Method of preparing dispersion of cross linking agents in water

FIELD: chemistry.

SUBSTANCE: method involves: (1) reacting a mixture of polyisocyanate and 5-30 wt % mono- or polyisocyanate with a hydrophobic group at 120-180°C in the presence of 0.5-5 wt % carbodiimide catalyst to form a polycarbodiimide containing isocyanate functional groups, with average number of carbodiimide functional groups equal to 1-10, in which the hydrophobic group is an alkyl containing 4-25 carbon atoms which, a fluorinated hydrocarbon, a silicon-containing hydrocarbon or an organosilicon polymer, (2) breaking and/or prolonging the chain from the polycarbodiimide containing isocyanate functional groups by adding a compound in amount of 0.1-1.0 equivalents with respect to content of isocyanate functional groups, where the said compound contains a hydrophilic group and one or more amine and/or hydroxyl functional group simultaneous or subsequent blocking of the remaining isocyanate functional group with a compound containing one or more amine and/or hydroxyl functional groups and, possibly, a hydrophobic group, where the hydrophobic group is an alkyl group containing 4-25 carbon atoms, a fluorinated hydrocarbon, a silicon-containing hydrocarbon or an organosilicon polymer, (3) dispersing the obtained compound in water, and (4) regulating pH of the formed dispersion to a value between 9 and 14 by adding to the obtained dispersion a hydroxide of an alkali metal or a buffer, where the buffer is effective at pH 9-14. The invention also relates to coating mixture containing polycarbodiimide dispersion prepared using the method described above, as well as a curable material obtained by applying said coating mixture onto a substrate.

EFFECT: meeting the requirement for low amount of hydrophilic material needed for dispersing polycarbodiimide, obtaining films or coatings which are less sensitive to water, more resistant to solvents and which have improved properties during attrition testing in wet state, and achieving high cross-link density of the polymer network.

21 cl, 38 ex, 5 tbl

 

Polycarbamide widely known as cross-linking agents for aqueous polymer containing a functional group of carboxylic acids.

Overview of achievements in the field of production and application of polycarbamide presented in WO 2005/003204.

This patent application describes the development of a dispersion of polycarbamide, which stabilized at a high value of pH by adding a base or buffer.

However, when using this method the average number of functional carbodiimide groups in the molecule of the polymer is limited due to the significant increase in viscosity of the reaction mixture, when polycarbamide chain becomes longer and longer with increasing time of reaction in the first stage of cooking. Therefore, it is difficult to mixing the intermediate containing isocyanate functional groups polycarbamide, as well as mixing the formed later intermediate product containing hydrophilic functional groups. Consequently, it becomes difficult dispersion of this intermediate in the water.

The purpose of this invention is the provision of means, in fact, devoid of the above disadvantages.

Description of the invention

According to the present invention is provided by way of sentence is the service of stable aqueous dispersions of polycarbamide, intended for use as cross-linking agents, characterized by the following:

- carrying out the reaction of MDI with 120-180°C in the presence of 0.5-5% of the catalyst for the formation of carbodiimide to obtain containing isocyanate functional groups polycarbamide with an average content of the carbodiimide functional groups is 1-10, and containing 5-30 wt.% mono - or MDI with a hydrophobic group, a mono - or polyisocyanate which is involved in the formation containing isocyanate functional groups polycarbamide, and in which the hydrophobic group is a hydrocarbon containing 4-25 carbon atoms, fluorinated hydrocarbon, silicon-containing hydrocarbon or kremnijorganicheskim polymer

- truncation and/or continue the chain from the containing isocyanate functional groups polycarbamide addition in quantities of from 0.1 to 1.0 equivalents with respect to the content of the isocyanate functional groups of the compound containing a hydrophilic group and one or more amine and/or hydroxyl functional group with simultaneous or sequential block the remaining isocyanate functional groups of a compound containing one or more amine and/or hydroxyl functional group and, possibly, a hydrophobic group, in which hydrophobia group is a hydrocarbon, containing 4-25 carbon atoms, fluorinated hydrocarbon, remasterise hydrocarbon or organosilicon polymer

by dispersing the compounds in the water

- regulation of the pH of the resulting dispersion to the level 9-14 adding a base or buffer during or after dispersion in water.

The amount of the carbodiimide functional groups in polycarbamide the chain can be chosen in the control flow of the first reaction stage. An indicator of this value is the amount remaining after the first stage reaction of the isocyanate.

Polycarbamide chain with a smaller number of functional groups is obtained by using a shorter time of reaction, and polycarbamide chain with a large number of functional groups is obtained by using a longer reaction time.

Dispersion polycarbamide contains 0-25% of an organic solvent, directionspanel towards polycarbamide. The examples are N-methylpyrrolidinone, N-ethylpyrrolidin, dimethyl ether of dipropyleneglycol, dimethyl ether of diethylene glycol, methoxypropylacetate. For environmental reasons it is preferable that the dispersion did not contain any organic solvents.

the hen hydrophobic group mono - or diisocyanate or connection, containing one or more amine and/or hydroxyl functional group that is a hydrocarbon, this compound preferably contains from 6 to 20 carbon atoms.

The block containing isocyanate functional groups polycarbamide chain compound containing a hydroxyl functional group occurs in normal conditions at a temperature between 50 and 120°C and with the possible use of a conventional catalyst, such as organic or compound of tin, aluminum, bismuth, zirconium, zinc or Nickel and/or the compound containing the functional group of the tertiary amine. Blocking a compound containing an amine functional group, is also under normal conditions and used a temperature between 0 and 60°C. in Addition, the compound containing an amine functional group may partially or entirely be added after dispersion in aqueous phase.

