CS210574B1 - The production of hydrophilic and / or hydrophilized macromolecular materials - Google Patents

Abstract

Hydrophilic and/or hydrophilized macromolecular materials based on polyurethanes, polyether and/or polyester prepolymers are produced in the presence of modifiers and possibly processing aids by adding polyethylene glycol with a molecular weight of 200 to 6000 and/or an alkali-soluble cellulose derivative (hydroxyethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose) in an amount of 1 to 50% by weight to these starting materials, containing at least one of the functional groups -NCO, -NH2, -NH, -OH, -COOH in the molecule. They are reacted at high temperatures (40 to 200°C), usually by grinding, and optionally an aliphatic (1,6-hexamethylene diisocyanate) or aromatic diisocyanate is added. (4,4'-diphenylmethane diisocyanate, toluene diisocyanate) and then after at least 70% of the isocyanate groups have reacted, the resulting material is further treated or processed into a final product.

Description

1 210 574

The present invention relates to the production of hydrophilic and / or hydrophilized materials to the base-grade materials of various raw materials and intermediates, and optionally to modified natural polymers, wherein the epoxy allows to control the degree of hydrophilicity of the final material and to be able to be converted into conventional production equipment.

It is known (fran. 2 250 793) that hydrophobic substrates are immersed in a hydrophobic substrate in a solution of a hydrophilic monomer as a result of polymerization or copolymerization of a hydrophilic monomer inside a bydrophobic substrate, as well as by contacting polymers and monomers with the aid of sensitizers and irradiated (NSR Pat. 2 625 389) or iododobenzoate by hydrophilization in an electroplating bath (auto-certificated USSR 524 820). Further, the preparation of the hydrophilic spongy polymer obscures the acrylic trii by dissolving the polymer in nitric acid (U.S. Pat. No. 4,021,382). However, hydrophilic membranes are suitable, for example, for the transport of sodium chloride and water, prepared by copolymerization of bydrophobic and hydrophilic monomer (Kopeček J., Vaoik J.Colleot.). Czeeb. Chem. Commun. 38, 854 (1973)], as well as a hydrophilic polyvinylloblor prepared by a copper-orange copolymerization with N-vinylpyrrolidone in a solution of cycloexanone (Rakitjanskij V., ZarubeUko R.M., Nauc.). Tr. Mosk. Teohnol. Inst. Lecbk. Further, hydrophilic materials with a three-dimensional cell structure are prepared by reacting a mixture consisting of a prepolymer with cono isocyanate groups, polyisocyanates and water (U.S. Pat. No. 4,137,200). However, these variants of the blend also have a relatively narrow application, and the last ei, on the one hand, asks for the exact dosing of the individual components and can also lead to premature cross-linking of the materials. The advantages of many of the known hydrophilic and hydrophilized materials retain other new features to obtain the epoch of the present invention.

According to the present invention and the process for the preparation of the hydrophilic and / or hydrophilicized polyurethane-based macromolecular materials, in particular polyurethane ureas, polyether alcohols or polyester polymers, it performs in a manner which is hydrophobic to the starting material. - Polyethane glycol having an average molecular weight of 200 to 6,000 and / or an alkali-soluble derivative is added to the polyurethane and / or prepolymer containing in the molecule and / or in the macromolecule and at least one of the functional groups -NCO, -NH2, NH, -OH, -COQH. % cellulose, in an amount of 1 to 50 wt. 0.2% to 20% by weight of polyurethane and / or prepolymer, by which it homogenizes and is allowed to react, optionally assisted by gelatinization. the aliphatic and / or aromatic of the diisocyanate or diisocyanate mixtures with stirring, at a temperature of 40 to 200 ° C, wherein after the reaction of at least 70% of the isocyanate groups, the formed hydrophilic and / or hydrophilized material is further processed or processed into the final product. An advantage of the process of the present invention, which can be used to produce hydrophilic and / or hydrophilic macromolecular materials with a wide range of physico-melanocysts, chemical and utility properties, is the availability of hydrophilic components, based on petrochemical or natural raw materials, on the other hand, the possibility of regulating and maintaining sufficient stability of the hydrophilic properties. This is related to the fact that the paro-bound hydrophilizing components are virtually non-extractive. In this way, the materials will not only contain hydrophilicity but also the stability of the manganese oxides. One advantage is the relatively high thermal stability of the hydrophilic poorly hydrophilic, so formed, in the eye, and the possibility of a final finish depending on the application.

