RU2554882C1 - Highly concentrated water nano-size pu-dispersion, which does not contain solvent, method of its obtaining and application - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: described is method of obtaining highly concentrated water nano-size polyurethane dispersion, which does not contain organic solvent, with concentration of basic substance 30-60%, which represents product of interaction of: A) at least, one polyisocyanate, which contains, at least, two isocyanate groups; B) one or several polyols with molecular weight (MW) from 1000 to 18000, which have, at least, two hydroxyl groups; C) one or several compounds, at least, with two OH-functional groups, which contain, at least, one carboxyl group, which can be transformed fully or partially into carboxyl group in presence of bases; D) possibly one or several polyols and/or glycidyl ethers of polyols with average molecular weight less than 500, which contain 2 or more hydroxyl and/or epoxy groups; E) one or several tertiary amines; F) one or several polyamines, which contain at least one NH-group. Components (A), (B) and (C) are subjected to simultaneous interaction to degree of conversion of isocyanate groups 70-98%, if necessary component (D) is introduced into reaction mass, with the following complete or partial neutralisation of carboxyl groups of component (C) with component (E), dispersion in water, introduction of component (F); dispersion is heated and exposed at temperature from 20 to 90°C for from one to four hours. Also described are highly concentrated water nano-size polyurethane dispersion, obtained by claimed method, and its application for obtaining coatings for different substrates, especially flexible substrates, hermetics and glues.EFFECT: obtaining coatings with high physical-mechanical properties, such as elasticity, durability, high water resistance.18 cl, 14 ex, 15 tbl

Description

The present invention relates to a new highly concentrated aqueous nanoscale polyurethane dispersion (PUD) that does not contain organic solvents, which allows to obtain coatings for various, especially flexible, substrates, sealants and adhesives with high physical and mechanical properties and water resistance. The invention also describes an improved method for producing nanoscale PUD.

The use of polyurethanes (PU) in the form of aqueous dispersions can significantly improve the environmental safety of materials. Sustained interest in water-dispersion systems is determined by strict legislative standards adopted in the USA and Europe regarding the regulation of the content of volatile organic solvents in the formulations of paints, adhesives, sealants. In this regard, over the past two decades, work has been carried out to create PUD formulations that do not contain organic solvents, the so-called "solvent-free" dispersions.

Currently, the quality of coatings obtained from aqueous PUDs is not inferior, and in some cases, exceeds organo-diluted analogues. High consumer characteristics of water-based coatings allowed them to penetrate into areas previously inaccessible to them, for example, such as corrosion-resistant coatings for the automotive industry.

Aqueous PUD is a stable colloidal system. Water acts as a dispersion medium in such a system, and polyurethane urea acts as a dispersed phase. To stabilize the dispersion of polyurethane ureas in water at the stage of prepolymer synthesis, hydrophilic groups of both ionic (anionic or cationic) and nonionic types are introduced into the polymer chain.

Methods for producing aqueous PUDs are widely represented in the literature, for example, in a review article on the latest advances in PUD synthesis: Samy A. Madbouly, Joshua U. Otaigbe // Recent advances in synthesis, characterization and rheological properties of polyurethanes and POSS / polyurethane nanocomposites dispersions and films. Progress in Polymer Science. 2009. V. 34 P. 1283-1332. The literature describes mainly two methods for the synthesis of PUD, namely: prepolymer and acetone. In these methods, the dispersion is obtained in two stages: in the first stage, the polyurethane prepolymer is synthesized by the reaction of polyisocyanates with polyols, in the second stage, the prepolymer is dispersed in water, followed by its extension by polyamines in the aqueous phase. However, both methods have one common drawback: the need to introduce a significant amount of solvent in the synthesis of the prepolymer to reduce its viscosity. The prepolymer process uses high boiling solvents such as N-methylpyrrolidone and dimethylformamide (in an amount up to 30 wt.%), Which remain in the final product. The acetone process uses low boiling solvents such as acetone or methyl ethyl ketone, which are removed from the final product by distillation under reduced pressure. This method allows you to widely vary the raw materials components, but the presence of an energy-intensive stage of distillation of large quantities of solvent, as well as its regeneration leads to a significant increase in the cost of the process.

Therefore, the task of obtaining PUD, without the use of a solvent in the synthesis at the stage of preparing the prepolymer, is very important.

US Pat. No. 5,270,433 claims a method for manufacturing an aqueous solvent-free PUD that can be used as a multi-purpose household adhesive. Preferably, polyoxypropylene glycols with a molecular weight of 200 to 5000 g / mol (particularly preferably 300 to 3000 g / mol) or mixtures thereof with polyesters or polyfurite are preferably used as a polyol component, and meta-tetramethylxylene diisocyanate (TXMDI) as a polyisocyanate component or a mixture thereof with other polyisocyanates is possible. The authors emphasize that in order to achieve acceptable adhesion values of PUs to various substrates (more specifically to plastic), TXMDI must be used as the main polyisocyanate component in the formulation. It should be noted that in the above examples, PUDs with a low concentration (30-35%) and with very high viscosity (3000-3500 mPa · s). Dispersions with this viscosity can only be used for specific purposes.

US Pat. No. 5,972,158 also describes a method for producing solvent-free PUDs for a narrow field of application, namely, as a primer for gluing PVC window profiles to plastic. The claimed primer is a two-component. Self-emulsifying diisocyanate is used as the second component. PUDs are synthesized based on a mixture of polyesters (in the examples with MM 2000), dimethylolpropionic acid (DMPC) and meta-tetramethylxylene diisocyanate (TXMDI). After dispersing the prepolymer in water, it is not chain extension, but chain termination by reaction of NCO groups with alkanolamines.

