Blocked polyisocyanates, method of their obtaining and application

FIELD: chemistry.

SUBSTANCE: invention relates to blocked polyisocyanates, applied for obtaining of bonding means for thermohardening lacquers, paints and such other subjected to thermo processing systems, as adhesive substances or elastomers, they serve as means for net-like structure formation for polyol components. Blocked polyisocyanates have general formula (I): Said polyisocyanates are obtained by interaction of polyisocyanates of general formula (II)

with secondary amines of general formula (III)

EFFECT: obtaining of polyisocyanates, which ensure lower temperature of net-like structure formation and, therefore thermoprocessing, they are also stable as to crystallisation in organic solutions, which favours appreciable reduction of viscosity of such solutions, because it allows to reduce solvent content.

14 cl, 2 tbl, 15 ex

 

The present invention relates to new polyisocyanates, more particularly to a blocked polyisocyanates, method of their production and use.

The use of locking means for the temporary protection of isocyanate groups is known from ancient times. The blocked polyisocyanates used including to obtain stable when stored at room temperature and cured at elevated temperature one-component polyurethane thermo-labile systems. To do this, the blocked polyisocyanates are mixed, for example, contains hydroxyl groups of the polyesters, polyacrylates, with other polymers, as well as other components of varnishes and paints as pigments, co-solvents and additives. Another form stable when stored at room temperature thermolabile varnishes are capable of Autonomous education reticulated structure thermolabile system, which as binders include polymers whose molecules include blocked isocyanate and a hydroxyl group.

Surveys on the use of blocked polyisocyanates are, for example, in the publications Z. Wicks, Progress in Organic Coatings, 3 (1975), 73-99; Z. Wicks, Progress in Organic Coatings, 9 (1981), 3-28; D.A.Wicks and Z.W.Wicks, Progress in Organic Coatings (1999), 148-172.

The most important compounds which are used to lock the deposits of polyisocyanates, are ε-caprolactam, methylethylketoxime (oxime of butanone), and diethyl ester of malonic acid, secondary amines, and derivatives of triazole and pyrazole described, for example, in applications to the European patent No. 0576952, No. 0566953, No. 0159117, in U.S. patent No. 4482721, in the application of international patent No. 97/12924 or in the application for the European patent No. 0744423.

Secondary amines as a blocking means described in the application for the European patent No. 0096210. It, however, as the blocking of funds specifically named only amines containing alkyl, cycloalkyl and arylalkyl group. In the application materials no specific guidance on amines, which contain carbon multiple bonds with heteroatoms or multiple bonds heteroatoms with heteroatoms. In addition, as described in the application for the European patent No. 0096210 blocked secondary amines, the polyisocyanates may be used in General to obtain a solvent-containing varnishes or lacquers with a high content of solids (lacquer "high solids"), because they are not soluble in organic solvents.

The most commonly used means for blocking isocyanates are ε-caprolactam and the oxime of butanone. If for the case of ε-caprolactam, typically use a heat treatment temperature of about 160°C. or higher, monocomponent temperature-sensitive polyurethane varnishes, in which as blocking agents were used, the oxime of butanone can thermoacoustics at temperatures 10-20°C below. However, in the case of modern lacquer systems aim to further reduce the required heat treatment temperature in order to, on the one hand, to save energy in furnaces for heat treatment, functioning at a lower temperature, and in order, on the other hand, to be able to coating such one-component polyurethane lacquers on heat sensitive substrates.

The blocked polyisocyanates, based on which the one-component heat-sensitive system with lower temperature heat treatment, can be obtained by blocking polyisocyanates diethyl ester of malonic acid, 1,2,4-triazole and diisopropylamino. However, they noted the disadvantage that they, in particular, in the form of compounds with polyisocyanates based on linear aliphatic diisocyanates, are not well soluble in organic solvents and crystallize from these solutions, they can not find General application. One-component polyurethane thermolabile system with low temperature curing can also be based on polyisocyanates blocked with 3,5-dimethyl what razolam. Their disadvantage is that the 3.5-dimethylpyrazol at room temperature is a solid and therefore it is difficult to dose. For dosing in liquid form, it must be dissolved at elevated temperatures in lacquer thinner or melted, which represents an additional manufacturing operation. However, in the application for the European patent No. 00713871 presents a method, in accordance with which blocked 3,5-dimethylpyrazole the polyisocyanates get through synthesis of 3,5-dimethylpyrazole in lacquer thinner and directly using the resulting reaction solution for blocking, bypassing the allocation of solids; however, this method requires additional instrumentation and/or spending extra time and also to obtain the blocking means have to use carcinogenic hydrazine. In addition, in this case, it is not always possible to prevent entering the product side product of the synthesis of 3,5-dimethylpyrazole, which affects the quality product, such as its color.

Accordingly the present invention is the task of obtaining blocked polyisocyanates, which are devoid of the above-mentioned disadvantages of the prior art and, in particular, provide a lower temperature of formation of setca the ow patterns and heat treatment, respectively, than the polyisocyanates blocked with oxime of butanone, which are also stable against crystallization in organic solvents and which can be obtained by a simple method.

The problem is solved offered blocked polyisocyanates of the formula (I)

where R1, R2, R3and R4may be the same or different and mean a hydrogen atom, alkyl group with carbon atoms of from one to six,

R5means alkyl group with the number of carbon atoms from one to ten or cycloalkyl group with the number of carbon atoms from three to ten,

the mean number of from 2 to 8,

And that means the core of isocyanate functionality equal,

In the mean group

in which R6means alkyl group with the number of carbon atoms of from one to six.

The object of the invention is also a method of obtaining blocked polyisocyanates of the formula (I), which is that carried out the interaction of polyisocyanates of the General formula (II)

where a and u have given for the formula I,the values

with secondary amines of General formula (III)

where the substituents from R1to R5and you have given for formula (I) value is expression.

Another object of the invention is the application of the relevant invention, the blocked polyisocyanates to obtain varnishes, paints and such other subjected to heat treatment systems, as adhesives or elastomers, as well as the use as an additive in the vulcanization of rubbers, as well as the method of applying to a substrate coating with paints that contain blocked in accordance with the invention, the polyisocyanates, and, in addition, products made of these materials and substrates coated with them coverings.

The blocking means of the formula (III) can be obtained, for example, by the reaction of primary amines with compounds with activated carbon-carbon double bonds, as described, for example, in Organikum, 19th edition, Deutscher Verlag der Wissenschaften, Leipzig, 1993, pages from 523 to 525. The primary amine selectively reacts with carbon-carbon double bond with the formation of secondary asymmetric amine. In the preferred case, as the locking means of the formula (III) use of substances that are products formed by the above scheme of sterically obstructed primary amines, such as sec-butylamine, tert-butylamine, cyclohexylamine, which may have alkyl substituents, Isopropylamine, cyclopropylamine, razwell is installed or cyclic isomers of pentyl-, hexyl-, heptyl-, octyl and nonylamine or benzylamine, and compounds with an activated carbon-carbon double bond, such as esters of α,β-unsaturated carboxylic acids, N,N-dialkylamide α,β-unsaturated carboxylic acids, nitroalkane, aldehydes and ketones. Particular preference is given to substances which are addition products of primary amines such alkilany esters of acrylic, methacrylic and crotonic acids as methyl methacrylate, isosorbidedinitrate, ethyl methacrylate, n-propylbetaine, isopropylacetate, n-butylmethacrylate, isobutyronitrile, 2-ethylhexylacrylate, methyl acrylate, acrylate, n-propylacetate, isopropylacetate, sorbonnelaan, n-butyl acrylate, tert-butyl acrylate, isobutylamine, 2-ethyl hexyl acrylate, methyl ester of crotonic acid, ethyl ester of crotonic acid, propyl ester of crotonic acid.

