CS229216B1 - Hydrophyllic polyurethanurea with increased resistance from hydrolytic degradation - Google Patents

Abstract

The invention relates to hydrophilic polyurethanes with increased resistance to hydrolytic degradation that are especially suitable for hydrophilic production materials. It is a polyurethane-urea preparation aliphatic, aromatic and / or alicyclic diisocyanate and polyol based components segmented ethylene oxide polymer a oxylated propylene oxide segments that contain 15 to 70% polyethoxamer in the molecule and preferably a molecular weight of 400 to 3,000; subsequent reaction of the obtained prepolymer with diamines, in synthesis in a solvent preferably with hydrazine. Reacting ratio of the components corresponds to the molar ratio functional groups OH: NCO: NH9 within the ranges lil, 4 to 2, 2: 0, 9 to 2.2 * The main advantage of hydrophilic polyurethanes according to the invention is compared to known hydrophilic types of polyurethanes their increased resistance to hydrolytic destruction. Polyurethaneureas in addition, this type can be synthesized and apply all known technologies preparation and processing of polyurethanes, such as synthesis and processing in a solvent environment, dispersion system or in the form of one or multi-component thermoreactive materials.

Description

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BACKGROUND OF THE INVENTION The present invention relates to hydrophilic polyurethanes with increased resistance to hydrolytic degradation, which are particularly suitable for the production of hydrophilic sheet materials. Nowadays, fiber-reinforced impregnated, laminated or coated polyurethanes are widely used in the field of clothing, clothing and coating materials. Among the requirements imposed on these materials, in addition to the appropriate physical-mechanical properties and aesthetic standards, the favorable physiological properties are very important. In this area, in comparison with natural materials, for example, leather is not, to the extent necessary, primarily satisfied with requirements for sufficient reversible sorption of water vapor. Therefore, a great deal of effort is being made to improve these sorbent properties, which is particularly evident in the attempts to improve the hydrophilic properties of polyurethanes by various treatments and modifications. These include, for example, the addition of various hydrophilic substances - inorganic compounds or polymers with hydrophilic groups to polyurethanes in order to increase their sorption capacity. Similarly, the hydrophilization of polyurethanes by the addition of polyalkylene oxides crosslinked by the action of ionizing radiation or by the addition of variously modified collagen has the same object.

In addition to the procedures based on the addition of hydrophilic substances and processes based on the modification of the prepared polyurethanes by introducing various hydrophilic groups - e.g. carboxyl or sulfo groups - processes / hydrophilic polyurethanes are also becoming very promising by synthesis from hydrophilic polyols, in particular polyester type polyols on ethylene oxide base polymer. For example, the use of 229,218 polyurethanes containing 2 .25% polyoxyethylene groups for the production of poromers is known in the art. In this application, hydrophilic polyurethanes are used either alone or in combination with polyurethane hydrophilics.

However, a significant disadvantage of all known types of polyurethane synthesized from hydrophilic polyols is that comparison with polyurethanes synthesized using non-hydrophilic polyols exhibits substantially lower hydrolysis resistance. This, in applications for poromeric materials, then progressively deteriorates the mechanical properties of these materials during use. During the study of the influence of the structure of the hydrophilic polyols on the properties of polyurethanes, a surprising deviation in the rate of hydrolysis was found. It has been found that the hydrophilic polyurethane ureas of the invention, the transportable polyadditional, poly (ethylene oxide and propylene oxide) segmented polyol component containing 15-70% polyethoxamer per molecule, have been found to have substantially lower hydrolysis degradation rates. preferably a molecular weight of 400 [mu] 3000, followed by reaction of the obtained prepolymer with diamines, preferably in a solvent with a shydrazine. The ratio of the reactants corresponds to the molar ratio of OHNGOiNHg in the range of 1: 1.4 < 2 &gt;

The main advantage of the hydrophilic polyurethanes according to the invention is their increased resistance to hydrolytic degradation compared to the known types of hydrophilic polyurethanes, as already mentioned. In addition, polyurethane ureas of this type can be synthesized and applied by all known polyurethane preparation and processing technologies, such as solvent synthesis and processing, dispersion systems or single or multi-component thermoreactive compositions. Of the isocyanates, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, diphenyl diisocyanate, toluene diisocyanate and isophorone diisocyanate are particularly suitable for the synthesis of the hydrophilic polyurethane ureas of the invention. Hydrazine is particularly suitable for the subsequent reaction of the obtained prepolymer with diamines in a solvent system solvent. The following examples serve to illustrate the nature and effects of the invention in greater detail. Example 1 describes an exemplary practice of carrying out the hydrophilic polyurethane urea synthesis of the invention in a solvent environment. Examples 2 and 3 then describe the synthesis of polyurethaneureas from hydrophilic polyols of another type, under the same stoichiometric ratios and conditions. A comparison of the mechanical properties of the polyurethane urea samples prepared according to Examples 1, 2 and 3 during the hydrolysis is then shown in the table. Example 4 shows the application of the hydrophilic polyurethane urea of the invention in the form of a thermoreactive solvent-free mixture. Example 1

A polyol-containing polymer was prepared by a polyaddition reaction of 250 parts by weight of 4,4 &apos; -diphenyl methanediisocyanate and 690 parts by weight of polyether glycol, which is a segmented polymer of ethylene oxide and propylene oxide with an oxypropylene chain terminating 50% of polyethoxamer in a molecule having an average molecular weight of 1360. 4.46% of free NCO groups. The polyaddition reaction was carried out with stirring under a dry air atmosphere at a temperature of 90 ° C for 4 hours. The prepolymer was dissolved in neat dimethylformamide to a solution of 30 wt.