External modifiers, comonomers, ethereal catalysts, ester blends and copolymers, fillers, salts, metallic and non-metallic powders, pigments, dyes, blowing agents, homopolymer powders and copolymers, e.g. copolymers, antistatic and antipyranes In the case of polyethylene glycols, respectively. polyetoxamers, it is necessary to make sure that they do not contain remarkable blends of your admixtures of bases and water. Most preferred are the water-soluble cellulose derivatives, most preferably in powder form.

Suitable aliphatic and / or aromatic diisocyanates are 4,4'-diphenylmethanedisocyanate (MDl), toluene diisocyanate (TDl), e.g. 2,4-isomer or a mixture of isomers, 1,6-hexamethylenediisocyanate (HD1), 1,5 naphthylene diisocyanate (ND1), 3,3 ' -dimethoxy-4,4 ' -biphenyldisocyanate, 3,3 ' -dimethyl-4,4 ' -biphenylenediisocyanate, and the like.

By treating the formed hydrophilic and / or hydrophilized material, it is to be understood, for example, by the addition of other modifiers and processing agents, optionally with the use of residual -NCO groups to form -NHg groups, admixing other polymers, forming, lacquering and the like. Further details and advantages of the method of the invention are apparent from the examples. Example 1

Pre-polymer containing 1.8 wt. The crude -NCO groups were obtained by reacting 200 g of polyethylene glycol adipate and 37.5 g of 4,4 ' -diphenylmethane diisocyanate (HD1) were stirred under nitrogen at 95 ° C for 20 min. The prepolymer prepared in this way was introduced at 500% water and contained 0.01 wt. dispersant (methylhydroxypropyloellulose), heated to 70 ° C. While stirring with a propeller stirrer (1500 rpm) for 5 minutes, the polymeric polyurethane salt in the form of a white powder precipitates out of the reaction medium, which is washed with distilled water and dried at 60 ° C with stirring pressure.

When reacting the prepolymer with water, there is not only the reactivity of -NCO groups and water to form NH 3 groups and carbon dioxide, but also the reactivity of the prepolymers of the molecules in the ampoule of macromolecules. The prepared polyurethane resin contains 94 wt. the proportion with a grain size below 0.4 mm (the distribution can be varied by the intensity of mixing, by the amount and type of dispersant and partly by the ratio of the prepolymer amount of 3 210 574 to water and by the dispersant). Polyurethane urea has a bulk density of 660 kg · m · 5, the relative viscosity of the dimethylformamide solution to kono. 1 wt%, 2.355, equilibrium torque of 1.8 Nm and plasticization temperature of 156-160 ° C. By GPC, the molar mass is 120,000, the polyaddition degree is about 25, and the content of -NH2 * hopia is 0.003% by weight.

Then, on the one hand, from a prepolymer containing 1.8 wt. free -NCO groups (prepared by polyoxyethylene glycosylate with 4,4 ' -difonylmethanediisocyanate) and water soluble precipitated hydroxyethyl cellulose by plasticization at 150-160 [deg.] C. for 5 min and, on the other hand, polyurethane urea and hydroxyethyl cellulose by plasticization on a dual calender at 165 [deg.] C. by combining montan wax as a lubricant, hydrophilic macromolecular foil materials are prepared. In the first case, 10 wt. 1.25 wt. parts of water-soluble hydroxyethyl cellulose and 0.12 wt. parts of montan wax. In the second case, 10 wt. of the polyurethane urea adds 1.25 wt. parts of water-soluble hydroxyethyl cellulose and 0.12 wt. parts of montan wax. Hydrophilic materials are obtained. While the first foliage has a water absorption of 15.5% by weight. and this after decade attempt to dhoxtrakoie and soak up with water drops to 14.3% by weight. and extracted from the sheet with 1.1% by weight, apparently hydroxyethyl cellulose, the second sheet initially absorbs 24% by weight of water, but decreases to 17.0% by weight over a decade of extracorporeal water. and extracting from the foil up to 16 wt. material. This is apparently due to the name of the hydroxyethyl cellulose polyurethane urea, while in the first case the free -NCO groups of the prepolymer are also consumed for the diffusion of hydroxyethyl cellulose. Example 2