In the preferred case of the use of substances that are a product of the merger of tert-butylamine or Isopropylamine, or cyclohexylamine to methyl or ethyl, or propyl, or isopropyl, or n-butyl or isobutyl, or tert-butyl ether, acrylic or methacrylic, or crotonic acid.

In a particularly preferred case of the use of substances that pose is a product of the merger of tert-butylamine to methyl acrylate or product fitting tert-butylamine to methyl methacrylate, or the product of the joining of tert-butylamine to tert-butyl acrylate.

Obtaining the blocking means may be suitable, in the preferred case, in a polar solvent. In the case of the target products can be separated from the solvent and/or by-products through distillation or extraction methods and after that they can react with polyisocyanates. However, it is not excluded the possibility of carrying out the reaction in a suitable solvent for lacquer with direct use of the obtained reaction mixture to obtain blocked polyisocyanates.

Needless to say, that can be used blocking means of the formula (III), which were obtained other than as described above, for example, by the transesterification of the ethyl ester of the formula (III) with methyl ether.

Needless to say, that can be used blocking means of the formula (III) in the form of any mixtures between them.

As polyisocyanates of the formula (II), which are used to retrieve relevant to the invention the blocked polyisocyanates may be used triisocyanate and all known aliphatic, cycloaliphatic and aromatic diisocyanates, and based on them polyisocyanates containing isocyanates about the 0.5 to 60, in the preferred case from 3 to 30, in a particularly preferred case from 5 to 25 wt.%, or mixtures thereof. For example, this polyisocyanates based on 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HMDI), 2-methyl-1,5-diisocyanatobutane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4 - or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatohexane, 1,3 - and 1,4-diisocyanatohexane, 2,6 - and 2,4-diisocyanato-1-methylcyclohexane, 1,3 - and 1,4-bis-(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (isophoronediisocyanate), 2,4 - and 4,4'-diisocyanatohexane, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl, bis-(isocyanatomethyl)norbornane, 1,3 - and 1,4-bis-(2-isocyanatopropyl-2-yl)benzene, 2,4 - and 2,6-diisocyanates (TDI), difenilmetana-2,4'- and/or -4,4'-diisocyanate, 1,5-diisocyanatobutane or the corresponding diisocyanates.

In the preferred case suitable polyisocyanates with oxadiazoline groups, carbodiimide groups, allophanate groups, which groups iminoimidazolidine groups, urethane groups and biuret groups. In accordance with the invention is most suitable known polyisocyanates which are primarily used to obtain varnishes containing, for example, oxidization, allophanate and/or biuret and/or from cyanurate, uretdione group and/or iminoimidazolidine group representing products modification of the above simple diisocyanates, in particular of hexamethylenediisocyanate or isophorondiisocyanate, or 2,4'- or 4,4'-diisocyanatohexane. In addition, suitable containing urethane groups of the low molecular weight polyisocyanates which can be obtained as a result of interaction taken in excess of isophorondiisocyanate or diisocyanate with simple polyhydric alcohols with molecular masses in the range from 62 to 300, in particular trimethylolpropane or glycerin.

Particular preference is given to polyisocyanates with which, iminoimidazolidine or biuret structures on the basis of hexamethylenediisocyanate (HMDI), isophorondiisocyanate and/or 2,4'- and/or 4,4'-diisocyanatohexane or mixtures of these compounds.

The above-described polyisocyanates obtained by modification of Monomeric diisocyanates, after receiving them can be cleared of excess monomers, for example, by distillation in a thin-film evaporator. However, you can also immediately be used to block formed after the modification reaction mixture containing Monomeric diisocyanates.

Suitable polyisocyanates are also known Pepoli is a career with terminal isocyanate groups, which, in particular, can be obtained by the interaction of the abovementioned simple polyisocyanates, in the preferred case, diisocyanates, taken with the lack of quantities of organic compounds with at least two functional groups that react with isocyanates. In these known prepolymers, the ratio of isocyanate groups to isocyanate-reactive groups of the hydrogen atoms is from 1.3:1 to 20:1, in the preferred case from 1.5:1 to 3:1. with preference being given to hydrogen atoms from the hydroxyl groups. The nature and quantitative proportions used to obtain the isocyanate prepolymers initial products in the preferred case are chosen so that in the preferred case, the average isocyanate functionality of prepolymer on isocyanate groups was in the range of from 2 to 3 and to srednekovoi is the molecular weight ranged from 500 to 10000, in the preferred case from 800 to 4000. After receiving prepolymer unreacted polyisocyanate may be separated, in the preferred case distillative way.

It is clear that the aforementioned polyisocyanates can also be used in mixtures with each other.

Obtaining relevant to the invention, the blocked polyisocyanates (I) can be carried out by known methods. For example, you can take one or more polyisocyanates and with stirring, add a blocking agent (for example, within about 10 minutes). Stirring is continued until such time as the analysis shows the absence of free isocyanate. You can also block one or more polyisocyanates with a mixture of two or more of the blocking means.

But you can also perform communication only part of the free isocyanate groups in the polyisocyanates with the relevant invention the blocking means and the remaining portion to enter into the reaction with an excess of containing a hydroxyl group described below in more detail polyesters, polyurethane and/or polyacrylate, and appropriate mixtures thereof so that there was a formation containing free hydroxyl groups and blocked isocyanate groups of the polymer, which when heated to the appropriate temperature heat treatment forms a mesh structure without adding substances containing more isocyanate groups and/or hydroxyl group.

You can also perform the reaction only part of the free isocyanate groups in the diisocyanate with the relevant invention the blocking means and then part of the non-blocked isocyanate groups to enter into reaction with the formation of MDI, constructed from at least two diisocyanates.

Getting blocked polyisocyanates and capable when heated to avtonomna education reticulated structure of one-component systems can be in the appropriate case, to carry out in a suitable organic solvent. On the role of a suitable solvent, for example, conventional solvents for varnishes, such as ethyl acetate, butyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, N-organic, chlorobenzene or reference gas. Also suitable mixture, which primarily contain higher substituted aromatic compounds, for example, marketed under the designation Solvent Naphtha, Solvesso®(Exxon Chemicals, Houston, USA). Cypar®(Shell Chemicals, Eschborn, Germany), Cycio Sol®(Shell Chemicals, Eschborn, Germany), Tolu Sol®(Shell Chemicals, Eschborn, Germany), Shellsol®(Shell Chemicals, Eschborn, Germany). However, the solvent can be added and after receipt of the relevant invention, the blocked polyisocyanates, for example, to reduce the viscosity. In this case, there may be used alcohols such as, for example, Isobutanol, because then contained isocyanate groups have completely reacted with the reactive towards isocyanate groups functional groups. Solvents which are preferred are acetone, butyl acetate, 2-butanone, 1-methoxypropyl-2-acetate, xylene, toluene, mixtures, which primarily contain higher substituted aromatic compounds, for example, marketed under the designation Solvent Naphtha, Solvesso®(Exxn Chemicals, Houston, USA), Cypar®(Shell Chemicals, Eschborn, Germany), Cyclo Sol®(Shell Chemicals, Eschborn, Germany), Tolu Sol®(Shell Chemicals, Eschborn, Germany), Shellsol®(Shell Chemicals, Eschborn, Germany).

Upon receipt of the relevant invention polyisocyanates can be used as catalysts, co-solvents and other AIDS and additives.

Corresponding to the invention, the blocked polyisocyanates used for binders for varnishes, paints and such other subjected to heat treatment systems, as adhesives and elastomers, while they serve as a means for the formation of a mesh structure for polyol as one of the components.