US Pat. No. 6,515,070 describes a process for the manufacture of solvent-free PUDs used as hot melt adhesives with a low activation temperature. The dispersion is prepared on the basis of polyesters and metatetramethylsilylene diisocyanate. The authors indicate that the use of this non-self-associating polyisocyanate allows to obtain PUD without the use of a solvent. In the examples presented in the patent, PUDs have a low concentration, mainly 29-30%.

US Pat. No. 8,058,343 discloses a method for manufacturing PUD for thermally activated adhesives. This dispersion is recommended as an adhesive or coating for flexible substrates, including stretch fabrics. As the polyol as one raw material, a polyester with an MM from 600 to 3500 g / mol (most preferably a polyester or polyfurite with an MM of about 2000 g / mol) is used, and an aromatic diisocyanate (metaphenylene diisocyanate with an isomer ratio of 4.4 and 2.4 is used as an isocyanate component) about 65:35), as a built-in stabilizer - DMPC. The prepolymer with a low content of DMPC (2.5-3%) is synthesized without the use of a solvent, but an external emulsifier, sulfanol, is additionally introduced at the dispersion stage.

The closest technical solution is the method claimed in US Pat. No. 6,635,723. The patent describes a method for producing solvent-free PUD with a high content of 40 to 70% of the main substance, including polyurethane or polyurethane ureas, as well as fillers. The PUD obtained by the patent is recommended to be used in the construction sector as various coatings, sealing and adhesive materials. According to the patent, PUDs are synthesized using the following steps: first, a prepolymer is obtained from polyols and polyisocyanates, it is neutralized, and then the neutralized prepolymer is dispersed in water with simultaneous extension or chain termination. During the synthesis, excipients can be introduced into the PUD: both directly into the prepolymer, and into water before dispersion. A variant is possible when the stage of neutralization is carried out simultaneously with dispersion. High molecular weight (MM 500-6000 Da) simple and complex polyesters, polyfurites, polycarbonates, optionally low molecular weight polyols (MM 60-150 Da), as well as low molecular weight polyols containing at least one carboxyl group are used as polyol components. More preferably, polyoxypropylene glycols with MM 3000-4000 and DMPK (dimethylolpropionic acid) are used as the internal dispersion stabilizer. Aromatic or aliphatic polyisocyanates are used as the isocyanate component. Isocyanates with different reactivity of isocyanate groups, for example, isophorondiisocyanate, are preferably used. The prepolymer according to the patent is obtained with a high isocyanate index, 1.8-2.2 is most preferred. According to the patent, prepolymer synthesis is carried out strictly in two stages: first, the high molecular weight polyol is reacted with the polyisocyanate, then DMPC is added and the synthesis is continued until the calculated mass fraction of NCO groups is reached. DMSA is metered in the form of finely ground powder for several minutes to several hours. The authors argue that as a result of this method of synthesizing a prepolymer, the latter has a narrow molecular weight distribution and an ordered structure, which allows one to obtain prepolymers with a low viscosity, easily dispersible in water. As a result, highly concentrated stable dispersions of polyurethane ureas of "ideally segmented structure" with a particle size of 200-400 nm and a sufficiently high viscosity of up to 800 MPa · s are obtained. In the description, it is noted that the dispersion of the prepolymer is carried out only after reaching the calculated value of the mass fraction of NCO groups (which is confirmed in the examples).

Obtaining a prepolymer using a polyester with an MM of more than 3000 is mentioned in Examples 2, 14, 15, 17. Examples 14, 15, 17 are carried out under the conditions of the prepolymer preparation method of Example 2. According to this example, only 10% of the mass is added to the polyester with MM 3000. , polyoxypropylene diol with MM 4000. Perhaps this is due to the fact that an increase in MM of polyoxypropylene glycols leads to an increase in the viscosity of the prepolymer. It should also be noted the rather low strength characteristics of the films obtained from PUD according to the patent: for a dispersion based on PPG with MM 3000, the breaking strength is only 12.2 MPa, based on a mixture of PPG with MM 3000 and 4000 (the content of PPG with MM 4000 is about 10 mass .%) - 12.1 MPa, on the basis of BCP with MM 2000 - 23.6 MPa, on the basis of BCP with MM 1000 - 40.8 MPa. Water absorption - not indicated in the patent.

The objective of the invention is to develop a method for producing a new highly concentrated aqueous nanoscale PUD that does not contain organic solvents, which allows you to adjust the viscosity of the prepolymer and the composition of PU. New PUDs allow to obtain coatings for various substrates, especially flexible substrates; sealants and adhesives with high water resistance and exceptional physical and mechanical properties such as strength and elasticity. The use of a highly concentrated aqueous nanoscale PUD of the specified composition obtained by the method according to the present invention allows to obtain coatings with significantly improved properties. Improving the properties of coatings, sealants and adhesives do not follow from the prior art and are not obvious to a specialist.

The problem is achieved by the method of obtaining an aqueous nanoscale polyurethane dispersion (PUD), not containing an organic solvent, with a concentration of the main substance of 30-60%, which is a product of the interaction:

A) at least one polyisocyanate containing at least two isocyanate groups;

B) one or more polyols with a molecular weight (MM) of from 1000 to 18000 having at least two hydroxyl groups;

C) one or more compounds with at least two OH-functional groups which contain at least one carboxyl group, which can be converted completely or partially into a carboxylate group in the presence of bases;

D) possibly one or more polyols and / or glycidyl ethers of polyols with an average molecular weight of less than 500, containing 2 or more hydroxyl and / or epoxy groups;

E) one or more tertiary amines;

F) one or more polyamines containing at least one NH ₂ group.