The polyurethane urea prepared according to Example 1 is used for the preparation of hydrophilic materials using powdered water-soluble hydroxyethyl cellulose, 4,4'-diphenylmethane diisocyanate as a partial " ampoule " ° C "Order of delivery of individual components: polyurethane urea with lubricant (montan wax), after 3 min of homogenization and reactivity to the oil, hydroxy-ethyl cellulose is added and 4,4'-diphenylmethane diisocyanate (MDI) is added for a further 2-4 minutes. After adding MDIsa finished foil they download in rdznyoh time intervalooh.

The components and the individual components of the hydrophilic materials to be prepared, the absorbency of the water immersed in water at a temperature of 1 to 3 h and the drying of the foil surface, as well as the extensibility, i.e. loss, of the first, second, sixth and tenth dip in the water tab. 4 210 374

Table 1

Wt. parts of the dispensed components Reaction time-Absorption * foil with water for single-layer wastes hydrophilic foilextraction in% after single- Mon- Syd- MDI oie chewing-up wetting-re-tantanethane wax roxy- ethyl - oel - addition of MDI urea to blame film removal (min) 1 2 6 8 9 10 1 2 6 8 9 10 10 0,12 1,25 0,00 - 15,3 16,0 7, 3 3,5 2,4 1,3 3,4 5,2 6,5 6,8 7,3 7,5 10 0,075 1,25 0,25 2 11,3 9,2 12,5 10,1 7,9 7.1 1.5 2.4 2.7 2.7 2.8 2.9 10 0.12 3.75 1.25 2 25.8 23.0 25.3 22.1 21.1 21.0 1.8 2.1 3.4 3.5 3.7 3.7 10 0.15 2.50 0.50 2 16.6 18.3 11.7 11.5 10.2 7.1 2.6 2.9 3.7 3.9 3.9 4.2 10 0.15 2.50 0.50 3 10.3 9.9 9.9 8.9 8.8 8.0 0.9 1.5 1.7 1.7 1.9 2.7 10 0.15 2.50 0.50 6 9.2 14.7 16.2 15.0 13.7 12.7 2.0 2.6 3.2 3.4 3.6 3.9 10 0.15 2.50 1.00 2 19.7 19.3 12.4 12.4 12.2 13.0 1.2 1.7 2.3 2.4 2.4 2.5 10 0.15 3.75 1.25 1 22.9 19.2 18.0 16.5 14.6 14.2 1.2 1.4 1.9 2.0 2.1 2.1 10 0.15 3.75 1.25 3 23.0 21.4 23.5 23.0 22.5 21.2 3.4 2.8 3.3 4.0 4.3 4.4 10 0.15 5.0 0.60 3 66.0 69.7 10.9 10.6 9.8 9.2 5.2 9.9 10.9 10.9 12.0 12 Example 3

At 90 [deg.] C. and 50 g of polyethylene glycol with an annular molecular weight of 625, 50 g of 4,4 ' -diphenylmethane diisocyanate (melting point 38 [deg.] C., NCO content 33.6% by weight) are reacted for 30 hours. min · Then 251.5 g of polyetherpolyolol of average molecular weight 3050 (hydroxyl number = 55.32 mg KOH / gj acid with 0.053 mg KOH / g) peroxides with 15.64 ppmj viscosity = 482.51 mPa.s) are added and The reaction mixture was allowed to react for 8 hours and a whiteish white polymer was obtained. 50 g of this are taken from this, 0.5 g of montene wax is added and after 3 minutes gelatinised and mixed with a two-calender calender at 150 ° C and folios are prepared (sample no. I). In the iaalomaa, it prepares folios similar to the foregoing, but leaves in the saline for 5 min and compresses at a temperature of 150 ° C thick folios (sample # 2). In the third case, however, 50 g of the elastic polymer adds 0.5 β of montan wax and plaatizes aa on a dual calender for 3 min at 150 ° C. Thereafter, 1 g of MDI is added, but after 3 min aafolium is not removed from the calenders, so 50 g of the elastic aafolia polymer are prepared by pressing after adding Salami. Thereafter, portions of the films are used as samples for hydrophilic, reap. water absorption, as well as extrakoia. So after 10 soaking up foil