Corresponding to the invention, the blocked polyisocyanates are, as mentioned above, the polymers that are capable of Autonomous formation of a mesh structure, and/or they can be used as vehicles for education net patterns for polyol as one of the components. As a polyol as one of the components that can be used as mixtures, can be considered polyhydroxylated polyesters, polyhydroxylated polyethers containing hydroxyl and other groups polymerizate, for example, known polyhydroxylated the polyacrylates with a hydroxyl number of from 20 to 200, in the preferred case from 50 to 130, from p which accounts for 100%green products, or polyhydroxylated polycarbonates or polyhydroxylated urethanes.

Examples of suitable polyester polyols are, in particular, is known in polyurethane chemistry interaction products, polyhydric alcohols, for example of alcantarillas, named here as an example, excessive amounts of polycarboxylic acids or anhydrides of polycarboxylic acids, in particular dicarboxylic acids or anhydrides of dicarboxylic acids. Suitable polycarboxylic acids or anhydrides of polycarboxylic acids are, for example, adipic acid, phthalic acid, isophthalic acid, phthalic anhydride, the anhydride tetrahydrophthalic acid anhydride hexahydrophthalic acid, maleic acid, maleic acid anhydride, it adducts the Diels-Alder reaction with cyclopentadiene, fumaric acid or dimeric or trimeric fatty acids. Upon receipt of polyester polyols can be used in any mixture mentioned as examples of polyhydric alcohols or any mixture mentioned as examples of acids or anhydrides of acids.

Production of polyester polyols carried out by known methods described, for example, in Houben-Weyl, Methods der organischen Chemie, Volume XIV/2, G.Thieme-Verlag, 1963, pages 1 to 7. Required in some cases, hydrophilic modification of these polyhydroxylated compounds carried out by known methods described, for example, in applications to the European patent No. 0157291 or No. And 0427028.

Suitable polyol as one simple polyesters are known in polyurethane chemistry products amoxilonline and/or propoxycarbonyl corresponding molecules with the number of functional groups of 2 to 4, for example, water, ethylene glycol, propandiol, trimethylolpropane, glycerol and/or pentaerythritol.

If polyhydroxylated polyacrylate we are talking about well-known mixed polymerizate styrene with conventional esters of acrylic acid and/or methacrylic acid, and for the introduction of hydroxyl groups optionally use such hydroxyalkyl ethers, such as 2-hydroxyethylamine, 2-hydroxypropylamino, 2-, 3 - or 4-hydroxybutyrate esters of these acids.

You can also obtain water-containing one-component polyurethane lacquers, dispersive in water corresponding to the invention, the blocked polyisocyanates, which may contain a solvent, together with a hydrophilic modified containing hydroxyl group of the polymer.

Getting varnishes, paints and other ready-to-use forms using appropriate invention polyisocyanates ASU is coming by known methods. In addition to the polyisocyanates and polyols in ready-to-use forms can be added conventional additives and other auxiliary substances (e.g. solvents, pigments, fillers, auxiliary means for processing, defoamers, catalysts) in quantities that are easily determined by the expert in the course of illustrative experiments.

As additional components for education of a mesh structure can also be used with other compounds which contain isocyanate-reactive groups of the functional group. This can be, for example, aminoplast resin. The concept aminoplastic resins is known in the technology clears the condensation products of melamine with formaldehyde or urea with formaldehyde. Fit all the usual condensation products of melamine with formaldehyde, which can be tarifitsirovana monohydroxy alcohols with the number of carbon atoms one to four. In case of additional use of other components for the formation of the mesh this must be agreed with the number of binders with reactive toward isocyanate groups with hydroxyl groups.

Corresponding to the invention, the blocked polyisocyanates can be used to obtain thermoeconomics akov, for example, for coloring in the factory or for the first painting of cars. For this, relevant to the invention the means for the formation of coatings may be applied to the doctor blade method, a dipping, using compressed air from sprinklers or without air, and electrostatic methods of application, for example, spray with high-speed cone. The thickness of the dry film may be, for example, from 10 to 120 μm. Curing of the dried films is carried out by heat treatment in the temperature range from 90 to 160°C, in the preferred case from 110 to 140°C. Corresponding to the invention, the blocked polyisocyanates can be used to obtain thermoeconomics varnishes for continuous coating on the strip, and a maximum heat treatment temperature, known to the expert as “peak temperature”, and for the case where the substrate is a metal known as “peak metal temperatures”, are in the range from 130 to 300°C., in the preferred case from 190 to 260°C and the dry thickness of the coating can achieve for example, from 3 to 40 microns.

As will be shown in the following examples, which may not be used to limit the scope of the claims set the basis of the invention the task is solved by the respective image the structure of polyisocyanates and systems capable of Autonomous education reticulated structure during heat treatment. Corresponding to the invention the polyisocyanates in combination with the polyols are characterized by lower values of the temperature for the formation of a mesh structure or heat treatment, respectively, than the polyisocyanates blocked with oxime of butanone, they are stable with respect to crystallization in organic solvents and they can be obtained by simple methods. Moreover, the solutions corresponding to the invention, the blocked polyisocyanates in organic solvents significantly less viscous than solutions of ordinary blocked polyisocyanates that it is desirable in obtaining modern lacquer systems, as it helps to reduce the solvent content.

Examples

Interest data, unless otherwise stated, refer to the percent by mass. The solids content and the content of blocked isocyanate groups represent the calculated values, determined in accordance with the equations:

Particle size was determined by laser correlation spectroscopy.

The original substances and their sources

The polyisocyanate A1

Desmodur®N3300, Bayer AG, which contains groups of the polyisocyanate for varnishes based on 1,6-diisocyanate the Ana (HMDE) with a content of isocyanate groups 21.8 wt.%, with a viscosity at 23°C of about 3000 MPa·s and with functionality isocyanate groups, equal to about 3.5.

The polyisocyanate A2

Desmodur®Z4470BA, Bayer AG, which contains groups of the polyisocyanate for varnishes based on isophorondiisocyanate containing 30 wt.% butyl acetate with a content of isocyanate groups of 11.8 wt.%, with a viscosity at 23°C. of about 700 MPa·s and with functionality isocyanate groups of about 3.4.

The polyisocyanate A3

Desmodur®Z4470MPA/X, Bayer AG, which contains groups of the polyisocyanate for varnishes based on isophorondiisocyanate containing 30 wt.% 1:1-mixture of xylene and methoxypropylacetate, with a content of isocyanate groups of 11.8 wt.%, with a viscosity at 23°C. of about 700 MPa·s and with functionality isocyanate groups of about 3.4.

Blocking means B1

To 73,14 g of tert-butylamine dissolved in 160,0 g of methanol, with stirring, was added at room temperature 86,09 g of methyl acrylate and mix the resulting clear solution at room temperature for another 16 hours. The solvent is distilled off and get 158,1 g of the product of the formula

The purity of the product is sufficient for the subsequent formation of the blocked MDI.

Blocking means B2

To 95,09 g of tert-butylamine dissolved in 175,0 g of ethanol, added with paramasivan and at room temperature 100,1 g of methyl methacrylate and mix the resulting clear solution for another 72 hours at 70°C. Volatile components are distilled, filtered and receive in the form of filtrate 165,7 g of the product of the formula

The purity of the product is sufficient for the subsequent formation of the blocked MDI.

Blocking means B3

To 73,14 g of tert-butylamine dissolved in 200,0 g of methanol, with stirring, was added at room temperature 128,1 g tert-butyl acrylate and mix the resulting clear solution at room temperature for another 16 hours. The solvent is distilled off and get 199,1 g of the product of the formula

The purity of the product is sufficient for the subsequent formation of the blocked MDI.