The method consists in reacting components (A), (B) and (C) at the same time to a degree of conversion of isocyanate groups of 70-98%, optionally introducing component (D) into the reaction mass, then completely or partially neutralizing the carboxyl groups of the component (C) component (E), dispersed in water, introduced component (F), heat the dispersion and incubated at a temperature of from 20 to 90 ° C for one to four hours.

The resulting aqueous nanoscale polyurethane dispersion has a ratio of isocyanate groups of component (A) to hydroxyl groups of components (B) and (C) (isocyanate index) in the range from 1.8 to 8.0, while the ratio of isocyanate groups of component (A) to hydroxyl groups of components (B), (C) and (D) is in the range from 1.8 to 2.4.

A distinctive feature of the proposed method from a previously known close analogue is the reaction of three components (B), (C) at once (as a mixture) with component (A), until the conversion of isocyanate groups of 70-98% is reached. Usually, this step is carried out at a temperature of 50 -100 ° C without or with catalyst. The difference is also a certain sequence of stages: introducing, if necessary, component (D), directly or completely neutralizing the carboxyl groups in the prepolymer using component (E), dispersing the prepolymer in water, introducing component (F) and maintaining the dispersion at 20-90 ° C for one to four hours.

In the obtained nanoscale dispersion, the proportion of polyurethane particles with a size <100 nm is 70-100%. Preferably, the prepolymer is synthesized to a conversion of isocyanate groups of 80-98%.

As component (B), low unsaturation polyoxyalkylene polyols obtained with a DMC catalyst are preferably used. Most preferably, polyoxyalkylene polyols with MM 1000-12000 are used as component (B). Component (D) is introduced immediately before neutralization. Immediately prior to dispersion, neutralization of 70-100 equiv.% Of the carboxyl groups of component (C) by component (E) is carried out, preferably at a temperature of from 50 to 80 ° C. The most preferred component (E) is triethylamine. After dispersion, component (F) is usually added in an amount of 60-100 equivalent% of the isocyanate groups of the prepolymer. A preferred component (F) is a bifunctional primary amine. After feeding component (F), the dispersion is stirred at a temperature of 50-80 ° C for one to four hours. The process can be carried out in the presence of a catalyst.

The object of the present invention is also a new highly concentrated aqueous nanoscale polyurethane dispersion (PUD), not containing an organic solvent, with a concentration of the main substance of 30-60%, which is the product of the interaction:

A) at least one polyisocyanate containing at least two isocyanate groups;

B) one or more low unsaturation polyols obtained with a DMC catalyst, with an average molecular weight (MM) of from 1000 to 18000, having at least two hydroxyl groups;

C) one or more compounds with at least two OH-functional groups which contain at least one carboxyl group, which can be converted completely or partially into a carboxylate group in the presence of bases;

D) possibly one or more polyols and / or glycidyl ethers of polyols with an average molecular weight of less than 500, containing 2 or more hydroxyl and / or epoxy groups;

(E) one or more tertiary amines;

(F) one or more polyamines containing at least one NH ₂ group.

The ratio of the isocyanate groups of component (A) to the hydroxyl groups of components (B) and (C) (isocyanate index) is in the range from 1.8 to 8.0, and the ratio of the isocyanate groups of component (A) to the hydroxyl groups of components (B ), (C) and (D) is in the range of 1.8 to 2.4.

The highly concentrated nanoscale PUD obtained according to the invention contains component A in an amount of 5-60%, preferably 10-45%, most preferably 15-35%; component B 5-90%, preferably 10-85%, most preferably 15-80%, component C 0.5-15%, preferably 1-12% and particularly preferably 2-10%, component D 0-10%, preferably 0-8% and particularly preferably 0-6%, component E 1-8%, preferably 1.5-6 and particularly preferably 2-4%, as well as component F 0.5-10%, preferably 1-8% and particularly preferably 2-6%, all of these percentages are by weight and refer to the total content of the basic substance (polyurethane contained in the dispersion), in the amount of 100.

In the present invention, the obtained nanoscale highly concentrated PUD, with the declared content of the internal emulsifier (component (C)), have a fairly narrow particle size distribution, the main proportion of the dispersion particles has a size of less than 100 nm, preferably less than 80 nm and particularly preferably less than 60 nm. The main proportion of particles is 70-100% of the total number of particles. Nanoscale particles in the resulting PUDs provide the formation of more durable films and expand their field of application.

As component (A), any aromatic and / or aliphatic polyisocyanate having two or more isocyanate groups can be used. Suitable are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, metaphenylene diisocyanate, 1-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophorondiisocyanate), 1,6-diisocyanatohexane, meta-tetramethylxilylene diisocyanate, hexamethylene diisocyanate. Isophorondiisocyanate is particularly preferred.

As component (B) of the proposed PUD, polyesters (homo- or copolymers) having two (or more) hydroxyl groups with MM from 1000 to 18000 obtained by polymerization of alkylene oxides, for example, ethylene oxide, propylene, butylene, in the presence of a DMC catalyst. Particularly preferred are polyoxyalkylenediols with MM from 1000 to 12000, even more preferably from 2000-8000. Such polyesters have ultra-low unsaturation and, consequently, low defectiveness at the terminal OH groups; due to this, PUs based on them have high MM, which in turn significantly increases its strength properties. The use of polyethers (homo- or copolymers) having two (or more) hydroxyl groups with an MM of more than 12000 (up to 18000) does not impair the properties of the composition when it is used.

LCA (bimetallocyanide) catalysts are known and the method for their preparation is described, for example, in patent RU 2191626.

