reaction mass is reacted with aromatic polyisocyanate based on 4,4-diphenylmethane diisocyanate. Ratio of components of the reaction mixture is as follows,wt. pts. : polyoxyethylene glycol with molecular weight 400, 100, orthophosphoric acid 12–20, triethanolamine 5–8, 4,4'-diphenylmethane diisocyanate 90–100, copper (II) chloride 0.01–0.15.

EFFECT: invention enables to manufacture a vapor-permeable membrane with a high vapor permeability coefficient from the obtained polyurethane composition.

1 cl, 1 tbl, 8 ex

Description

The invention relates to membrane technology, namely to a method for producing a polyurethane composition for the manufacture of a vapor-permeable membrane and can later be used as a diffusion, waterproof layer in sportswear.

With the development of membrane technology, polymer membrane materials have found wide application in the textile industry as a waterproof, vapor-permeable layer in outerwear for various purposes, tents, shoes and gloves. Currently, the most promising class of polymers for laminating textile materials are polyurethanes, since they have high vapor permeability, excellent physical and mechanical characteristics, and resistance to various environments. Much attention of scientists has recently been focused on the creation of polyurethane compositions based on aqueous dispersions or melts without the use of solvents in order to minimize the release of toxic wastewater into the environment and achieve a high vapor permeability coefficient.

Vapor permeability coefficient (WVP) is a measure of the efficiency of vapor permeable membranes and determines the mass of water vapor passing through a certain membrane surface area per unit time. The vapor permeability coefficient of membranes is traditionally examined by the ASTM E 96-80 V method and is measured in g/m ² × 24 h.

Moisture absorption - the property of vapor-permeable membranes to absorb and retain water. When a large amount of water is absorbed, the membranes soften, lose their mechanical strength and adhesion to textile materials decreases. Therefore, the lower the moisture absorption value, the longer the membrane material will last. Moisture absorption is measured by the weight method according to GOST 22900-78 and expressed as a percentage by weight.

A known method for producing a polyurethane composition for the manufacture of a vapor-permeable membrane by reacting the polyol component of polytetramethylene glycol with a molecular weight of 2900 or polycaprolactone diol with a molecular weight of 3000 or polypropylene glycol with a molecular weight of 3000, an aromatic isocyanate - 4,4 - diphenylmethane diisocyanate and polyoxyethylene glycol with a molecular weight of 3400. Then into the reaction mass add 50 ml of N,N-dimethylformamide and the interaction is carried out at 80°C for 2 hours. At the second stage, a solution of 1,4-butanediol in N,N-dimethylformamide is added to the reactor, and the process is carried out at a temperature of 80°C for 2 hours. If necessary, the reaction mixture is diluted with N,N-dimethylformamide to reduce the viscosity of the system.

From the resulting composition, a vapor-permeable membrane with a thickness of 90 μm is made by pouring a polyurethane composition onto a Teflon-coated steel plate. Next, the polymer membrane is cured for 12 hours at 60°C, followed by drying in a vacuum oven for 12 hours at 80°C. Then the Teflon plates were removed from the vacuum oven and kept at room temperature for 2 hours to separate the polymeric membranes from the Teflon substrate.

At a temperature of 25°C, the vapor permeability coefficient of the membrane is 600 g/m ² ×24 h, and at 45°C - 1450 g/m ² ×24 h, see S. Mondal, JL Hi, Z. Yong // Free volume and water vapor permeability of dense segmented polyurethane membrane / Journal of Membrane Science, Vol. 280, No. 1-2, pp. 427-432.

The disadvantages of the known method for producing a polyurethane composition for the manufacture of a vapor-permeable membrane is the multi-stage process, which leads to high energy and resource costs, a vapor-permeable membrane made from the resulting composition has a low vapor permeability coefficient, and a toxic solvent is used to obtain a vapor-permeable membrane.