Blocking means B4

To 99,18 g cyclohexylamine dissolved in to 185.0 g of methanol, with stirring, was added at room temperature 86,09 g of methyl acrylate and mix the resulting clear solution at room temperature for another 16 hours. The solvent is distilled off and get 184,2 g of the product of the formula

The purity of the product is sufficient for the subsequent formation of the blocked MDI.

Blocking means B5

To 59.0 g of Isopropylamine dissolved in 135,0 g of methanol, with stirring, was added at room temperature 100,1 g methyl is of ethacrylate and mix the resulting clear solution at room temperature for another 12 hours. The solvent is distilled off and get 158,2 g of the product of the formula

The purity of the product is sufficient for the subsequent formation of the blocked MDI.

Blocking means B6

To 73,14 g of tert-butylamine dissolved in 175,0 g of ethanol, was added under stirring at room temperature 100,1 g of methyl ester of crotonic acid and stirred the resulting clear solution for another 72 hours at 70°C. the Solvent is distilled off and get 168,9 g of the product of the formula

The purity of the product is sufficient for the subsequent formation of the blocked MDI.

Example 1

(Receipt invention polyisocyanate education reticulated structure containing solvent)

To 192,7 g (1 isocyanate equivalent) of MDI A1, dissolved in 88.0 g of butyl acetate, 10 minutes are added dropwise 159,3 g (1 equivalent) of the blocking means B1. The temperature rises to about 40°C. According to IR-spectroscopy after stirring at this temperature for 4 hours free isocyanate groups are absent. Get 440,0 g transparent product with the following characteristics.

80%
The content of blocked isocyanate groups9,54%
Viscosity at 23°C3500 MPa·s

Example comparison 1

(Getting blocked MDI blocked 3,5-dimethylpyrazole)

To 192,7 g (1 isocyanate equivalent) of MDI A1, dissolved in to 72.2 g of butyl acetate, add 96,0 g (1 equivalent) of 3,5-dimethylpyrazole. The temperature rises to about 60°C. According to IR-spectroscopy after stirring at this temperature for 2 hours free isocyanate groups are absent. Get 360,9 g transparent product with the following characteristics.

The solids content80%
The content of blocked isocyanate groups11,6%
Viscosity at 23°C10000 MPa·s

Example 2

(Receipt invention polyisocyanate education reticulated structure containing solvent)

To 356 g (1 isocyanate equivalent) of MDI A2, restoran is th at of 69.0 g of butyl acetate, within 10 minutes are added dropwise 159,3 g (1 equivalent) of the blocking means B1. The temperature was raised to about 60°C. According to IR-spectroscopy after stirring at this temperature for 6 hours free isocyanate groups are absent. Get 584,3 g transparent product with the following characteristics.

The solids content70%
The content of blocked isocyanate groups7,19%
Viscosity at 23°C10000 MPa·s

Example 2 comparison

(Getting blocked MDI blocked 3,5-dimethylpyrazole)

To 356 g (1 isocyanate equivalent) of MDI A2 dissolved in 41,0 g of butyl acetate, add 96,0 g (1 equivalent) of crystalline 3,5-dimethylpyrazole. The temperature was raised to about 60°C. According to IR-spectroscopy after stirring at this temperature for 2 hours free isocyanate groups are absent. Get 493 g of a transparent product with the following characteristics.

The solids content70%
The content of blocked isocyanate groupscharged 8.52%
Viscosity at 23°C70000 MPa·s

Example 3

(The receipt to the invention, one-component system, capable when heated to the self-education of a mesh structure)

To 391,6 g (1.1 isocyanate equivalent) of MDI A2 dissolved in 85 g of butyl acetate, 10 minutes are added dropwise 127,4 g (0.8 equivalent) of the blocking means B1. The temperature rises to about 40°C. After stirring at this temperature for 4 hours add 935 g (1.1 equivalent), Desmophen®T XP 2013, Bayer AG, representing free from oils containing hydroxyl group of the polyester in the form of a 75%solution in Solvent-naphtha 100 with the content of hydroxyl groups of 2.0% by the method of DIN 53240/2, and stirred for further 4 hours at 70°C; after this, according to IR-spectroscopy of free isocyanate groups in the mixture itself. After dilution by adding 300 g of butyl acetate receive 1839,0 g transparent product with the following characteristics.

The solids content60%
The content of blocked isocyanate what's groups 0.8 equivalent
The content of free hydroxyl groups0.8 equivalent
Viscosity at 23°C750 MPa·s

Example 3 comparison

(Getting blocked with oxime of butanone one-component system, capable when heated to the self-education of a mesh structure)

To 391,6 g (1.1 isocyanate equivalent) of MDI A2 for 10 minutes, added dropwise to 69.6 g (0.8 equivalent) of the oxime of butanone. The temperature rises to about 40°C. After stirring at this temperature for 4 hours add 935 g (1.1 equivalent), Desmophen®T XP 2013, BayerAG, representing free from oils containing hydroxyl group of the polyester in the form of a 75%solution in Solventnaphtha 100 with the content of hydroxyl groups of 2.0% by the method of DIN 53240/2, and stirred for further 4 hours at 70°C; after this, according to IR-spectroscopy of free isocyanate groups in the mixture itself. After dilution by the addition of 345 g of butyl acetate receive 1741,2 g transparent product with the following characteristics.

The solids content60%
The content of blocked isocyanate groups0.8 equivalent
The content of free hydroxyl groups0.8 equivalent
Viscosity at 23°C900 MPa·s

You can see that is blocked by the blocking means B1 polyisocyanates in examples 1-3 have a lower viscosity than the corresponding blocked 3,5-dimethylpyrazole or oxime of butanone the polyisocyanates according to the comparison examples 1-3.

Example 4

(Getting polyisocyanate education reticulated structure containing solvent)

To 192,7 g (1 isocyanate equivalent) of MDI A1, dissolved in 157,0 g of butyl acetate, 10 minutes are added dropwise to 173.3 g (1 equivalent) of the blocking means B2. The temperature rises to about 40°C. According to IR-spectroscopy after stirring at this temperature for 4 hours free isocyanate groups are absent. Get 523,0 g transparent product with the following characteristics.

The solids content70%
The content of blocked isocyanate what's groups 8,03%
Viscosity at 23°C2000 MPa·s

Example 5

(Getting polyisocyanate education reticulated structure containing solvent)

To 192,7 g (1 isocyanate equivalent) of MDI A1, dissolved in 131,0 g of butyl acetate, 10 minutes are added dropwise 201,3 g (1 equivalent) of the blocking means B3. The temperature rises to about 40°C. According to IR-spectroscopy after stirring at this temperature for 4 hours free isocyanate groups are absent. Get 525.0 g transparent product with the following characteristics.

The solids content75%
The content of blocked isocyanate groups8,00%
Viscosity at 23°C2500 MPa·s

Example 6

(Getting polyisocyanate education reticulated structure containing solvent)

To 192,7 g (1 isocyanate equivalent) of MDI A1, dissolved in 126,0 g of butyl acetate, 10 minutes are added dropwise 185,3 g (1 equivalent) of the blocking means B4. At this rate the temperature rises to about 40°C. According to IR-spectroscopy after stirring at this temperature for 4 hours free isocyanate groups are absent. Get 504,0 g transparent product with the following characteristics.

The solids content75%
The content of blocked isocyanate groups8,33%
Viscosity at 23°C3000 MPa·s

Example 7

(Getting polyisocyanate education reticulated structure containing solvent)

To 192,7 g (1 isocyanate equivalent) of MDI A1, dissolved in 145,0 g of butyl acetate, 10 minutes are added dropwise 145,3 g (1 equivalent) of the blocking means B5. The temperature rises to about 40°C. According to IR-spectroscopy after stirring at this temperature for 4 hours free isocyanate groups are absent. Get 482,9 g transparent product with the following characteristics.