A suitable component (C) is one or more compounds with at least two OH-functional groups that contain at least one carboxyl group, which can be converted completely or partially into a carboxylate group in the presence of bases. Preferred are 2-hydroxymethyl-3-hydroxypropanoic acid, 2-hydroxymethyl-2-methyl-3-hydroxypropanoic acid, 2-hydroxymethyl-2-ethyl-3-hydroxypropanoic acid, 2-hydroxymethyl-2-propyl-3-hydroxypropanoic acid. Particularly preferred is 2-hydroxymethyl-2-methyl-3-hydroxypropanoic acid (dimethylolpropionic acid).

As component (D), polyols and / or glycidyl ethers of polyols with an MM of less than 500, such as ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol; ether-bond diols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols, polypropylene glycols or polybutylene glycols, trimethylolpropane, glycerol; and their glycidyl ethers, for example, trimethylolpropane triglycidyl ether and 1,4-butanediol diglycidyl ether. Particularly preferred are 1,4-butanediol, neopentyl glycol, trimethylol propane, 1,2-propanediol, trimethylol propane triglycidyl ether.

Suitable components (E) are organic bases and / or alkaline inorganic compounds or mixtures of these substances. Tertiary amines such as triethylamine, triisopropylamine, N-methylmorpholine, N-ethylmorpholine are preferred, triethylamine is particularly preferred.

As component (F), any polyamine having amino groups reactive with isocyanate groups can be used. Preferred are hydrazine, ethylenediamine, 1,4-diaminobutane, isophorondiamine, 4,4′-diaminodicyclohexylmethane, 1,2-diamino-cyclohexane, 2-methyl-1,5-diaminopentane, diethylene triamine, triethylenetetramine and N-methyldiethanolamine.

In accordance with this invention, to carry out the dispersion step and obtain a stable dispersion, it is sufficient to synthesize a homogeneous prepolymer. Homogenization of the reaction mixture occurs when the degree of conversion of NCO groups is above 60%. Dispersion is carried out at a degree of conversion of the NCO groups of the prepolymer above 70%, preferably above 80%. It is necessary that the degree of conversion does not exceed 98%, because then there is an intensive increase in the viscosity of the prepolymer.

The neutralization of the carboxyl groups of component (C) by component (E) can be carried out by direct or inverse methods to a degree of neutralization of 70-100 equiv.%, Preferably 90-100 equiv.%. It is preferable to carry out the process of direct neutralization, in which case it is carried out at a temperature of 50-80 ° C, preferably 60-80 ° C, particularly preferably 70-80 ° C. In the case of reverse neutralization, component (E) is added to water and neutralization is carried out simultaneously with dispersion.

At the dispersion stage, the neutralized prepolymer is supplied to water, or water is supplied to the neutralized prepolymer with vigorous stirring, forming a stable dispersion. The aqueous medium at this stage has a temperature of not higher than 60 ° C, preferably not higher than 45 ° C, particularly preferably not higher than 30 ° C.

The viscosity of PU prepolymers increases rapidly at high degrees of conversion (more than 98%). At lower degrees of conversion, a noticeable amount of free polyisocyanate is present in the reaction mixture. On the one hand, free polyisocyanate, acting as a solvent, significantly reduces the viscosity of the prepolymer, on the other hand, it is known from the literature that the presence of free polyisocyanate impairs the properties of PUDs, leading to the formation of polyureas unstabilized in water, the formation of which is also accompanied by abundant foaming at the stage of dispersion, greatly complicating this process. The solid polyurea precipitate formed in this case leads to turbidity and other defects in the final coating. It was found that after dispersing the prepolymer obtained according to this invention, a stable dispersion forms in water in which the NCO groups of the prepolymer and free polyisocyanate do not react with water for more than one hour. Obviously, this is due to the special structure of micelles in which NCO groups are “hidden” inside the polyester shell. The discovered property allows the use of high MM polyols as component (B), as well as a variety of extension cords and chain splitters, introducing some of them into the prepolymer at the end of synthesis, before neutralization. These reagents, introduced in this way, not only do not increase the viscosity of the prepolymer, but acting as a diluent, they decrease it, which facilitates the course of dispersion and the formation of a dispersion. After dispersion, the urethane formation reaction continues inside the micelles. In known methods for the synthesis of PUD with the introduction of extenders and splitters in the synthesis of prepolymers, it is necessary to use solvents to reduce its viscosity, which is their significant drawback.

There is no need to obtain a prepolymer in two stages with a sequential dosage of components. It is sufficient to obtain the prepolymer in one step by mixing components A, B and C immediately, however, the prepolymer is synthesized in such a way as to obtain a homogeneous reaction mixture, i.e. to the degree of conversion of NCO groups above 70%. This allows to reduce the total process time and the viscosity of the prepolymer, compared with the prototype.

The synthesis of the prepolymer is possible, both in the presence and in the absence of a catalyst. The amount of catalyst required for the process is in the range of 0.01-1% by weight of the total charge at the prepolymer synthesis stage. Suitable catalysts are tin dibutyl dilaurate (DBDLO), tin octoate, chelating compounds of copper, iron, vanadium and zirconium.

Extenders with amine groups (component (F)), due to their high reactivity, are added to the dispersion after dispersion for several minutes to one hour. After the introduction of component (F), the dispersion is continued to mix at a temperature of from 10 to 90 ° C, preferably at 40-90 ° C, particularly preferably at 50-80 ° C for one to several hours. During this time, the reaction of the functional groups of the extender, splitter and / or breaker with unreacted NCO-groups of the prepolymer inside the micelles, as a result, the dispersed polyurethane has a high MM, which ensures its excellent physicomechanical properties and high water resistance. Exposure to dispersion at high temperatures leads to a more complete reaction inside micelles.