A known method of obtaining a polyurethane composition for the manufacture of a vapor-permeable membrane in two stages. At the first stage, the loading of the polyol component is carried out, which is taken as polytetrahydrofuran with a molecular weight of 1000, 2000 or polycaprolactone diol with a molecular weight of 2000 and an aromatic isocyanate - isophorone diisocyanate, which are loaded into a four-necked round-bottom flask with a volume of 250 ml, equipped with a mechanical stirrer and a nitrogen inlet. The resulting reaction mass is heated in a nitrogen atmosphere to a temperature of 80°C with constant stirring at 300 rpm for 1 hour. Then dimethylpropionic acid is added and the process is carried out at 95°C for 70 minutes. In the second stage, the resulting reaction mass is dispersed with vigorous stirring in deionized water containing triethylamine at 28°C, and then 1,4-butanediol is added. The interaction is carried out for 70 min at 500 rpm, and methanol is introduced at the end of the process.

From the resulting composition in the form of a dispersion, a vapor-permeable membrane is made by casting into a Teflon mold, followed by curing at room temperature for 24 hours and drying at 60°C for one night.

At a temperature of 25°C, the vapor permeability coefficient of the membrane is 430 g/m ² ×24 h, and the moisture absorption is 7.5%. At 50°C, the vapor permeability coefficient of the membrane is 1600 g/m ² × 24 h, and the moisture absorption is 17.3%, see A. Morel, F. Salau, G. Bedek, D. Dupont, S. Giraud // Water vapor permeability of thermosensitive polyurethane films obtained from isophorone diisocyanate and polyester or polyether polyol / Journal of Materials Science, Vol. 52, no. 2, pp. 1014-1027.

The disadvantages of the known method for producing a polyurethane composition for the manufacture of a vapor-permeable membrane is the multi-stage process, which leads to high energy and resource costs, a vapor-permeable membrane made from the resulting composition has a low vapor permeability coefficient.

The closest in technical essence is a method for obtaining a polyurethane composition for the manufacture of a vapor-permeable membrane by reacting a polyol - polyoxyethylene glycol with a molecular weight of 400 and phosphoric acid, followed by stirring for 2 minutes, triethanolamine is added to the reaction mass and the process is carried out with constant stirring, at a temperature 80±2°C and a residual pressure of 0.7 kPa for 2 hours, then enter the aromatic isocyanate - 4,4 - diphenylmethanediisonianate and stirred for 5 minutes at room temperature, in the following ratio, wt. hours:

fulloxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 12-24.5 triethanolamine 5.5 4,4'-diphenylmethane diisocyanate one hundred.

A vapor-permeable membrane is made from the resulting composition by distributing it with a doctor blade over an inert surface (glass, ceramics) and curing at room temperature for 24 hours, followed by drying at 100°C for 10 minutes.

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 664 g/m ² ×24 h, and the moisture absorption is 9.4%. At 40°C, the vapor permeability coefficient of the membrane is 3091 g/m ² × 24 h, and the moisture absorption is 18.2%, see I. M. Davletbaeva, O. O. Sazonov, IN Zakirov, AM Gumerov, AV Klinov, AR Fazlyev, AV Malygin // Organophosphorus Polyurethane Ionomers as Water Vapor Permeable and Pervaporation Membranes // Polymers, Vol. 13, No. 9, pp. 1442.

The known method for producing a polyurethane composition does not allow the production of a vapor permeable membrane with a high vapor permeability coefficient.

The technical problem is the development of a method for obtaining a polyurethane composition for the manufacture of a vapor-permeable membrane with a high coefficient of vapor permeability.

The technical problem of increasing the vapor permeability coefficient of the membrane is solved by the method of obtaining a polyurethane composition for the manufacture of a vapor-permeable membrane by reacting polyoxyethylene glycol with a molecular weight of 400, ortho-phosphoric acid and triethanolamine, the process is carried out with stirring, a temperature of 80±2°C and a residual pressure of 0.7 kPa for 2 hours, followed by the interaction of the reaction mass with an aromatic polyisocyanate based on 4,4 - diphenylmethane diisocyanate, according to the invention, before reacting the reaction mass with an aromatic polyisocyanate based on 4,4 - diphenylmethane diisocyanate, copper (II) chloride is introduced into the reaction mass and dissolved in reaction mass at a temperature of 85-90°C, in the following ratio, wt. hours:

fulloxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 12-20 triethanolamine 5-8 4,4'-diphenylmethane diisocyanate 90-100 copper(II) chloride 0.01-0.15

The solution of the technical problem makes it possible to manufacture a vapor-permeable membrane from the resulting composition with a vapor permeability coefficient exceeding 766 g/m ² ×24 h while maintaining the same level of moisture absorption.