The solids content70%
The content of blocked isocyanate groups 8,71%
Viscosity at 23°C2500 MPa·s

Example 8

(Getting polyisocyanate education reticulated structure containing solvent)

To 192,7 g (1 isocyanate equivalent) of MDI A1, dissolved in 157,0 g of butyl acetate, 10 minutes are added dropwise to 173.3 g (1 equivalent) of the blocking means B6. The temperature rises to about 40°C. According to IR-spectroscopy after stirring at this temperature for 4 hours free isocyanate groups are absent. Get 523,0 g transparent product with the following characteristics.

The solids content70%
The content of blocked isocyanate groups8,03%
Viscosity at 23°C2000 MPa·s

Example 4 comparison

(Blocked by diisopropylamino or 1,2,4-triazole, or, respectively, the diethyl ester of malonic acid polyisocyanates containing solvent)

The addition of 136 g of butyl acetate diluted 192,7 g MDI A1 and with stirring in a dry nitrogen atmosphere was added 101.0 g (1 EQ whom Valens) Diisopropylamine, thus, there is a weak exothermic effect. After adding heated to 70°C. and after stirring at this temperature for 30 minutes, cooled the reaction mass to room temperature. After that, according to IR-spectroscopy of free isocyanate groups in the product are not available. Get clear, virtually colorless product with the following characteristics.

The solids content65%
The content of blocked isocyanate groupsof 9.30%
Viscosity at 23°C1900 MPa·s

After storage for 14 days at room temperature began the formation of a solid phase in the crystallization. After storage for 18 days at room temperature formed a solid white opaque mass. The products according to examples 1-8, even after storage for 12 weeks did not show signs of crystallization or formation of a solid phase. Obtained by analogy with the previous blocked 1,2,4-triazole-based polyisocyanate A1 blocked polyisocyanate crystallizes already in the process of obtaining. Obtained by analogy with the previous BL is karavany diethyl ester of malonic acid and based on the polyisocyanate A1 blocked polyisocyanate crystallizes after approximately 21 days.

Example example comparison 9

(To obtain coverage from a single component of a system capable when heated to the self-education of a mesh structure, for example 3 and example comparison 1)

In each case, to 142,9 g of product from example 3 and example of comparison 1 was added 1.4 g of dilaurate dibutylamine, 0.15 g Modaflow®(aid to improve processing AIDS, acrylic copolymer of the company Solutia, 10% in methoxypropylacetate) and 0.15 g Baysilon®OL 17 (aid to improve processing AIDS, polyester polysiloxane, 10% in methoxypropylacetate, Bayer AG, Leverkusen) and mix thoroughly each individual mix. Using the squeegee both mixtures applied to taken for each experiment three glass plates and fanned them with air for 10 minutes. After heat treatment for 30 minutes in an oven with air circulation at 100°C, 140°C and 160 respectively°To obtain coatings with a layer thickness of the dried film is 40 μm. To study the degree of branching of retinal patterns determine the stability of the obtained films in relation to solvents.

As shown in table 1, in the case of one-component systems according to example 3, is capable when heated to the self-education of a mesh structure, after 30 minutes of heat treatment n and 140°C is achieved, the same resistance to solvents, when heat-treated at 160°C, whereas in the case of one-component systems, which when heated to the self-education of a mesh structure, for example as in comparison 1, the final properties of the coatings are achieved only after heat treatment at higher temperatures.

The example and the comparison example to 10

(Getting a one-component polyurethane clear lacquer from the corresponding invention blocked MDI of example 1 and one-component polyurethane clear lacquer from a locked 3,5-dimethylpyrazole MDI)

To 44,0 g of the product of example 1 and 57.5 g of Desmophen®A 870 (polyacrylate polymer with a hydroxyl functional groups, Bayer AG, 70% in butyl acetate with a content of hydroxyl groups according to DIN 53240/2, equal to 3.0%) was added 0.75 g of dilaurate dibutylamine, 0.08 g Modaflow® (an adjuvant to improve processing AIDS, acrylic copolymer of the company Solutia, 10% in methoxypropylacetate) and 0.08 g Baysilon OL 17 (aid to improve processing AIDS, polyester polysiloxane Bayer AG, Leverkusen, 1% methoxypropylacetate) and mix thoroughly blend. Using a squeegee mixture is applied on two pieces of aluminum sheet, which have been previously coated with white water primer paint and fanned them with air for 10 minutes. After Ter the of a for 30 minutes in an oven with air circulation at 120°C and, respectively, at 140°C receive coatings with a layer thickness of the dried film, equal to 40 microns. The selection of the received data on the technical characteristics properties of lacquer coatings are presented in table 2.

To 40,0 g Desmodur®BL VP LS 2253 (Bayer AG, blocked by dimethylpyrazolo the polyisocyanate based on Desmodur®N 3300, Bayer AG, 75% of the mixture of methoxypropylacetate and Solvent Naphta) and 57.5 g of Desmophen® A 870 (polyacrylate polymer with a hydroxyl functional groups, Bayer AG, 70% in butyl acetate with a content of hydroxyl groups according to DIN 53240/2, equal to 3.0%) was added 0.7 g of dilaurate dibutylamine, 0.07 g Modaflow®(aid to improve processing AIDS, acrylic copolymer of the company Solutia, 10% in methoxypropylacetate) and 0.07 g of Baysilon OL 17 (aid to improve processing AIDS, polyester polysiloxane Bayer AG, Leverkusen, 1% methoxypropylacetate) and mix thoroughly blend. Using a squeegee mixture is applied on an aluminum sheet which has been coated with white water primer paint, and fanned it with air for 10 minutes. After heat treatment for 30 minutes in an oven with air circulation at 140°To obtain coatings with a layer thickness of the dried film is 40 μm. The selection of the received data on the technical characteristics properties of lacquer coatings are presented in table 2.

Table 2
Comparison of polyisocyanates blocked with methyl ester of N-tert-butyl-β-alanine, with polyisocyanates, blocked 3,5-dimethylpyrazole
Materials and testsCorresponding to the invention, the blocked polyisocyanate according to example 1VP LS 2253
Polyisocyanate baseN 3300N 3300
The blocking toolMethyl ester of N-tert-butyl-β-alanine3,5-Dimethyl-pyrazole
PolyolAnd 870And 870
Catalyst1,0% of dilaurate dibutyrate (DBTL)1,0% DBTL
Visual assessment of lacquertransparenttransparent
Heat treatment conditions30', 120°C30', 40°C 30', 140°C
Visual assessment of the lacquer coatingtransparenttransparenttransparent
The damping of the pendulum by könig [with]183191197
Resistance against
solvents
[assessment]1)
(X/MPA/EA/AC)
1 minute1 2 3 40 1 2 31 1 2 3
5 minutes2 2 4 42 2 4 42 2 4 4
Stability with respect to chemical reagents [°C]
(gradient furnace)
Wood tar363636
Brake fluid363636
Pancreatin, 50%363636
Sodium hydroxide, 1%404344
Sulfuric acid, 1%444545
Liquid no FAM DIN 51604-And, 10 minutes
[assessment]1)
112
Resistance to mechanical damage
(laboratory washing at the stop Amtec Kistler)
The initial gloss [20°]91,5for 91.3to 91.1
Loss of gloss (ΔGl) after 10 washing cycles [20°]29,528,132,8
Relative residual gloss [%]67,869,264,0
Thermal yellowing
Transparent varnish water priming lacquer
Initial yellowing [b]1,51,80,8
Yellowing from overheating at 30' 140°C [Δ b]1,52,11,0
Yellowing from overheating 30' 160°C [Δ b]0,00.3 0,2
1) 0 - good, 5 - bad

In table 2 data show that based on the invention the lacquer polyisocyanate system after heat treatment at 120°C has properties that are comparable with the properties of the previous heat treatment at 140°C lacquer systems based on MDI blocked 3,5-dimethylpyrazole. At 140°C on the respective invention varnishes receive coatings with very good performance in terms of resistance to solvents, mechanical damage and chemical attack, in addition, they are less prone to yellowing.