80 parts by weight of dimethylformamide and 1 part by weight of hydrazine hydrate were introduced into a reactor equipped with an effective stirrer. To this solution, a decreasing velocity of the prepolymer solution was dosed with intensive stirring at room temperature up to a viscosity of about 2 Pa.s (at 30 ° C). -5-229 216

A total of 162 parts by weight of the pre-polymer solution was consumed, the resulting reactant ratio corresponding to the molar ratio of the functional groups of 0Η: Ν00: ΝΗ2, which was 1: 1.96: 1.08. hmoto

This solution was applied to a glass substrate and the coating was dried for 4 hours at 110 ° C. The foils obtained after hydrolysis were subjected to hydrolytic removal in distilled water at 90 ° C. Samples for physical-mechanical evaluation were taken prior to hydrolytic degradation and then every 25, 50 and 100 hours of hydrolysis. The values of physical-mechanical properties are summarized in the table. Example 2

A prepolymer of the corresponding reaction conditions was prepared by the polyaddition reaction of 250 parts by weight of 4,4'-diphenylmethane diisocyanate and 600 parts by weight of a mixture of polyether glycols consisting of an average molecular weight polymers of ethylene 1200 and a polymer of propylene oxide of 1200 in a weight ratio of 1: 1. 1. Also, the reaction polymer with the hydrate hydrate in a solution of dimethylformamide was run under the same conditions as in Example 1. The resulting ratio of reactants corresponded to a molar ratio of OH: NCO: NH2 of 1: 1.92: 1.04. during the hydrolysis test, as in Example 1, the values of the physico-mechanical properties are summarized in the table. Example 3

Polyaddition reaction of 250 parts by weight of 4,4-diphenylisocyanate and 600 parts by weight of polyether glycols by which the ethylene oxide / propylene oxide chain-ending polymer of ethylene oxide and propylene oxide containing 50% polyethoxamer in the molecule and having an average molecular weight of 1200 was Also, the prepolymer reaction with hydrazine hydrate in a dimethylformamide solution was carried out under the same conditions as in Example 1, and the resulting reactant ratio corresponded to a molar ratio of O 2 NCO 3 NH 4 functional groups of 1: 1.92: 1.04. The preparation of samples for hydrolysis and their collection during the hydrolysis test was carried out in the same way as in Example 1. The values of physico-mechanical properties are summarized in the table.

Table: Changes in physico-mechanical properties in the course of the hydrolytic degradation of polyurethane

Property Unit 1-1 1 1 sample from example 1 1 2 3 no dul 100% MPa /% original value 0 25 50 100 5,71 / 100 5,89 / 103 5,78 / 1015,60 / 98 4 , 84/100 4.97 / 102 4.86 / 100 4.73 / 97 5.47 / 1005.62 / 1025.21 / 95 '4.37 / 79 Strength MPa /%% 0 31.6 / 100 23,58 / 100 22,30 / 100 water value 25 50 100 24,5 / 77 18,5 / 58 15,0 / 48 13,23 / 56 11,45 / 48 9,83 / 41 14, 06/63 11,86 / 57 10,49 / 47 ductility% /% of soil value 0 25 50 100 974/100 1144/117 988/101 908/93 1064/100 1024/96 896/84 566/53 1115/100 1024 / 91 716/64 770/69 Example 4

A 0.2 mm solvent-free thermoreactive blend composed of 100 parts by weight of prepolymer prepared by polyaddition reaction of 14.9 parts by weight of toluene diisocyanate and 85.1 parts by weight of polyether glycol based on segmented polymer polyethylene oxide and propylene oxide with oxypropylene ending chains of medium molecular weight was applied to the release paper. the polyaddition reaction was carried out at 80 ° C for 6 hours 229 2.6 parts by weight of ethylenediamine carbamate, 3.5 parts by weight of aminoethylethanolamine carbamate, 30 parts by weight of finely divided calcium carbonate, 15 parts by weight of the colored batch.

After curing of the deposited layer at 125 ° C for 5 minutes, a porous film was obtained with water vapor sorption of% wt%; the resulting ratio of reactants corresponded to the molar ratio of functional groups, OH 1 NCO 3 NH 3, which was 1,2,5,5O 10,98.

Claims (1)

DETAILED DESCRIPTION OF THE INVENTION Hydrophilic polyurethane ureas with enhanced resistance to hydrolytic degradation, particularly suitable for the preparation of hydrophilic sheet materials, the ready-to-use polyadditional, aromatic and / or alicyclic diisocyanate polyol component of ethylene oxide and propylene oxide segmented ethylene oxide 15% by weight of polyethoxamer in the molecule and preferably has a molecular weight of 400-3000, followed by reaction of the obtained prepolymer with diamines, in a solvent with a preferred hydrazine, the reactant ratio corresponding to the molar ratio of functional groups 0H: NG0 : NH2 in ranges1: 1,4 - 2, 2: 0,9-2, 2e Morav Printed Moravské tiskařské závody, provoz 12, Leninova 21, Olomouc Price: 2,40 Kčs