Characteristics of the substances used in the claimed method for obtaining a polyurethane composition for the manufacture of a vapor-permeable membrane:

- polyoxyethylene glycol with a molecular weight of 400 manufactured by OAO Nizhnekamskneftekhim, Russia;

- ortho-phosphoric acid according to GOST 6552-80;

- triethanolamine, production of Kazanorgsintez PJSC, Russia TU 2423-168-00203335-2007;

- polyisocyanate based on 4,4'-diphenylmethane diisocyanate brand Wannate PM-200, manufactured by Wanhua-Borsodchem, China;

- copper chloride (II) - CuCl ₂ ⋅H ₂ O, GOST 4167-74

The polyurethane composition for the manufacture of a vapor-permeable membrane is carried out by the interaction of polyoxyethylene glycol with a molecular weight of 400, ortho-phosphoric acid and triethanolamine, the process is carried out with stirring, a temperature of 80 ± 2 ° C and a residual pressure of 0.7 kPa for 2 hours, then into the reaction copper (II) chloride is added to the mass and dissolved in the reaction mass at a temperature of 85-90 ° C, after which an aromatic isocyanate based on 4,4 - diphenylmethane diisocyanate is introduced into the reaction mass, in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 12-20 triethanolamine 5-8 4,4'-diphenylmethane diisocyanate 90-100 copper(II) chloride 0.01-0.15

From the resulting composition, a vapor-permeable membrane is made by spreading with a doctor blade over an inert surface (glass, ceramics) and cured at room temperature for 48 hours, with the formation of vapor-permeable membranes with a thickness of 80 μm.

The invention is illustrated by the following specific examples:

Example 1

The polyurethane composition for the manufacture of a vapor-permeable membrane is carried out by the interaction of polyoxyethylene glycol with a molecular weight of 400, ortho-phosphoric acid and triethanolamine, the process is carried out with stirring, a temperature of 80 ± 2 ° C and a residual pressure of 0.7 kPa for 2 hours, then into the reaction copper (II) chloride is added to the mass and dissolved in the reaction mass at a temperature in the range of 85-90 ° C, after which an aromatic isocyanate based on 4,4 - diphenylmethane diisocyanate is introduced into the reaction mass, in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 10 triethanolamine five 4,4'-diphenylmethane diisocyanate 90 copper(II) chloride 0.01

From the resulting composition, a vapor-permeable membrane is made by spreading with a doctor blade over an inert surface (glass, ceramics) and cured at room temperature for 48 hours, with the formation of vapor-permeable membranes with a thickness of 80 μm.

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 697 g/m ² ×24 h, and the moisture absorption is 9.3%. At a temperature of 40°C, the vapor permeability coefficient of the membrane is 3245 g/m ² ×24 h, and the moisture absorption is 18.1%.

Example 2 is similar to example 1, but:

Polyurethane composition for the manufacture of a vapor-permeable vapor-permeable membrane obtained in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 16.25 triethanolamine 6 4,4'-diphenylmethane diisocyanate one hundred copper(II) chloride 0.05

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 739 g/m ² ×24 h, and the moisture absorption is 9.2%. At a temperature of 40°C, the vapor permeability coefficient of the membrane is 3443 g/m ² ×24 h, and the moisture absorption is 17.9%.

Example 3 is similar to example 1, but:

Polyurethane composition for the manufacture of a vapor-permeable membrane obtained in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid twenty triethanolamine 8 4,4'-diphenylmethane diisocyanate one hundred copper(II) chloride 0.05

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 748 g/m ² ×24 h, and the moisture absorption is 9.2%. At a temperature of 40°C, the vapor permeability coefficient of the membrane is 3485 g/m ² ×24 h, and the moisture absorption is 17.9%.