The synthesis of the prepolymer with a high isocyanate index, to a lower conversion of 70-98%, allows you to adjust the viscosity of the prepolymer, and to carry out the urethane formation reaction after dispersion in micelles. This approach allows you to widely vary the composition of PU (use polyesters with high MM, extenders, splitters), their consumer properties.

According to the described method receive nanoscale highly concentrated PUD with a mass fraction of polyurethane (dry residue) of 35-65%, preferably 35-55% and particularly preferably 40-50%.

Proposed in the invention PUD are used as binders for coatings and adhesives, cured by removal of water. Coatings based on them can be applied to any substrates, for example, to metal, paper, leather, textile materials, wood, polymer substrates, glass or mineral substrates, as well as substrates with a coating already applied to them. The most suitable area of application for the described polyurethane dispersions is the coating of textiles, leather and other flexible substrates.

The PUDs proposed in the invention can be used for coating as such or in combination with auxiliary substances or additives known from the technology of paints and varnishes, such as, for example, fillers, pigments, solvents and means for improving the surface wetting.

The application of PUD can be carried out by various known methods, for example, by spreading, pouring, using a doctor blade, by spraying, irrigation (in vacuum), centrifugation, roll method or dipping. The film can be dried at room or elevated temperature.

A specific implementation of the claimed invention is illustrated by the following examples, but does not limit it. Example 1 (BCP 4000).

A three-necked round-bottom flask equipped with a glass stirrer and a thermometer is charged with 223.40 g of polyoxypropylene diol with an MM of 4000 g / mol (Laprol 4002D, Macromer) synthesized with a DMC catalyst, 64.60 g of isophorone diisocyanate (Vestanat IPDI, Evonik), 12 0 g of DMPC (bis-MPA, Perstorp) and carry out synthesis in a nitrogen atmosphere at 75 ° C for 3.5 hours (NCO / OH = 2). When the degree of conversion of the isocyanate groups is 80%, the prepolymer is cooled to 70 ° C and 8.15 g of triethylamine (90 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 2650 MPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 20 ° C in 420 g of distilled water. Immediately after dispersion is complete, 15.7 g of ethylenediamine are added in the form of a 50% aqueous solution (90 equiv.% Of isocyanate groups) over 10 minutes. After the filing of the chain extender is completed, the dispersion is maintained at a temperature of 20 ° C for 2 hours. The ratio of the components to obtain the main substance PUD is as follows: isophorondiisocyanate 20.4%; Laprol 4002D 70.5%; DMPC 3.8%; triethylamine 2.6%; ethylene diamine 2.7%.

Example 2 (BCP 4000).

The synthesis is carried out according to the downloads and the synthesis method of example 1. The synthesis is carried out to a degree of conversion of isocyanate groups of 90%. Get prepolymer with a viscosity of 3040 MPa · s at 70 ° C. After the filing of the chain extender is completed, the dispersion is maintained at a temperature of 20 ° C for 2 hours. The ratio of the components to obtain the main substance PUD is as follows: isophorondiisocyanate 20.4%; Laprol 4002D 70.7%; DMPC 3.8%; triethylamine 2.6%; ethylenediamine 7.85%.

Example 3 (BCP 4000).

The synthesis is carried out according to the downloads and the synthesis method of example 1. The synthesis is carried out to a degree of conversion of isocyanate groups of 98%. Get a prepolymer with a viscosity of 3310 MPa · s at 70 ° C. After the filing of the chain extender is completed, the dispersion is maintained at a temperature of 20 ° C for 2 hours. The ratio of the components to obtain the main substance PUD is as follows: isophorondiisocyanate 20.4%; Laprol 4002D 70.5%; DMPC 3.8%; triethylamine 2.6%; ethylene diamine 2.7%.

Example 4 (comparative, BCP 4000).

In a three-necked round-bottom flask equipped with a glass stirrer and a thermometer, 222.50 g of “traditional” polyoxypropylenediol with an MM of 4000 g / mol (Laprol 4002D, Macromer) synthesized with a KOH catalyst, 65.49 g of isophorondiisocyanate (Vestanat IPDI, Evonik) are charged 12.0 g of DMPC (bis-MPA, Perstorp) and synthesized under nitrogen at 75 ° C for 4.0 hours (NCO / OH = 2). Upon reaching the degree of conversion of the isocyanate groups to 90%, the prepolymer is cooled to 70 ° C and 8.15 g of triethylamine (90 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 2890 MPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 20 ° C in 420 g of distilled water. Immediately after dispersion is completed, 14.7 g of ethylenediamine are added in the form of a 50% aqueous solution (90 equiv.% Of isocyanate groups) over 10 minutes. After the filing of the chain extender is completed, the dispersion is maintained at a temperature of 20 ° C for 2 hours. The ratio of components to obtain the main substance PUD is as follows: isophorondiisocyanate 20.7%; Laprol 4002D 70.4%; DMPC 3.8%; triethylamine 2.6%; ethylene diamine 2.55%.

Example 5 (comparative, BCP 4000).

The synthesis is carried out according to the downloads of example 1, but according to the method of patent US 6 635 723 example 1.