Surprisingly, the viscosity containing isocyanate functional groups polycarbamide and then the resulting intermediate product with a broken or continue the chain, prepared in this way was lower than the viscosity of the respective intermediate products with a similar amount of carbodiimide functional groups formed by the method, do not use the next containing a hydrophobic functional group compounds, which is described in WO 2005/003204. Thus it is possible for the preparation of polycarbamide even with a large number of functional groups. The second effect of lengthening polycarbamide chain is that it increases the average concentration of carbodiimide, as it reduces the contribution of molecular weight end-group.

Another advantage is that the product possesses emulsifying ability as a consequence of combining in a single connection hydrophobic and hydrophilic material. Compared with the previous development shows the need for fewer hydrophilic material required for the dispersion of polycarbamide, and that after use as a cross-linking agent polycarbamide dried film or coating are less sensitive to water. A further advantage is that after applying polycarbamide as a crosslinking agent in the polyurethane, the resulting film or coating are more resistant to solvents and demonstrate the best characteristics when tested for abrasion in the wet state. Finally, there is a higher density of crosslinking of the polymer grid.

Hydrophobic group polycarbamide containing fluorinated hydrocarbons, contribute to protivotarannymi action and more is markedly pronounced hydrophobic crosslinked film or coating.

Hydrophobic group polycarbamide containing silicon-containing components, contributing to the best rheological properties of the mixture used, to the more hydrophobic character and to the best tactile qualities crosslinked film or coating.

There are several options for the composition of mono - and/or diisocyanate suitable for use in the method.

Containing a hydrophobic group monoisocyanates may be an isocyanate containing a linear or branched alkyl, alkylenes, alcylaryl or alkylenedioxy group 4-25 carbon atoms. For example, it may be an isocyanate-containing alkyl, cycloalkyl, alcylaryl or arylalkyl functional groups, such as utilitzant, mexilitine, acterization, undecision, dodecylsulfonate, hexadecanesulfonate, octadecylsilane, cyclohexylsulfamate, phenylisocyanate, trilinolenin, 2-heptyl-3,4-bis(9-isocyanatophenyl)-1-pentylcyclohexane.

An additional choice is that monoisocyanates and/or polyisocyanate is MDI adduct containing hydroxyl or amine functional group of compounds with a linear or branched alkyl, alkilinity, alcylaryl or alkylenediamines group 4-25 carbon atoms.

A further choice is that containing the Hydra is fabou group monoisocyanates is an isocyanate, containing alkyl, alkylenes, alcylaryl or alkylenedioxy group that contains 1-50 of fluorine atoms. Examples of this are forgenerations, fertilisation, portail-3-(trifluoromethyl)phenylisocyanate.

In addition, there is a choice that monoisocyanates and/or polyisocyanate is MDI adduct containing hydroxyl or amine functional group of compounds with a linear or branched alkyl, alkilinity, alcylaryl or alkylenediamines group containing 1-50 fluorine atoms.

Moreover, the choice is that monoisocyanates and/or polyisocyanate is MDI adduct and organosilicon compounds containing hydroxyl or amine functional group, organosilicon compounds containing hydroxyalkyl or aminoalkyl functional group.

Breakage or the continuation of a chain of carbodiimide containing isocyanate functional groups, a compound containing a hydrophilic group and one or more amine and/or hydroxyl functional group, and a compound containing one or more amine and/or hydroxyl functional group and containing no hydrophilic groups, can be carried out during the formation of polycarbamide at 120-180°C, after the formation of polycarbamide at 0-120°is or after dispersion in water at 0-60°C.

With the purpose of obtaining a stable dispersion pH polycarbamide dispersion preferably is regulated to a value between 11 and 13. Used in the way that the catalyst obtain a carbodiimide can be any conventional catalyst for the formation of carbodiimide, but preferably is 1-methylphosphono-1-oxide.

The polyisocyanate used to prepare polycarbamide is toluyl-2,4-diisocyanate, toluyl-2,6-diisocyanate and their mixtures, difenilmetana-4,4-diisocyanate, 1,4-phenylendiamine, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 1,6-hexyldecanol, 1,4-cyclohexyldiamine, norbornadiene or their mixture and, preferably, dicyclohexylmethane-4,4'-diisocyanate.

Used at the last stage of the way the connection with the basic properties intended to stabilize variance. This alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide, or trialkylamine, or trialkylamine containing hydroxyl functional groups.

A further choice is that the specified radix or part thereof introduced into polycarbamide chain when blocking polycarbamide chain of dialkylamino-alkylamino or alcohol, and/or adding tretin the th Amin, containing polyhydric alcohol or polyamine in quantities from 0.01 to 0.3 equivalents in relation to the contents of the MDI, during or after the formation of polycarbamide.

As an alternative to the base, in order to regulate the pH value to the desired value and maintaining it at this level can use the buffer. For this it is convenient the use of buffers, which are now in the range of pH values between 9 and 14. Their examples are phosphate, carbonate, Tris(hydroxymethyl)aminomethane buffer or buffer from the amino-alkylsulfonic acid.

The compound containing a hydrophilic group and one or more amine and/or hydroxyl functional groups, is politicsi-mono - or diola, politicsi/polypropene-mono - or diola, politicsi-mono - or diamine, politicsi/polypropene-mono - or diamine, diol or diemonsterdie polyalkoxyalkyl end chain, hydroxy - or aminoalkylsilane, dialkylaminoalkyl alcohol or amine, or mixtures thereof, with a molecular mass of this compound is between 100 and 6000 and preferably between 200 and 2000.