Example 11

(Getting aqueous one-component polyurethane clear lacquer on the blocked polyisocyanate of example 1)

To 95,41 g (0,86 isocyanate equivalents) of isophorondiisocyanate for 5 minutes at 50°C. are added dropwise with stirring a solution of 28,77 g (0.43 equivalent of hydroxyl groups) dimethylpropionic acid in 57,54 g of N-methylpyrrolidone. After stirring at 80°C for 150 minutes, the content of isocyanate groups reaches 9,19 wt.%. After adding 28,08 g (0,08 isocyanate equivalent) of MDI A3 and 446,72 g (1,404 equivalent of hydroxyl groups) of the polyester formed from adipic acid, isophthalic acid, Tr is metropropol, neopentylglycol and propylene glycol, the reaction mixture is stirred for 180 minutes at 80°C, then IR spectroscopy shows no more having isocyanate groups. In conclusion, at 70°C add 198,02 g corresponding to the invention MDI of example 1 and continue stirring for another 10 minutes. Then add 19,12 g (0,215 mole) of dimethylethanolamine and stirred for another 10 minutes. Then with vigorous stirring add 833,23 g heated to 70°C. deionized water, stirred for 90 minutes and allowed to cool under stirring. The resulting dispersion has the following characteristics.

The solids content45%
PH8,08
Viscosity at 23°C3400 MPa·s
Particle size59 nm

1. The blocked polyisocyanates of the formula (I)

where independently from each other
R1, R2, R3and R4may be the same or different and mean a hydrogen atom, alkyl group with carbon atoms of from one to six,
R5means alkyl group with the number of atmosukarto from one to ten or cycloalkyl group with the number of carbon atoms from three to ten,
the mean number of from 1 to 8
A represents the residue of the isocyanate functionality which are equal to,
In the mean group

in which R6means alkyl group with the number of carbon atoms of from one to six.

2. The blocked polyisocyanates according to claim 1, wherein R5means amily, ISO-propyl, isobutylene or tert-botilony the rest.

3. The blocked polyisocyanates according to claim 1, wherein R1means metal residue and R2, R3, R4means a hydrogen atom.

4. The blocked polyisocyanates according to claim 1, wherein R3means metal residue and R1, R2, R4means a hydrogen atom.

5. The blocked polyisocyanates according to claim 1, wherein R1, R2, R3and R4means a hydrogen atom.

6. The blocked polyisocyanates according to claim 1, characterized in that the molecule contains as blocked polyisocyanate groups and free hydroxyl groups.

7. The method of obtaining the blocked polyisocyanates of the formula (I) according to claim 1, characterized in that conduct the interaction of polyisocyanates of the General formula (II)

where a and u have given for formula (I) in claim 1 is,
with secondary amines of General formula (III)

where is zamestitel from R 1to R5and you have given for formula (I) in claim 1 value.

8. The method according to claim 7, characterized in that the blocking means of the formula (III) immediately after receiving them in used to obtain the solvent and without subsequent selection is introduced into the reaction with the polyisocyanates of the formula (II).

9. The use of blocked polyisocyanates according to claim 1 as a means for the formation of a mesh structure when heat-treated for polyol as one component in a one-component polyurethane systems.

10. The use of blocked polyisocyanates according to claim 1 to obtain elastomers.

11. Varnishes, paints and adhesives containing blocked polyisocyanates according to claim 1.

12. Aqueous dispersions containing blocked polyisocyanates according to claim 1.

13. The solution of the blocked polyisocyanates according to claim 1 in organic solvents.

14. Method of applying coatings to substrates, characterized in that the composition for a coating containing blocked polyisocyanates according to claim 1, applied to the substrate and the coating is subjected to heat treatment at temperatures of from 90 to 160°C, and consequently the peak temperatures are in the range from 130 to 300°C.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: anticorrosive composition for primer coat contains finely dispersed powder of zinc, polystyrene and/or styrene copolymer with rubber used as a binding agent, aromatic solver and 4,4'-diphenylmethanediisocyanate additionally. The method of anticorrosive treatment is carried out by applying over preliminary treated surface at least one primer coat prepared from the mentioned above composition with further applying at least one finishing coat.

EFFECT: preparation of one-package anticorrosive composition, flowability and plasticity of which is unchanged in water presence, providing high anticorrosive and chemical stability of treated surface designed for using articles in the conditions of continuous contact with water medium and atmosphere, having of higher mechanical and adhesive properties and providing with decreased material consumption during coat formation.

3 cl, 5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to water one-component systems for covering, which are used in glue compositions, in sealants, lacquers and size. Said systems contain (I) at least one polyurethane (A), which contains chemically bound hydrophilic groups, and, in which groups containing active by Tzerevitinov hydrogen atoms are present in amount from 0 to 0.53 mmole/g in terms of relative content of non-voletile dispersion components, (II) at least one blocked polyisocyanate (B), which does not contain hydrophilic groups, and (III) water, weight component ratio between components A and B being chosen in such way that content of blocked isocyanate constitutes from 0.01 to 1.0 mole per 100 g of hard resin. Also described are method of obtaining said systems, their application in sizes for glass fibre, method of obtaining from them covering on carriers, as well as carriers with applied on them preparations for covering, containing systems for covering of composition described above.

EFFECT: obtaining system which ensures stability in storage, reduced water-absorption, higher water-resistance and improved adhesive strength in wet state.

11 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: group of inventions refers to making paint compositions, such as enamels, namely, to making various-palette alkyd-urethane enamels to be used for protective decorative coating of various surfaces. Paint alkyd-urethane enamel compositions contain a combination of, at least, one alkyd varnish, and, at least, one alkyd-urethane varnish, dye-forming pigment additive component necessary to form enamel colour, at least, one organic solvent, dispersant, siccative and other auxiliary base additives, including, at least, one rheological additive, antiskinning additive, antidimpling additive. Herewith alkyd-urethane varnish content in the composition is at least 10% of total weight of the specified varnishes and/or at least 8% of paint composition weight.

EFFECT: high stress-strain properties and processing behaviour of produced enamels.

13 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to paint-and-varnish industry, in particular to method for production of alkyd-urethane enamels of various colours, and may be used to produce protective-decorating enamel coatings applied onto various substrates. Method for production of alkyd-urethane enamel is described. This method implies preparation of individual precursor components, their dosing, preparation of intermediate enamel product by combining alkyd pentaphthalic lacquer with dispersing medium, organic solvent and rheological agent, the mixture being stirred at 300-500 rpm, followed by introduction of free-flowing pigments into the mixture, together with filler, when required. Pigments and filler are pre-dispersed under stirring at a speed up to 1000 rpm until homogenous suspension is obtained. Then intermediate product is further dispersed until required degree of grinding is obtained, alkyd-urethane lacquer is added under stirring and, when required, anti-crater additive and paint dryer are added. Then, pigment tinting paste is added, the mixture is stirred to obtain homogenous suspension, and antiskinning agent is added.

EFFECT: production of alkyd-urethane enamels of various colours, with high physical and chemical properties.