Example 4 is similar to example 1, but:

Polyurethane composition for the manufacture of a vapor-permeable membrane obtained in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 16.25 triethanolamine five 4,4'-diphenylmethane diisocyanate 90 copper(II) chloride 0.1

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 773 g/m ² ×24 h, and the moisture absorption is 9%. At a temperature of 40°C, the vapor permeability coefficient of the membrane is 3603 g/m ² ×24 h, and the moisture absorption is 17.6%.

Example 5 is similar to example 1, but:

Polyurethane composition for the manufacture of a vapor-permeable membrane obtained in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 10 triethanolamine 8 4,4'-diphenylmethane diisocyanate 90 copper(II) chloride 0.1

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 769 g/m ² ×24 h, and the moisture absorption is 9.1%. At a temperature of 40°C, the vapor permeability coefficient of the membrane is 3582 g/m ² ×24 h, and the moisture absorption is 17.7%.

Example 6 is similar to example 1, but:

Polyurethane composition for the manufacture of a vapor-permeable membrane obtained in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 16.25 triethanolamine 8 4,4'-diphenylmethane diisocyanate one hundred copper(II) chloride 0.125

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 799 g/m ² ×24 h, and the moisture absorption is 8.9%. At a temperature of 40°C, the vapor permeability coefficient of the membrane is 3722 g/m ² ×24 h, and the moisture absorption is 17.3%.

Example 7 is similar to example 1, but:

Polyurethane composition for the manufacture of a vapor-permeable membrane obtained in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid twenty triethanolamine 7 4,4'-diphenylmethane diisocyanate one hundred copper(II) chloride 0.1

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 816 g/m ² ×24 h, and the moisture absorption is 8.5%. At a temperature of 40°C, the vapor permeability coefficient of the membrane is 3802 g/m ² ×24 h, and the moisture absorption is 16.5%.

Example 8 is similar to example 1, but:

Polyurethane composition for the manufacture of a vapor-permeable membrane obtained in the following ratio, wt. hours:

polyoxyethylene glycol with a molecular weight of 400 one hundred orthophosphoric acid 10 triethanolamine 7 4,4'-diphenylmethane diisocyanate 90 copper(II) chloride 0.15

At a temperature of 22°C, the vapor permeability coefficient of the membrane is 828 g/m ² ×24 h, and the moisture absorption is 8.7%. At a temperature of 40°C, the vapor permeability coefficient of the membrane is 3857 g/m ² ×24 h, and the moisture absorption is 16.8%.

Data on examples of a specific implementation - vapor permeability coefficient and moisture absorption are summarized in table 1

As can be seen from the examples of a specific implementation, the claimed method for producing a polyurethane composition, from which the vapor-permeable membrane is made, at 22°C has a vapor permeability coefficient exceeding 164 g/m ² × 24 h, and at 40°C it has a vapor permeability coefficient exceeding 766 g/ m ² ×24 h coefficient of vapor permeability of the prototype while maintaining the same level of moisture absorption.

Claims (2)

A method for producing a polyurethane composition for the manufacture of a vapor-permeable membrane by reacting polyoxyethylene glycol with a molecular weight of 400, ortho -phosphoric acid and triethanolamine, the process is carried out with stirring, a temperature of 80±2°C and a residual pressure of 0.7 kPa for 2 hours, followed by interaction of the reaction mass with an aromatic polyisocyanate based on 4,4-diphenylmethane diisocyanate, characterized in that before the interaction of the reaction mass with an aromatic polyisocyanate based on 4,4-diphenylmethane diisocyanate, copper (II) chloride is introduced into the reaction mass and dissolved in the reaction mass at a temperature of 85 -90°C, with the following ratio of components, wt.h.: polyoxyethylene glycol with a molecular weight of 400 one hundred ortho -phosphoric acid 12-20 triethanolamine 5-8 4,4'-diphenylmethane diisocyanate 90-100 copper(II) chloride 0.01-0.15