Just as described in WO 2005/003204, before, during or after the formation of polycarbamide can be added mono - or polyol or a mono - or polyamine in an amount of from 0.01 to 0.30 equivalents of the about toward polyisocyanates, such polyhydric alcohol or polyamine are, for example, mono - or polyhydroxyalkane, polyester mono - or polyhydric alcohol, polyetherpolyols, polycarbonate polyol, polycaprolactone-polyol, a mono - or polyamidoamine, polyester mono - or polyamine. As described in WO 2005/003204, the goal is to increase the distance between the forming cross-linking functional groups.

In the process of dispersing in water blocked or extendable chain compounds can be used in conventional non-ionic, anionic or cationic emulsifier.

The invention also relates to a mixture for coating containing a dispersion of polycarbamide as a cross-linking agent and dispersed in water, the polymer, and the polymer contains a functional group of carboxylic acid, and may contain a solvent. Examples of such polymers are polyurethanes, acrylate or methacrylate polymers or copolymers, polyvinyl acetate, latexes.

In addition, a mixture for coating may contain solvents or conventional additives, such as emulsifiers, dyes, pigments, moisturizers, a leveling additive, silicone materials, fillers, plasticizers, matting agents.

Finally, the invention applies to the cured material, acaemy applying the mixture to a coating on the substrate and the evaporation of water and, in the presence of solvent.

Suitable substrates are, for example: leather, artificial leather, plastic masses, such as polyurethanes, polyacrylates, polyethylene, polypropylene, PVC or polyester, paper, cardboard, fabric, nonwoven material, foam, wood, glass, metal. Further, the present invention is illustrated in the following the invention non-limiting examples. Needless to say that within the defined scope of the present invention, there are many other incarnations.

Examples

Examples 1-19. Preparation of aqueous dispersions of polycarbamide based on dicyclohexylmethane-4,4'-diisocyanate and octadecylsilane.

Presented in the Table And the mixture dicyclohexylmethane-4,4'-diisocyanate (hereinafter referred to as HMDI), octadecylsilane (hereinafter referred to as ODIC) and 2 g of 1-methylphosphono-1-oxide was heated in nitrogen atmosphere to 140°C with stirring and heating continued until the content of isocyanate according to the table A. the mixture is Then cooled to 90-100°C. the reaction Time was 8 hours. Added are listed in the Table And compounds containing hydroxyl functional group, so that their total number was equimolecular in relation to the number of isocyanate functional groups. As a catalyst EXT is ulali dibutyltin tin in an amount of 0.01 wt.% and further the reaction mixture was held at 90-100°C. until the disappearance of the signal of the isocyanate in the IR spectrum, that took about 3 hours. In the case of Example 11 after 1 hour after start of the reaction was added dimethylethanolamine. The mixture was cooled to 60-65°C and dispersible in water at 60-65°C, and the solid content was set equal to 35%. In the case of Examples 12 and 13 in the future, to the dispersion was added compound containing amine functional groups, and the mixture was stirred for 10 minutes was Added 10%sodium hydroxide solution to set the pH of 11-12. The samples were tested for stability at 50°C. the Amount of the carbodiimide was checked every 2 weeks. The products were stable for at least 8 weeks at 50°C.

Examples 20-22. Comparative example: preparation of aqueous dispersions of polycarbamide based on dicyclohexylmethane-4,4'-diisocyanate.

Presented in the Table In the variance of polycarbamide based on cyclohexylmethyl-4,4'-diisocyanate and blocked PEG-350 (polyethoxyethanol with an average molecular weight of 350), was prepared according to the method described in WO 2005/003204. These polycarbamide not contain any additional hydrophobic groups. In order to avoid content in the final products too a large number of hydrophilic material used in these cf is niteljnykh examples polyethoxysiloxane compounds have a lower molecular weight, than that used in examples 1-19.

When comparing the viscosity in Examples 20, 21 and 22 with a viscosity of Examples 1, 2 and 3 and Examples 5 and 6 shows that the viscosity of Examples 1, 2 and 3 and Examples 5 and 6 are much lower than the viscosity in Examples 20, 21 and 22, while the carbodiimide functional groups present in the polymer in similar estimated amounts.

Examples 23-35. Preparation of aqueous dispersions of polycarbamide based on HMDI.

Was repeated way of Examples 1-13, except that an aqueous solution of sodium hydroxide was replaced with 5 g of a solution of 0,01M disodium phosphate buffer. The samples were tested for stability at 50°C. the Amount of the carbodiimide was checked every 2 weeks. The products were stable for at least 8 weeks at 50°C.

Example 36. Check products Examples 1, 2, 3, 4, 5, 6, 7 as cross-linking agents for polyurethane dispersion in comparison with the products of Examples 20 and 21.

6% of the variance of Examples 1, 2, 3, 4, 5, 6, 7, 20 and 21 was mixed with EN-5509 (dispersion of polyurethane Stahl Europe).

Each dispersion was sprayed on a piece of leather to the formation of the layer thickness of 50 μm, and the piece of skin was pre-treated EN-3952 (ground floor Stahl Europe), and skin with powder was dried for 3 minutes in a preheated 80°C oven. The skin samples with coating was tested on the East is unknown in the wet state on the device Veslic. In this test, the skin samples were rubbed a small piece of wet felt under pressure 500, After every 250 rubbing of their total number, equal to 1000, the surface subjected to abrasion of the skin was checked for damage. For special applications, the coating must withstand without damage at least 1000 rubbing. The results of this test are presented in Table C.