A four-necked round-bottom flask equipped with a glass stirrer, reflux condenser and thermometer is charged with 223.40 g of polyoxypropylenediol with MM 4000 g / mol (Laprol 4002D, Macromer), 64.60 g of isophorondiisocyanate (Vestanat IPDI, Evonik) and nitrogen is synthesized in the atmosphere at 80-90 ° C for 2 hours. Then, 12.0 g of finely dispersed DMPC (bis-MPA, Perstorp) was added to the reaction mixture and stirring was continued at 80-90 ° C under nitrogen until the calculated amount of isocyanate groups was reached (100% conversion, NCO / OH = 2). After the degree of conversion of the isocyanate groups to 100% was reached, the prepolymer was cooled to 50 ° C and 8.15 g of triethylamine (90 equiv.% Carboxyl groups) was added. Get prepolymer with a viscosity of 4080 MPa · s at 70 ° C. Then 280 g of the prepolymer are dispersed in 420 g of distilled water at high stirring speeds. Immediately after dispersion is completed, 13.04 g of ethylenediamine are added in the form of a 50% aqueous solution (90 equiv.% Of isocyanate groups). The ratio of the components to obtain the main substance PUD is as follows: isophorondiisocyanate 20.5%; Laprol 4002D 70.9%; DMPC 3.8%; triethylamine 2.6%; ethylenediamine 2.3%.

Example 6 (a mixture of BCP 2000 and 8000).

156.70 g of polyoxypropylene diol with MM 8000 g / mol (Laprol 8002D, Macromer) and 66.7 g of polyoxypropylene diol with MM 2000 g / mol (Laprol-2002D, Macromer) synthesized are loaded into a three-necked round-bottomed flask equipped with a glass stirrer and a thermometer. with a DMC catalyst; 64.60 g of isophorondiisocyanate (Vestanat IPDI, Evonik), 12.0 g of DMPC (bis-MPA, Perstorp) and synthesized under nitrogen at 75 ° C for 5 hours (NCO / OH = 2). When the degree of conversion of the isocyanate groups is 90%, the prepolymer is cooled to 70 ° C and 8.60 g of triethylamine (95 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 3600 mPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 20 ° C in 420 g of distilled water, and immediately after dispersion is completed, 13.97 g of ethylenediamine are added in the form of a 50% aqueous solution (80 equiv.% Of isocyanate groups) over 10 minutes. After the filing of the chain extender is completed, the dispersion is maintained at a temperature of 20 ° C for 2 hours). The ratio of the components to obtain the main substance PUD is as follows: isophorondiisocyanate 20.5%; Laprol 8002D 49.5%; Laprol 2002 D 21.1; DMPC 3.8%; triethylamine 2.6%; ethylene diamine 2.4%.

Get a storage stable nanoscale dispersion with the following characteristics:

Example 7 (a mixture of BCP 2000 and 12000).

82.19 g of polyoxypropylene diol with MM 12000 g / mol (Laprol 8002D, Macromer) and 139.94 g of polyoxypropylene diol with MM 2000 g / mol (Laprol-2002D, Macromer) synthesized are loaded into a three-necked round-bottom flask equipped with a glass stirrer and a thermometer. with a DMC catalyst; 65.27 g of isophorondiisocyanate (Vestanat IPDI, Evonik), 12.6 g of DMPC (bis-MPA, Perstorp) and synthesized under a nitrogen atmosphere at 75 ° C for 5.5 hours (NCO / OH = 2). When the degree of conversion of the isocyanate groups reaches 90%, the prepolymer is cooled to 70 ° C and 9.05 g of triethylamine (100 eq.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 3790 MPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 20 ° C in 420 g of distilled water and 15.0 g of ethylenediamine in the form of a 50% aqueous solution (85 eq. Of isocyanate groups) are added immediately after dispersion over 10 minutes. After the filing of the chain extender is completed, the dispersion is maintained at a temperature of 20 ° C for 2 hours). The ratio of the components to obtain the main substance PUD is as follows: isophorondiisocyanate 20.6%; Laprol 12002D 25.9%; Laprol 2002 D 44.1; DMPC 4.0%; triethylamine 2.9%; ethylenediamine 2.6%.

Example 8 (BCP 2000)

In a three-necked round-bottom flask equipped with a glass stirrer and a thermometer, 206.32 g of polyoxypropylene diol with an MM of 2000 g / mol (Laprol 2002D, Macromer) synthesized with a DMC catalyst are charged, 82.58 g of isophorone diisocyanate (Vestanat IPDI, Evonik), 11, 1 g of DMPC (bis-MPA, Perstorp) and synthesized in a nitrogen atmosphere at 75 ° C for 3.5 hours (NCO / OH = 2). When the degree of conversion of the isocyanate groups reaches 90%, the prepolymer is cooled to 70 ° C and 7.54 g of triethylamine (90 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 2200 MPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 25 ° C in 420 g of distilled water, and immediately after completion, 21.88 g of ethylenediamine are added in the form of a 50% aqueous solution (98 equiv.% Of isocyanate groups) over 10 minutes. After the filing of the chain extender is completed, the dispersion is maintained at a temperature of 20 ° C for 2 hours). The ratio of components to obtain the main substance PUD is as follows: isophorondiisocyanate 25.8%; Laprol 2002D 64.6%; DMPK 3.5%; triethylamine 2.4%; ethylenediamine 3.8%.

Example 9 (BCP 1000)

180.68 g of polyoxypropylenediol with MM 1000 g / mol (Voranol 1010 L, DOW), 109.42 g of isophorondiisocyanate (Vestanat IPDI, Evonik), 9.9 g of DMPC (bis) are charged into a three-necked round bottom flask equipped with a glass stirrer and a thermometer. -MPA, Perstorp) and carry out synthesis in a nitrogen atmosphere at 75 ° C for 3.0 hours (NCO / OH = 2). When the degree of conversion of the isocyanate groups reaches 90%, the prepolymer is cooled to 70 ° C and 6.72 g of triethylamine (90 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 1520 MPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 25 ° C in 420 g of distilled water, after dispersion is completed, 26.62 g of ethylenediamine are added in the form of a 50% aqueous solution (90 equiv.% Of isocyanate groups) over 10 minutes. After the filing of the chain extender is completed, the dispersion is maintained at a temperature of 20 ° C for 2 hours). The ratio of the components to obtain the main substance PUD is as follows: isophorondiisocyanate 34.1%; Laprol 1002D 56.2%; DMPC 3.1%; triethylamine 2.1%; ethylene diamine 4.5%.