10 cl, 5 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a composition that can be used for protection of metal surfaces of whatever machinery in contact with corrosion provoking media against corrosion. The composition includes the following components with their ratio in wt %, i.e. 100 of polymer binding epoxy dianic pitch, 20 to 30 of epoxyurethane oligomer modifier, 42 to 48 of organo-silicon amine hardener - γ-aminopropyletoxysilane, 25 to 30 of mineral filler, i.e. titanium dioxide (rutile), 22 to 25 of chromium phosphate inhibiting pigment, 20 to 60 of organic solvents, 3 to 4 of aerosol thixotropic agent, 10 to 20 of anti-rust additive of metal zinc. Xylene or acetone, either butyl acetate, or ethylcellosolve are used as organic solvents.

EFFECT: production of benzene-and water-proof coat with high adhesion properties.

2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: hydropyle blocked polyisocyanates are produced by the method wherein: A) one or the several organic polyisocyanates interact with B) one or several organic compounds, containing, at least, one isocyanate reactive group and comprising b1) non-ionic hydropyle groups based on simple poly-alkylenoxide-polyethers containing at least 30 wt % of ethylene-oxide links, and/or b2) ionic or potentially ionic hydropyle groups a forming dissociation equilibrium depending upon pH in interaction with water, and, depending upon pH not having a charge and being charged positively or negatively, or interact with C) one or several blocking means containing, at least, one cyclic ketone with CH-acidity of the general formula (2) where X is the electron-acceptor group, R1, R2 mean independently from each other the hydrogen atom, saturated or unsaturated aliphatic residual containing up to 12 carbon atoms, n is 1, and, if necessary, interacting with one or several (cyclic)aliphatic mono- or polyamines with the amount of amino groups in a molecule of 1 to 4 and molecular weight of up to 400 note that, if necessary, it interacts with one or several multinuclear spirits with the number of hydroxyl groups in a molecule from 1 to 4 and molecular weight of up to 400, and, if necessary, with amino spirits in the presence D) of one or several catalysts or, if necessary, with auxiliary substances and additives and, if necessary E), with solvents. Polyisocyanates can be used for manufacturing varnishes, coatings, sizes, glues and molded products.

EFFECT: improved method of producing hydropyle blocked polyisocyanates.

6 cl, 6 ex

FIELD: metallurgy.

SUBSTANCE: invention concerns field of tubes or fittings protection against corrosion or against formation of undesirable deposition, and also concerns field of metallic material multiple coating. It is implemented consecutive plating on metallic surface layers with different coefficients of thermal dilatation from suspension of polymer compound, containing polyurethane compound with admixture, influencing on coefficient of thermal dilatation and soaking of each layer till composition polymerisation. In the capacity of admixture influencing on coefficient of thermal dilatation of polymeric composition, it is used catalytic admixture and applied each of following layers from suspension of polymeric composition, containing greater quantity of catalytic admixture, than previous layer. Suspension contains catalytic admixture in amount 0.01-3 wt % per 1 kg of suspension.

EFFECT: providing of creation of durable and lasting anticorrosive coating, not subjected to destruction in conditions of temperature cycling, impingement attack and abrasive action.

5 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns quickly solidifying polyurethane-based polymer compositions with enhanced adhesion to metal surfaces and can be applied in production of protective coatings, sealing glues, mastics, particularly for sealing of perforated holes in paper-making machines. Composition includes polyfurite urethane forpolymer, liquid solidifier based on 3,3'-dichlor-4,4'-diaminodiphenylmethane and polyoxytetramethyleneglycol with molecular weight of 1000 at mol ratio of 0.95:0.1, aerosil, and additionally contains glycidylmetacrylate as adhesion additive, and can include di-(2-ethylhexyl)phthalate as plastifyer.

EFFECT: obtaining composition with high adhesion to metal surfaces and improved thixotropy without impairing high physical and mechanical characteristics level.

2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to polyurethane resin, which is a product of a reaction between at least one diisocyanate and components, containing functional groups, which have capacity to react with isocyanates, with the following composition: (a) first group, which is formed by one or more polyester-polyols based on ethers, each of which has average molecular mass ranging from 400 to 12000 g/mol, (b) second group, formed by one or more poly hydroxilated resins, chosen from a defined group of resins, (c) optional third group, formed by one or more polyols, each of which has average molecular mass, equal to or less than 800 g/mol, which are also chosen from a defined group of polyols, and (d) at least one amine and a reaction chain-stopping agent. The ratio of equivalent masses of diisocyanate and components, containing functional groups, with capacity to react with isocyanates, is chosen such that, naturally all isocyanate groups of diisocyanate are present as a product of the reaction with one of the above mentioned functional groups, with capacity to react with isocyanates. The invention also relates to the method of obtaining the above mentioned polyurethane resin, to polyurethane resin obtained through such methods, to coating for plastic substrates, containing the proposed resin, as a polyolefin binding substance, to use of such a polyurethane resin as a film forming substance in printing ink for printing on plastic substrates, as well as to the method of obtaining a laminate, which has a layer obtained when printing an image, including stages (a)-(d), with use of coating from polyurethane resin, and to a laminate, obtained using such a method.

EFFECT: obtaining a coating from polyurethane resin, with good heat resistance and excellent initial adhesiveness.

20 cl

FIELD: chemistry.

SUBSTANCE: coating for application to worn surfaces comprising composition including at least one curable polyurethane and at least one chlorinated polyolefine which provides improved adhesion to a worn surface as compared to adhesion of a coating composition including the same at least one curable polyurethane but not including at least one chlorinated polyolefine. The method of refinishing a worn surface comprises application of a curable polyurethane top finishing coating that includes at least one chlorinated polyolefine to the worn surface, and curing the curable polyurethane top finishing coating, wherein, before application of the curable polyurethane top finishing coating, the worn surface is treated with a solvent without any mechanical scraping.

EFFECT: improved interlayer adhesion.

37 cl, 3 tblr

FIELD: chemistry.

SUBSTANCE: hydropyle blocked polyisocyanates are produced by the method wherein: A) one or the several organic polyisocyanates interact with B) one or several organic compounds, containing, at least, one isocyanate reactive group and comprising b1) non-ionic hydropyle groups based on simple poly-alkylenoxide-polyethers containing at least 30 wt % of ethylene-oxide links, and/or b2) ionic or potentially ionic hydropyle groups a forming dissociation equilibrium depending upon pH in interaction with water, and, depending upon pH not having a charge and being charged positively or negatively, or interact with C) one or several blocking means containing, at least, one cyclic ketone with CH-acidity of the general formula (2) where X is the electron-acceptor group, R1, R2 mean independently from each other the hydrogen atom, saturated or unsaturated aliphatic residual containing up to 12 carbon atoms, n is 1, and, if necessary, interacting with one or several (cyclic)aliphatic mono- or polyamines with the amount of amino groups in a molecule of 1 to 4 and molecular weight of up to 400 note that, if necessary, it interacts with one or several multinuclear spirits with the number of hydroxyl groups in a molecule from 1 to 4 and molecular weight of up to 400, and, if necessary, with amino spirits in the presence D) of one or several catalysts or, if necessary, with auxiliary substances and additives and, if necessary E), with solvents. Polyisocyanates can be used for manufacturing varnishes, coatings, sizes, glues and molded products.

EFFECT: improved method of producing hydropyle blocked polyisocyanates.

6 cl, 6 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to mixtures consisting of blocked polyisocyanates designated as hardening agents in monocomponent lacquers of hot drying and comprising: (a) blocked polyisocyanate based on 1,6-diisocyanate hexane; (b) blocked polyisocyanate based on cycloaliphatic diisocyanates chosen from group comprising 1-isocyanato-3,3,5-trimethyl-5-ixocyanatomethylcyclohexane, bis-(4-isocyanatocyclohexyl)methane, 2,6-bis-isocyanatonorbornane, 2,5-bis-isocyanatonorbornane, 1,4-bis-isocyanatomethylcyclohexane and their mixtures, and (c) 3,5-dimethylpyrazole as a single blocking agent of agent of polyisocyanates named in (a) and (b). Blocked polyisocyanates are taken in the weight ratio (a) : (b) = 1:(1.8-2.2). Using mixtures of blocked polyisocyanates provides preparing clear lacquers with good acid resistance, stability against scratching and thermal yellowing.