Presented in a Table With the results show that more than 1000 rubbing without damaging the film of RU-5509 and crosslinking agent are provided only if the estimated amount of the carbodiimide functional groups in the polymer is greater than 4 and if, in addition, the composition is cross-linked polymer contains at least 5-30 wt.% mono - and/or MDI containing a hydrophobic group, referring to the polyisocyanate, participating in education containing isocyanate functional groups polycarbamide.

Table
A crosslinking agent of ExampleThe number of rubbing wet film of RU-5509 and cross-linking agent
1Less than 1000
2More than 1,000
3More than 1,000
4More than 1,000
5More than 1,000
6More than 1,000
7More than 1,000
20Less than 1000
21Less than 1000

Example 37. Product testing Examples 1, 2, 3, 4, 5, 6, 7 as cross-linking agents in polyurethane dispersion with a comparison with the products of Examples 20 and 21.

6% of the variance of Examples 1, 2, 3, 4, 5, 6, 7 20 and 21 was mixed with EN-3901 (dispersion of polyurethane Stahl Europe).

Each dispersion was applied with a layer thickness of 200 μm on a sheet of glass and glass coated sheet was dried for 1 day at room temperature and then 1 hour at 80°C. Samples of the dried film was tested for absorption of ethyl alcohol. In this test, samples are dried and weighed film for 1 hour immersed in ethanol, and then was determined by the increase in the mass of the film.

In addition, the measured mechanical properties and elongation of the films using the device MTS Synergy 200. The results of the tests are presented in Table D.

The results show that cross-connection, receiving the data using a cross-linking agent of Examples 1, 2, 3, 4, 5, 6 and 7, more durable than obtained by using a crosslinking agent, Examples 20 and 21, which shows a higher stress in the film, developing tensile film, and lower weight gain caused by immersion of the film in ethyl alcohol.

350
Table D
A crosslinking agent of ExampleMechanical properties (MPa)a)The increase in mass (%)
M-100M-200M-300M-400Elongationb)
13,956,2010,017,8460190
2of 5.05the 7.8513,2-370170
35,208,1514,0-155
4of 5.408,6515,4-370155
55,00---190160
6the 5.258,2513,8-310160
75,158,05--240160
204,106,109,315,9440200
214,407,1--290190
a) MPa - megapascal (106Nm-2). Mechanical properties were measured using the MTS device Synergy 200. M-100, M-200, M-300 and M-400 is the magnitude of the elastic stress of the films when the 100%modulus, 200%, 300% and 400%, respectively
b) Elongation - the maximum elongation at the moment of rupture, as defined on the device MTS Synergy 200
c) weight Increase - percentage increase in mass of the film when it is immersed in ethyl alcohol

Example 38. The test products of Examples 14, 15, 16, 17, and 19 as cross-linking agents in polyurethane dispersion using the product of Example 21 as a comparative example.

10% dispersions of Examples 14, 15, 16, 17, and 19 were mixed with EN-13-085 (dispersion of a polyurethane from the company Stahl Europe).

Each dispersion was applied with a layer thickness of 200 μm on a sheet of soft PVC and PVC coated was dried for 1 day at room temperature and then 1 hour at 80°C. Samples of PVC coated were tested for soil release properties. In this test, the coating was rubbed over 1000 cycles with a piece of cloth that contained control the amount of dirt, despite the fact that the fabric clung to the floor with a constant force. Then half of the worn surface was irrigated with water containing some quantity the quantity of soap. Dirt-repellent effect was determined visually by comparing the color intact cover, cover after cleaning and coating after cleaning and washing, where bright colour was assigned to category 1, while no staining was designated a category 5. The results are presented in Table E. in Addition, were evaluated water-repellent properties, the obtained data are also collected in Table E. In this test, the coating surface was placed drops of various mixtures of water and 2-propanol, and, depending on the spreading of these drops were given the assessment category 6 displays a strong water-repellent properties, and category 1 indicates poor water repellency.

The results show that cross-linking agents containing a hydrophobic group, have a beneficial effect on soil-repellent quality, and water-repellent properties. Cross-linking with cross-linking agents of Examples 14, 15, 16, 17, 19 provided improved soil release quality compared with the cross-linking agent of Example 21, which demonstrated a higher assessment of their warning of pollution qualities. And stitching using crosslinking agents of Examples 14, 15, 16, 17, 19 provided improved water resistant, which is evident from higher estimates of the results of their tests, videotalk the matter of property.

Table E
An example of a cross-linking agentGazetteliveWater resistant
Without washingAfter washing
2124
14245,5
15235
16235
17235
19245
21224

1. Method of preparation of stable aqueous dispersions of polycarbamide intended for COI is whether as cross-linking agents, including:
- the interaction of a mixture of MDI and 5-30 wt.% mono - or MDI with a hydrophobic group at 120-180°C in the presence of 0.5-5 wt.% carbodiimide catalyst for the formation containing isocyanate functional groups polycarbamide with an average number of carbodiimide functional groups 1-10, in which the hydrophobic group is containing 4-25 carbon atoms by alkyl, fluorinated hydrocarbon, silicon-containing hydrocarbon or organosilicon polymer
- break and/or continue the chain from the containing isocyanate functional groups polycarbamide by adding in an amount of from 0.1 to 1.0 equivalents with respect to the content of the isocyanate functional groups of the compound containing a hydrophilic group and one or more amine and/or hydroxyl functional group with simultaneous or subsequent lock the remaining isocyanate functional groups of a compound containing one or more amine and/or hydroxyl functional group and, possibly, a hydrophobic group, the hydrophobic group is an alkyl group containing 4-25 carbon atoms, fluorinated hydrocarbon, silicon-containing hydrocarbon or organosilicon polymer
- the dispersion of the compounds in the water,
- regulation of the show is La pH of the resulting dispersion to a value of 9 to 14 by adding to the resulting aqueous dispersion of a hydroxide of an alkali metal or buffer, when this buffer is effective in the range of pH 9 to 14.