Example 10 (BCP 4000, 1,4-butanediol)

165.13 g of polyoxypropylenediol with MM 4000 g / mol (Laprol 4002D, Macromer) synthesized with a DMC catalyst, 112.37 g of isophorone diisocyanate (Vestanat IPDI, Evonik), 10, are loaded into a three-necked round-bottomed flask equipped with a glass stirrer and a thermometer, 10, 5 g of DMPC (bis-MPA, Perstorp) and synthesized in a nitrogen atmosphere at 75 ° C for 3 hours (NCO / OH = 4.23). When the degree of conversion of isocyanate groups to 90% is reached, 12 g of 1,4-butanediol (ΣNCO / ΣОН = 2) are added to the prepolymer, cooled to 70 ° C and 7.13 g of triethylamine (90 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 2740 MPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 20 ° C in 420 g of distilled water, after which 29.78 g of ethylenediamine are added in the form of a 50% aqueous solution (90 equiv.% Of the calculated amount of isocyanate groups) over 10 minutes. Upon completion of the filing of the chain extender, the dispersion is heated to 85 ° C and maintained at this temperature for 2 hours. The ratio of components to obtain the main substance PUD is as follows: isophorondiisocyanate 34.7%; Laprol 4002D 51.0%; DMPK 3.2%; 1,4-butanediol 3.7%; triethylamine 2.2%; ethylenediamine 5.0%.

Example 11 (comparative, BCP 4000, 1,4-butanediol).

165.13 g of polyoxypropylenediol with MM 4000 g / mol (Laprol 4002D, Macromer) synthesized with a DMC catalyst, 112.37 g of isophorone diisocyanate (Vestanat IPDI, Evonik), 10, are loaded into a three-necked round-bottomed flask equipped with a glass stirrer and a thermometer, 10, 5 g of DMPC (bis-MPA, Perstorp), 12 g of 1,4-butanediol and are synthesized under nitrogen at 75 ° C for 8 hours (NCO / OH = 2). When the degree of conversion of isocyanate groups is reached, 100% of the prepolymer is cooled to 70 ° C and 7.13 g of triethylamine (90 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 4560 MPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 25 ° C in 420 g of distilled water, and after feeding is completed, 29.78 g of ethylenediamine are added in the form of a 50% aqueous solution (90 equiv.% Of the calculated value of the isocyanate groups). Upon completion of the filing of the chain extender, the dispersion is heated to 85 ° C and maintained at this temperature for 2 hours. The ratio of components to obtain the main substance PUD is as follows: isophorondiisocyanate 34.7%; Laprol 4002D 51.0%; DMPK 3.2%; 1,4-butanediol 3.7%; triethylamine 2.2%; ethylenediamine 5.0%.

Example 12 (BCP 4000, glycerin)

160.18 g of polyoxypropylenediol with MM 4000 g / mol (Laprol 4002D, Macromer) synthesized with a DMC catalyst, 119.72 g of isophorone diisocyanate (Vestanat IPDI, Evonik), 11, are loaded into a three-necked round-bottomed flask equipped with a glass stirrer and a thermometer; 1 g of DMPC (bis-MPA, Perstorp) and synthesized in a nitrogen atmosphere at 75 ° C for 3.5 hours (NCO / OH = 4.39). When the degree of conversion of isocyanate groups to 90% is reached, 9 g of glycerol (ΣNCO / ΣОН = 2) is added to the prepolymer, cooled to 70 ° C and 7.13 g of triethylamine (90 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 2820 MPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 20 ° C in 420 g of distilled water, after which 29.78 g of ethylenediamine are added in the form of a 50% aqueous solution (90 equiv.% Of the calculated amount of isocyanate groups) over 10 minutes. Upon completion of the filing of the chain extender, the dispersion is heated to 85 ° C and maintained at this temperature for 2 hours. The ratio of components to obtain the main substance PUD is as follows: isophorondiisocyanate 37.0%; Laprol 4002D 49.5%; DMPC 3.4%; glycerol 2.8; triethylamine 2.2%; ethylenediamine 5.0%.

Example 13 (comparative, BCP 4000, glycerin).

160.18 g of polyoxypropylenediol with MM 4000 g / mol (Laprol 4002D, Macromer) synthesized with a DMC catalyst, 119.72 g of isophorone diisocyanate (Vestanat IPDI, Evonik), 11, are loaded into a three-necked round-bottomed flask equipped with a glass stirrer and a thermometer; 1 g of DMPK (bis-MPA, Perstorp), 9 g of glycerol and synthesized in a nitrogen atmosphere at 75 ° C (NCO / OH = 2). After 2 hours, due to a strong increase in the viscosity of the prepolymer, synthesis was stopped.