EFFECT: improved and valuable properties of agents.

1 cl, 6 ex

FIELD: self-crossing dispersion for dressing of glass-fiber.

SUBSTANCE: the invention is pertaining to the field of the self-crossing dispersion for dressing of glass-fiber on the basis of polyurethane, polyurethane-polyurea or polyurea used for dressing glass-fiber. The invention is also dealt with a method of production of the indicated dispersion and with a sizing compound for glass-fiber. The indicated dispersion contains the blocked isocyanate groups bound with the polymer and in addition the reaction-capable hydroxyl or amino groups bound with the polymer. The dispersion is stable at storing up to 50 °C and is self-crossing at the temperature of 90°C up to 280°C. The dispersion represents a reaction product - a) at least one polyolic component; b) at least one di-, tri- and / or a polyisocyanate component, c) at least one hydrophilic nonionic or a (potentially) ionic component; d) at least one component, which is distinct from a)- or b)-, having molecular mass - 32-500 and at least one isocyanate-reaction capable group; and e) at least one monofunctional blocking component. The offered dispersions are suitable for use in the capacity of coatings for mineral emulsion carriers, textile and leather, lacquers and polishes for wood, and also may be applied as paint primers, bases, joint fillers or finishing coatings.

EFFECT: the invention allows to use the dispersions as coatings for mineral emulsion carriers, textile and leather, lacquers and polishes for wood and to applied them as paint primers, bases, joint fillers or finishing coatings.

21 cl, 4 ex

Ionic polyurethanes // 2214423
The invention relates to a charged polyurethanes, intended for use as an additive in the manufacture of paper

FIELD: chemistry.

SUBSTANCE: composition is characterised with viscosity 1500-25000 mPa·s at 25°C and contains fine-dispersed material 1-80 wt % at total polyol composition in polyol with equivalent weight 500 to 5000 and average nominal hydroxyl functionality 2 to 6, representing polyoxyethylene polyoxypropylene polyol with oxyethylene content 15-49 wt % at total oxyalkylene where oxyethylene group 20-80% being arranged on ends of polymer chains. Fine-dispersed material contains polyol reaction interaction with equivalent weight to 400, and diphenylmethandiisocyanate optionally containing its homologs with isocyanate functionality 3 or more, and/or modified versions of such polyisocyanates. There is also disclosed production process of such polyol compositions, and another polyol composition being mixed declared polyol composition and polyesterpolyol with average equivalent weight 500 or more, other than used to produce the composition specified above. There is also disclosed production process of elastic polyurethane foam with using said polyol compositions. Block (plate-shaped) or moulded elastic foam plastics are made of such polyol compositions.

EFFECT: improved load-sensitive characteristics, good fire resistance, easily recycled, internal defectless.

10 cl, 2 tbl

FIELD: technological processes, chemistry.

SUBSTANCE: invention is related to method for production of polyurethane foam with application of secondary waste of polyethylene terephtalate, and may be used for production of hard polyurethane foams. Polyurethane foam is produced by interaction of polyisocyanate with polyol component containing secondary waste of polyethylene terephtalate dissolved in triethanolamine or in mixture of mono-, di-, trichloracetic acids, in amount of not more than 67 wt % from total weight of polyol component. At that interaction is carried out at the ratio of polyol component : polyisocyanate as 1:1 - 1:2. Prepared polyurethane foams have good consumer properties, such as compression strength, oil-, heat resistance and reduced inflammability.

EFFECT: recycling of polymer wastes in the form of containers and package from polyethylene terephtalate, considerable reduction of polyurethane foam cost with simultaneous solution of environmental problems due to recycling of secondary polyethylene terephtalate.

16 ex

FIELD: chemistry.

SUBSTANCE: invention concerns humid-hardening compositions with high elasticity. Claimed composition includes at least one silane-functional polymer A, at least one amonisilane AS2, and at least one α-functional organodialcoxysilane in amount of 0.6-5.0 weight parts per 100 weight parts of polymer A. Additionally invention claims solidification of the composition and its application as sealants, glues and coatings, as well as methods of gluing and sealing using the composition.

EFFECT: humid-hardening composition with high elasticity and good mechanical and adhesive properties at the same time.

25 cl, 5 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyurethanedi(met)acrylates applicable as binders for powder coatings applied on metal substrates, plastic parts, fiber-reinforced plastic parts. Polyurethanedi(met)acrylates are obtained by interaction of diisocyanate component, diol component and hydroxy-C2-C4-alkyl(met)acrylate at mol ratio of x:(x-1):2, where x takes any value from 2 to 5. 1,6-hexanediisocyanate comprises 50 to 80 mol % of diisocyanate component, and one or two diisocyanates selected out of defined diisocyanate group where mol content of respective diisocyanates amount to 100 mol % comprise(s) 20 to 50 mol %, so that each diisocyanate comprises at least 10 mol % of diisocyanate component. Diol component includes not more than four different diols, and at least one linear aliphatic alpha, omega-C2-C12-diol comprises 20 to 100 mol % of diol component, while at least one (cyclo)aliphatic diol different from linear aliphatic alpha, omega-C2-C12-diols comprises 0 to 80 mol %. Each diol of the diol component comprises at least 10 mol % of diol component, and mol content or respective diols amounts to 100 mol %. Due to the absence of solvent in polyurethanedi(met)acrylate production, further cleaning of end product is not required, thus increasing process product output.

EFFECT: higher acid resistance of coating films applied and solidified with the use of powder coatings containing claimed polyurethanedi(met)acrylates.

6 cl, 15 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining compounded foam polyurethanes for operation as shock, heat and sound absorbing layers. Compounded foam polyurethanes are obtained by interaction of 100 weight parts of polyol component and 20 weight parts of polyisocyanate component, where polyol component is mixed preliminarily with 70-100 weight parts of rubber chips, and reaction mix is foamed and solidified at 160°C or higher to component destruction temperature. Butadiene and piperylene copolymer with 1200-3200 molecular weight and 0.8-1.1% content of hydroxylic groups is used as polyol component, and polymethylenepolyphenylisocyanate with 29-31% content of isocyanate groups is used as polyisocyanate component.

EFFECT: simplified composition and technological process for mix processing in elastic foam material production, facilitated utilisation of rubber industry waste, particularly rubber chips, and higher compounding degree and tension at 40% compression of foam polyurethanes obtained by the claimed method.

2 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to water one-component systems for covering, which are used in glue compositions, in sealants, lacquers and size. Said systems contain (I) at least one polyurethane (A), which contains chemically bound hydrophilic groups, and, in which groups containing active by Tzerevitinov hydrogen atoms are present in amount from 0 to 0.53 mmole/g in terms of relative content of non-voletile dispersion components, (II) at least one blocked polyisocyanate (B), which does not contain hydrophilic groups, and (III) water, weight component ratio between components A and B being chosen in such way that content of blocked isocyanate constitutes from 0.01 to 1.0 mole per 100 g of hard resin. Also described are method of obtaining said systems, their application in sizes for glass fibre, method of obtaining from them covering on carriers, as well as carriers with applied on them preparations for covering, containing systems for covering of composition described above.

EFFECT: obtaining system which ensures stability in storage, reduced water-absorption, higher water-resistance and improved adhesive strength in wet state.

11 cl, 1 tbl, 10 ex

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