2. The method according to claim 1, characterized in that the dispersion polycarbamide contains 0-25% of an organic solvent, directionspanel towards polycarbamide, and preferably does not contain any organic solvents.

3. The method according to claim 1, characterized in that the hydrophobic group is mono - or MDI or compounds containing one or more amine and/or hydroxyl functional group is an alkyl containing from 6 to 20 carbon atoms.

4. The method according to claim 1, in which monoisocyanates and/or polyisocyanate is MDI adduct containing hydroxyl or amine functional group of compounds with a linear or branched alkyl, alkilinity, alcylaryl or alkylenediamines group 4-25 carbon atoms.

5. The method according to claim 1, characterized in that the containing hydrophobic group monoisocyanates is an isocyanate containing alkyl, alkylenes, alcylaryl or alkylenedioxy group that contains 1-50 fluorine atoms.

6. The method according to claim 1, characterized in that monoisocyanates containing a hydrophobic group, is perteneciente, fertilisation, 3-(trifluoromethyl)phenylisocyanate.

7. The method according to claim 1, in which monoisocyanates and/or isocyanate are MDI adduct containing hydroxyl or amine functional group compounds with alkyl, alkilinity, alcylaryl or alkylenediamines group containing 1-50 fluorine atoms.

8. The method according to claim 1, in which monoisocyanates and/or polyisocyanate is MDI adduct and organosilicon compounds containing hydroxyl or amine functional group, organosilicon compounds containing hydroxyalkyl or aminoalkyl functional group.

9. The method according to claim 1, characterized in that the breakage or the continuation of a chain of carbodiimide containing isocyanate functional groups, a compound containing a hydrophilic group and one or more amine and/or hydroxyl functional group, and a compound containing one or more amine and/or hydroxyl functional group and containing no hydrophilic groups, carried out during the formation of polycarbamide at 120-180°C, after the formation of polycarbamide at 0-120°C or after dispersion in water at 0-60°C.

10. The method according to claim 1, characterized in that the pH of the dispersion of polycarbamide adjust to a value between 11 and 13.

11. The method according to claim 1, characterized in that the catalyst obtain a carbodiimide is 1-methylphosphono-1-oxide.

12. The method according to claim 1, characterized in that used for the preparation of polycarbamide the polyisocyanate is toluyl-24-diisocyanate, toluyl-2,6-diisocyanate and their mixtures, difenilmetana-4,4-diisocyanate, 1,4-phenylendiamine, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 1,6-hexyldecanol, 1,4-cyclohexyldiamine, norbornadiene or their mixture.

13. The method according to claim 1, characterized in that the polyisocyanate is dicyclohexylmethane-4,4'-diisocyanate.

14. The method according to claim 1, characterized in that the alkali metal hydroxide is lithium hydroxide, sodium hydroxide or potassium hydroxide.

15. The method according to claim 1, characterized in that the alkali metal hydroxide or part thereof is introduced into polycarbamide chain when blocking polycarbamide chain by dialkylaminoalkyl or alcohol, and/or by adding a tertiary amine containing a polyhydric alcohol or polyamine in quantities from 0.01 to 0.3 equivalents in relation to the contents of the MDI, during or after the formation of polycarbamide.

16. The method according to claim 1, characterized in that the effective pH of the buffer is in the range between 9 and 14.

17. The method according to claim 1, characterized in that said buffer is a phosphate, carbonate, Tris(hydroxymethyl)aminomethane buffer or buffer aminoalkylsilanes acid.

18. The method according to claim 1, characterized in that the connection sod is rashee hydrophilic group and one or more amine and/or hydroxyl functional groups, is politicsi - mono - or diola, politicsi/polypropene - mono - or diola, politicsi - mono - or diamine, politicsi/polypropene - mono - or diamine, diol or diemonsterdie polyalkoxyalkyl end chain, hydroxy - or amino-alkylsulfonate, or dialkylaminoalkyl alcohol or amine, or mixtures thereof, with a molecular mass of this compound is between 100 and 6000 and preferably between 200 and 2000.

19. The method according to claims 1 to 18, characterized in that before, during or after the formation of polycarbamide add mono - or polyol or a mono - or polyamine in an amount of from 0.01 to 0.30 equivalents relative to the polyisocyanates, such polyhydric alcohol or polyamine are, for example, mono - or polyhydroxyalkane, simple ester of mono - or polyhydric alcohol, a complex ester of a polyhydric alcohol, polycarbonate polyol, polycaprolactone-polyol, a mono - or polyamidoamine, polyester mono - or polyamine.

20. The mixture coating containing a dispersion of polycarbamide prepared by the method according to one of claims 1 to 19, as a crosslinking agent and dispersed in water, the polymer, and the polymer contains a functional group of carboxylic acid, and may contain a solvent.

21. Cured material obtained by applying a mixture for coating the about paragraph 20 on the substrate and the evaporation of water and, in the presence of solvent.



 

Same patents:

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: protective coatings.

SUBSTANCE: invention relates to a method for applying onto wood substrate coating with increased resistance to effects of chemical products. Method comprises following stages: (i) addition, to aqueous polyatomic alcohol suspension, of composition based on isocyanate(s) and anionic surfactant having hydrophilic portion containing anionic group and lipophilic portion containing hydrocarbon radical, isocyanate(s)-based composition containing no more than 30% surfactant bound to isocyanate group, to form aqueous emulsion of isocyanate(s) and surfactant; (ii) applying resulting mixture onto wood surface of substrate; and (iii) aging to complete reaction of isocyanate(s) with polyatomic alcohol required to form polyurethane coating.