Example 14 (BCP 4000, Laproxide TMP)

In a three-necked round-bottom flask equipped with a glass stirrer and a thermometer, 218.42 g of polyoxypropylenediol with an MM of 4000 g / mol (Laprol 4002D, Macromer) synthesized with a DMC catalyst, 59.08 g of isophorone diisocyanate (Vestanat IPDI, Evonik), 10 are charged, 10 5 g of DMPC (bis-MPA, Perstorp) and synthesized in a nitrogen atmosphere at 75 ° C for 3 hours (NCO / OH = 2). When the degree of conversion of isocyanate groups to 90% is reached, 12 g of trimethylolpropane triglycidyl ether (Laproxide TMP, Macromer) are added to the prepolymer, cooled to 70 ° C, and 7.13 g of triethylamine (90 equiv.% Carboxyl groups) are directly neutralized. The viscosity of the prepolymer at 70 ° C is 3100 mPa · s. Then 280 g of the prepolymer are dispersed at high stirring speeds and a temperature of 25 ° C in 420 g of distilled water, and after completion, 18.9 g of ethylenediamine are added in the form of a 50% aqueous solution (90 equiv.% Of the amount of epoxy and the calculated amount of isocyanate groups). Upon completion of the filing of the chain extender, the dispersion is heated to 85 ° C and maintained at this temperature for 3 hours. The ratio of components to obtain the main substance PUD is as follows: isophorondiisocyanate 18.6%; Laprol 4002D 68.8%; DMPK 3.3%; Laproxide TMP 3.8; triethylamine 2.2%; ethylene diamine 3.3%.

Claims (18)

1. A method of obtaining a highly concentrated aqueous nanoscale polyurethane dispersion that does not contain an organic solvent, with a concentration of the main substance of 30-60%, which is the product of the interaction:
A) at least one polyisocyanate containing at least two isocyanate groups;
B) one or more polyols with a molecular weight (MM) of from 1000 to 18000 having at least two hydroxyl groups;
C) one or more compounds with at least two OH-functional groups which contain at least one carboxyl group, which can be converted completely or partially into a carboxylate group in the presence of bases;
D) possibly one or more polyols and / or glycidyl ethers of polyols with an average molecular weight of less than 500, containing 2 or more hydroxyl and / or epoxy groups;
E) one or more tertiary amines;
F) one or more polyamines containing at least one NH ₂ group,
characterized in that components (A), (B) and (C) are subjected to simultaneous interaction to a degree of conversion of isocyanate groups of 70-98%, if necessary, component (D) is introduced into the reaction mass, then the carboxyl groups of component (C) are completely or partially neutralized ) by component (E), dispersed in water, component (F) is introduced, the dispersion is heated and kept at a temperature of from 20 to 90 ° C for one to four hours. 2. The method according to p. 1, according to which in the obtained highly concentrated aqueous nanoscale polyurethane dispersion, the ratio of the isocyanate groups of component (A) to the hydroxyl groups of components (B) and (C) (isocyanate index) is in the range from 1.8 to 8.0 the ratio of the isocyanate groups of component (A) to the hydroxyl groups of components (B), (C) and (D) is in the range from 1.8 to 2.4. 3. The method according to p. 1, characterized in that the synthesis of the prepolymer is carried out to a degree of conversion of isocyanate groups of 80-98%. 4. The method according to p. 1, characterized in that as component (B) use polyoxyalkylene polyols with low unsaturation obtained using a DMC catalyst. 5. The method according to p. 1, characterized in that as component (B) use polyoxyalkylene polyols with MM 1000-8000. 6. The method according to p. 1, characterized in that the component (D) is introduced immediately before neutralization. 7. The method according to p. 1, characterized in that immediately before dispersion, neutralization of 70-100 eq. % carboxyl groups of component (C) by component (E). 8. The method according to p. 1, characterized in that the neutralization is carried out at a temperature of from 50 to 80 ° C. 9. The method according to p. 1, characterized in that component (E) is triethylamine. 10. The method according to p. 1, characterized in that after dispersion, component (F) is introduced in an amount of 60-100 equiv.% Of prepolymer isocyanate groups. 11. The method according to p. 1, characterized in that component (F) is a bifunctional primary amine. 12. The method according to p. 1, characterized in that after the supply of component (F), the dispersion is stirred at a temperature of 50-80 ° C for 2 hours. 13. The method according to p. 1, according to which a highly concentrated aqueous nanoscale polyurethane dispersion is obtained, where the main proportion of polyurethane particles is 70-100% of the total number of particles and has a size <100 nm. 14. The method according to p. 1, characterized in that the process is carried out in the presence of a catalyst. 15. Highly concentrated aqueous nanoscale polyurethane dispersion, not containing an organic solvent, with a concentration of the main substance of 30-60%, which is the product of the interaction:
A) at least one polyisocyanate containing at least two isocyanate groups;
B) one or more polyols with an average molecular weight (MM) of from 1000 to 18000 having at least two hydroxyl groups obtained using a DMS catalyst;
C) one or more compounds with at least two OH-functional groups which contain at least one carboxyl group, which can be converted completely or partially into a carboxylate group in the presence of bases;
D) possibly one or more polyols and / or glycidyl ethers of polyols with an average molecular weight of less than 500, containing at least 2 hydroxyl and / or epoxy groups;
(E) one or more tertiary amines;
(F) one or more polyamines containing at least one NH ₂ group,
when the ratio of the isocyanate groups of component (A) to the hydroxyl groups of components (B) and (C) (isocyanate index) in the range from 1.8 to 8.0 and the ratio of the isocyanate groups of component (A) to the hydroxyl groups of components (B), ( C) and (D) in the range of 1.8 to 2.4. 16. A highly concentrated aqueous nanoscale polyurethane dispersion according to claim 15, which as component (B) contains polyoxyalkylene polyols having a low degree of unsaturation and MM 2000-8000. 17. A highly concentrated aqueous nanoscale polyurethane dispersion according to claim 15, in which the main proportion of polyurethane particles is 70-100% of the total number of particles and has a size <100 nm. 18. The use of a highly concentrated aqueous nanoscale polyurethane dispersion according to claim 15 for producing coatings for various substrates, especially flexible substrates, sealants and adhesives with high physical and mechanical properties, such as elasticity and strength, and high water resistance.