Claims (2)

5,210,574 in water at the temperature (each soaking for 2 to 3 h) is based on the folios of the sample. 1 absorb 8.6 wt. water, while the losses of the mass of the foil reach only 0.3 during the 10 measurements of the sample. 2 water absorption is 10.8% by weight. and losses of only $ 0.18 and δ in the case of pressed film. The 3 water absorbance reaches-$ 6.3 and the hydrophilic material loss is only $ 0.006. Example 4 To a prepolymer specified in Example 1 containing 1.8 wt. -NCO groups are per 10 wt. 0.15 wt. wax of montan wax, 1 wt. part of water-soluble hydroxyethyl cellulose, 0.5 wt. Of 6-weight polyethylene glycol of average molecular weight of 625 and 0.3 wt. powdered methylhydroxypropylcellulose. The mixture is treated at 165 ° C on a two-bed calender for 3 min and then 0.2 parts by weight of 1,6-hexamethylenediisocyanate is added and the foil is removed for a further 3 min. This has a hydrophilicity expressed as water absorption of 16-20 a and a loss, i.e. the extraction of water-soluble parts of unbound hydrophilic material components during 10 soaks reaches 1.2.. EXAMPLE 5 A prepolymer having a content of 4 wt. -NCO groups by not reacting 250 g of poly (ethylene glycol butylene glycol) adipate with 70.2 g of 4,4'-diphenylmethane diisocyanate (Desmodur 44) at 80 ° C in an inert (nitrogen) atmosphere with stirring over time 30 min. From the liquid viscous prepolymer thus prepared, 10 parts by weight are added to which 1.25% by weight are added. hydroxyethyloellulose. Hydroxyethyloellulose is generally homogenized with the prepolymer to form a paste. After the pre-addition of 0.1 part by weight of montan wax as a lubricant on the twin roll, a paste is then applied, the aanee being run at 170 ° C for 5 min. The reaction mixture is then pressed into a coarse-grained powder at 180 ° C for a further 5 minutes. The folios obtained are first washed with gasoline, with the lubricant removed, the mixture can be dried to constant weight. It is then soaked in distilled water at 30 DEG C. for 1 hour, then freed from surface moisture, then weighed and re-immersed in warm water at 84 DEG C. for a further 30 minutes. The water absorption of the film reaches 13% by weight, while the losses of the film extraction are only 1.04%. A process for the preparation of hydrophilic and / or hydrophilized macromolecular materials based on polyurethanes, in particular polyurethane ureas, polyether and / or polyester prepolymers, generally with the aid of modifiers and processors, characterized in that they are generally hydrophobic polyurethane and / or - 6 210 574 too prepolymers containing in the molecule * and / or in the macromolecule at least one of the functional groups -NCO, the polyethylene glycol having an average molecular weight of 200 to 6,000 and / or the alkali-soluble cellulose derivative in the amount of * 1 to 50 ounces. to the starting polyurethane and / or the prepolymers with which it is homogenized and non-reactive, optionally assisted by gelatinization, preferably 0.2 to 20% by weight are added. an aliphatic and / or aromatic diisocyanate or a mixture of dicyanicates under stirring, at a temperature of 40 to 200 ° C, after the reaction of at least 70% of the isocyanate groups, the hydrophilic and / or hydrophilized material formed is treated or processed into the final product. 2. Process according to claim 1, characterized in that the alkali-soluble cellulose derivative, preferably the water-soluble cellulose derivative, is a hydroxyalkylo-cellulose having a carbon number of 2 to 4, preferably hydroxyethyl-cellulose, carboxymethyl-cellulose and methyl-hydroxypropyl cellulose. Printed by Moravské tiskařské závody, provoz 12, Leninova 15, Olomouc Price: 2,40 Kčs