EFFECT: increased strength of coating (at a level of 90 units) and acquired resistance to a variety of chemical, cosmetic, and woof products according to corresponding standard.

18 cl, 4 dwg, 5 ex

FIELD: rocket technique, chemical technology.

SUBSTANCE: invention relates to a method for preparing a hardening agent for polyurethane compositions based on oligodiene rubbers. Invention describes a method for preparing a hardening agent for polyurethane compositions consisting of the following components, wt.-%: oligodiene urethane prepolymer, 80-91; 20% solution of triphenylmetane triisocyanate in dichloroethane, or 27% solution of triphenylmethane triisocyanate in ethyl acetate, 7-13, and, optionally, transformer oil, 0-10. The process is carried out in the range of temperatures 55-65°C, under residual pressure 1333 Pa for 6 h. Invention provides preparing polyurethane compositions possessing the rupture strength value at the level 38 kgf/cm2, relative elongation 350-600%, elasticity modulus at 50°C at the level 41 kgf/cm2 and adhesion strength to ballistic fuel 41 kgf/cm2. Proposed compositions are able to provide working ability of articles in the range of temperature from -50°C to +50°C.

EFFECT: improved preparing method.

2 tbl, 4 ex

Disperse system // 2204570
The invention relates to one-component dispersion, which has the ability of blending at low (room) temperatures

The invention relates to the production of flexible foams and can be used in the automotive industry, furniture industry, for the production of sports equipment

The invention relates to the field of production of two-component compounds with increased strength and can be used to seal the membrane elements

FIELD: process engineering.

SUBSTANCE: invention relates to flexible elastomer polyurethane skin for decoration of car interior and method of its production. Proposed skin comprises first and second flexible layers produced by spraying first and second reaction mixes on each other to produce polyurethane. Spraying of second reaction mix is started in no later than 90 s after termination of spraying first reaction mix. First reaction mix is intended for producing aliphatic polyurethane and consists of isocyanate component, components reactive with respect to isocyanate, and catalytic component with lead content less than 2 molar fractions. Second reaction mix is intended for producing aromatic polyurethane. Mean weight of unit surface of proposed skin makes, at least, 0.6 kg/m2 and mean flexure modulus makes less than 30 MPa.

EFFECT: higher flexibility, no lead, stability of colour.

24 cl, 6 tbl, 6 ex, 4 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to foamed polyurethane which can be used in many fields with strict environmental safety requirements, where the percentage content of renewable resources and high tear resistance are required. Foamed polyurethane is a product of reaction of at least one polyisocyanate with a polyol component, in the presence of at least one foaming agent and at least one catalyst selected from a group comprising amine catalysts and organotin catalysts, if needed, in the presence of at least one surfactant, other cross-linking agents, chain extenders, pigments, flame retardants and filling materials. The polyol component contains a polymer-polyol (PMPO) selected from a group comprising styreneacrylonitrile (SAN) polymer-polyols, PHD polymer-polyols and PIPA polymer-polyols, at least 25 wt % of the weight of the polyol component of the vegetable oil hydroxylate with functionality between 1.5 and 6 and molecular weight between 300 and 10000, and 0-3 wt % of the weight of the polyol component of a polyatomic aliphatic alcohol with functionality between 3 and 8 and molecular weight less than 350, and if needed, a polyol not based on vegetable oil. The invention also describes a method of producing the foamed polyurethane described above.

EFFECT: obtaining foamed polyurethane, having considerably improved tear resistance, breaking strength and relative elongation.

27 cl, 22 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to a single-component primer composition for substrates made from glass and/or plastic, having setting time of at least 1 month. Said composition includes: a base primer composition including (a) an isocyanate functional prepolymer derived from the reaction of an aliphatic polyisocyanate and a polyol, and which is partially reacted with an amino group of a secondary aminosilane, wherein the aminosilane includes two or three methoxy groups bound to a silicon atom, two or three ethoxy groups bound to a silicon atom, or a combination thereof; (b) an isocyanate functional prepolymer with an isocyanate content greater than 1%, which is the reaction product of an aromatic polyisocyanate and a polyol of Mn>300; and (c) at least one solvent for the components (a) and (b); and an ingredient including an oxazolidine ring or derivative thereof; a second adduct (i) of an aromatic polyisocyanate and (ii) mercaptosilane, aminosilane or both; a film-forming polymer. The invention also describes glued structure having a glass or plastic panel, containing the said composition, a method of gluing the glass panel to the frame of a vehicle, comprising a step for applying said composition and a glued structure made using said method.

EFFECT: obtaining primer with long setting time, which exhibits excellent stability during storage, during application of which the surface does not swell.

13 cl, 4 tbl

Foamed polyurethane // 2411254

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethane used, for example, as seat cushions, decorative elements for the inside of cars etc, and to methods of producing said polyurethane via radical-initiated cross-linking in the presence of at least one agent which produces radicals and under the effect of ionising radiation, respectively. According to the given method, at least one polyfunctional isocyanate, at least one polyol which is completely or mainly polyether polyol with molecular weight higher than 1500, and foaming ingredients are subjected to addition polymerisation and a foaming reaction in the presence of at least one component with a reactive double bond to obtain a foamed mass with a polyurethane matrix. The polyfunctional isocyanate is not 4,4'-diisocyanate diphenylmethane or does not contain 4,4'-diisocyanate diphenylmethane, and the foamed mass undergoes radical-initiated cross-linking with the component with the reactive double bond which is an acrylate or methacrylate polymer containing at least two hydroxyl groups which also react with the said isocyanate so as to be embedded into the polyurethane matrix.

EFFECT: obtaining elastic, semi-rigid and rigid open-pore and closed-pore foam with virtually no change in colour and precuring effect, which are stable, can withstand high loads and have sufficient rigidity for retaining the shape during use.

30 cl, 2 ex, 11 tbl

FIELD: chemistry.

SUBSTANCE: composition is obtained by mixing of (a) first polyurethane with end silane groups obtained by interreaction of: (i) monofunctional compounds with (ii) isocyanate component containing two isocyanate groups and following interreaction of reaction product of components (i) and (ii) with (iii) compound containing group reactive toward isocyanate and one or more reactive silane groups whereat at least 10 mole % of component (iii) is compound of formula (I): with formation of moisture-crosslinked alcoxysilane functional polyesterurethane; and (b) second polyurethane with end silane groups obtained by interreaction of: (i) linear, branched or cyclic alkylmonofunctional alcohol containing 1-20 of carbon atoms, amine and/or thiol with (ii) isocyanate component containing two isocyanate groups and with product of the interreaction of components (i) and (ii) with compound (iii) containing group reactive toward isocyanate and one or more reactive silane groups corresponding to formula (I).

EFFECT: coating films applied to the substrate possess excellent tensile strength and tensile elongation which provides reducing of film cracking, blistering and peeling.

17 cl, 4 ex

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 two-pack composition for ground reinforcement by compression in mining and construction engineering. Composition includes forpolymer component based on methylenediphenyldiisocyanate and multiatom alcohol component with several functional groups, mixing and compression of which ensures fast polymerisation, reaction temperature of 130°C, foaming below five times increase of initial volume, mechanical tension of 1 MPa by ageing for 30 minutes to 5 hours after gluing, and devoid of significant fissuring caused by internal tension during polymerisation. Limited reaction capability is achieved by volumetric mixing of components at 1:1 ratio of methylenediphenyldiisocyanate forpolymer with N=C=O number from 18 to 24, preferably 22, to multiatom alcohol with several functional groups maintaining N=C=O number from 1.1 to 1.4, and ensures good adhesion to carrier. One of the composition components includes foam suppressant consisting of non-ion surfactants and non-saponifying substances.

EFFECT: obtaining composition with enhanced fireproof properties, limited foaming at contact with unlimited water quantity, ensuring reduced danger of forming fractures and heating related to possible air leakage, and good mechanical properties.

15 cl

FIELD: chemistry.

SUBSTANCE: invention concerns multicomponent local foam system for obtaining foam polyurethanes for local construction purposes, consisting of polyisocyanate (component A), and polyene containing water (component B), stored in separate containers, and epoxy resin based on bisphenol A and bisphenol F, and/or siloxane forpolymer with average mol weight from 200 g/mol to 10000 g/mol with reactive end alcoxy groups (component C), generic catalyst for polyurethane generation reaction and/or generic binding agent for siloxane forpolymer (component D) in spatially divided form, and optional filler, one or more colourants or pigments and generic additives. When mixed, the components of foam system form interpenetrating polymer mesh structure out of foamed polyurethane and at least one other polymer, with excellent adhesion to adjoining wall material, thus reducing water penetration or forming mechanically stable cork in case of fire to render resistance to fire. Claimed foam system is foaming and solidifying in severe conditions on construction site, e.g. at temperatures from 0°C to 40°C, and non-homogeneously filling of volume.

EFFECT: sealing of fractures and/or through orifices in building walls and/or floors.

23 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention concerns expandable polyamide composition consisting basically of: (A) compound with at least one isocyanate group, possible blocked one, (B) polyamide, and (C) compound with at least one acid group, preferrably carboxyl one. The invention also concerns production of polyamide foam from the said composition and the foam produced in this process. The said process allows obtaining foam directly from the said composition, i.e. without addition of any extra compounds, as well as foaming reaction control. Moreover, according to the invention, this foam has regular cell distribution conforming to the closed type and can be applied in various fields, e.g. in thermal or sound insulation and saddlery.

EFFECT: obtainment of foams of various types and properties.

30 cl, 1 tbl, 7 ex, 1 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing stable aqueous dispersions of polycarbodiimide for using as a cross-linking agent and no containing organic solvents. Method is realized by carrying out interaction of polyisocyanate in the presence of 0.5-3% of catalyst in reaction for formation of carbodiimide to form polycarbodiimide intermediate substance at 120-1800C for aliphatic polyisocyanate and at 80-1200C for aromatic polyisocyanate up to preparing 5-10% of NCO wherein polyisocyanate is represented by toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or their mixture, diphenyl-4,4'-diisocyanate, 1,4-phenylenediisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 1,6-hexyldiisocyanate, 1,4-cyclohexyldiisocyanate, norbornyldiisocyanate or their mixture. Then method involves carrying out break and/or elongation of polycarbodiimide chain of intermediate substance by addition of equivalent compound comprising hydrophilic group and one or more amino- and/or hydroxyl functional groups during formation of polycarbodiimide intermediate substance or after formation of polycarbodiimide at temperature 70-1000C for aliphatic polycarbodiimide intermediate substance and at temperature 40-700C for aromatic polycarbodiimide intermediate substance. Then reaction in mixture is carried out up to disappearance of isocyanate functional group wherein a hydrophilic group-containing compound is represented by polyethoxymono- or diol, polyethoxy/polypropoxymono- or diol, polyethoxymono- or diamine, polyethoxy/polypropoxymono- or diamine, diol or diamine with polyalkoxy-containing by-side chain, hydroxy- or aminoalkylsulfonate, or dialkylaminoalkyl alcohol or -amine, or their mixture. Prepared compound is dispersed in water at temperature 40-1000C at pH 11-14 by addition of a base and/or buffer to water used for dispersing, and/or to prepared aqueous dispersion wherein a base is represented by alkaline metal hydroxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or trialkylamine, or trialkylamine containing hydroxy-groups, and wherein buffer is represented by usually used buffer with effective pH value 11-14. Polycarbodiimide dispersions prepared by above described method are stable for at least some weeks at temperature 500C. Also, invention describes a covering mixture comprising polycarbodiimide dispersions and solidified material prepared by applying abovementioned covering mixture on substrate and evaporation of water.

EFFECT: improved preparing method of dispersions.

3 cl, 2 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention concerns polymer material displaying optically detectable response to load (pressure) change, including polyurethane elastomer adapted for load change detection, containing aliphatic diisocyanate, polyol with end hydroxyl, and photochemical system including fluorescent molecules for distance probing, modified and transformed into chain-extending diols, with molar diol to polyol ratio approximately within 10:1 to 1:2 range, and photochemical system selected out of group of exciplex and fluorescence resonance energy transfer (FRET) systems. The invention also concerns solution containing the said polymer material, and polymer material displaying detectable response to pressure change, including polyacryl or silicon elastomer and photochemical system including definite number of fluorescent molecules for distance probing, modified for penetration into the said elastomer, selected out of group including exciplex and fluorescence resonance energy transfer (FRET), and solution containing this polymer material. To eliminate oxygen sensitivity in pressure detection the material includes photochemical system selected out of group including exciplex and fluorescence resonance energy transfer (FRET). Systems including these photochemical systems enable fast response to pressure change; in addition, compression of material containing these systems is reversible, therefore elimination of oxygen influence on pressure change detection allows shorter response time and higher sensitivity when the claimed material is used.

EFFECT: increased material sensitivity to loads and reduced sensitivity to oxygen presence.

24 cl, 2 ex, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining diaminephenylmethane and its highest homologues by the condensation of aniline and formaldehyde in the presence of heterogeneous solid acid catalysts, which are characterised by the fact that the utilised catalysts are catalysts selected from (a) split zeolites and/or (b) alumo-silicate catalysts, which have the regulated hexagonal mesoporous structure with the size of 3-10nm.

EFFECT: it makes it possible to get diaminephenylmethane with the increased contents of primary amines.

4 cl, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing stable aqueous dispersions of polycarbodiimide for using as a cross-linking agent and no containing organic solvents. Method is realized by carrying out interaction of polyisocyanate in the presence of 0.5-3% of catalyst in reaction for formation of carbodiimide to form polycarbodiimide intermediate substance at 120-1800C for aliphatic polyisocyanate and at 80-1200C for aromatic polyisocyanate up to preparing 5-10% of NCO wherein polyisocyanate is represented by toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or their mixture, diphenyl-4,4'-diisocyanate, 1,4-phenylenediisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 1,6-hexyldiisocyanate, 1,4-cyclohexyldiisocyanate, norbornyldiisocyanate or their mixture. Then method involves carrying out break and/or elongation of polycarbodiimide chain of intermediate substance by addition of equivalent compound comprising hydrophilic group and one or more amino- and/or hydroxyl functional groups during formation of polycarbodiimide intermediate substance or after formation of polycarbodiimide at temperature 70-1000C for aliphatic polycarbodiimide intermediate substance and at temperature 40-700C for aromatic polycarbodiimide intermediate substance. Then reaction in mixture is carried out up to disappearance of isocyanate functional group wherein a hydrophilic group-containing compound is represented by polyethoxymono- or diol, polyethoxy/polypropoxymono- or diol, polyethoxymono- or diamine, polyethoxy/polypropoxymono- or diamine, diol or diamine with polyalkoxy-containing by-side chain, hydroxy- or aminoalkylsulfonate, or dialkylaminoalkyl alcohol or -amine, or their mixture. Prepared compound is dispersed in water at temperature 40-1000C at pH 11-14 by addition of a base and/or buffer to water used for dispersing, and/or to prepared aqueous dispersion wherein a base is represented by alkaline metal hydroxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or trialkylamine, or trialkylamine containing hydroxy-groups, and wherein buffer is represented by usually used buffer with effective pH value 11-14. Polycarbodiimide dispersions prepared by above described method are stable for at least some weeks at temperature 500C. Also, invention describes a covering mixture comprising polycarbodiimide dispersions and solidified material prepared by applying abovementioned covering mixture on substrate and evaporation of water.

EFFECT: improved preparing method of dispersions.

3 cl, 2 tbl, 15 ex

FIELD: building materials.

SUBSTANCE: invention relates to polyisocyanate compositions used for impregnation of concrete construction surfaces for aims of their anti-corrosive protection, and to a method for concrete impregnating by using the indicated composition. The claimed composition comprises earth-alkali metal salt dissolvable in polyisocyanate taken in the amount 0.1-5 mas. p. p. per 100 mas. p. p. of polyisocyanate. Except for, the composition can comprise additionally a hydrophobic solvent and a hydrophobic plasticizer. The claimed composition provides the deep penetration of impregnation up to 9.5 mm. The composition can be used in impregnation of brick masonry, sandy-cement covering for floors, in reconstruction of reservoirs for liquids storage and ferroconcrete constructions.

EFFECT: improved and valuable properties of composition.

6 cl, 1 tbl, 27 ex

The invention relates to methods for producing polyisocyanates used for various polymeric materials, as well as to compositions based on polyisocyanates
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