Biuret group-containing polyisocyanates or blocked biuret group-containing polyisocyanates

FIELD: chemistry.

SUBSTANCE: polyisocyanate contains biuret groups, has functionality on isocyanate groups of not less than 4 and not more than 10 and is obtained using a method which includes (A) reaction of a polyisocyanate adduct with a secondary monoamine of formula (R1)(R2)NH, with the ratio of the isocyanate equivalent to the amine equivalent ranging from approximately 4:1 to approximately 14:1 to introduce biuret groups into said polyisocyanate, and (B) reaction of the polyisocyanate containing biuret groups with a blocking reagent. The polyisocyanate adduct (a) is obtained from 1,6-hexamethylenediisocyanate, (b) has average functionality on isocyanate groups of not less than 2.5 and not more than 8, and (c) contains isocyanurate groups. The blocking reagent is selected from a group comprising phenol, cresol, amides, oximes, hydrazones, pyrazoles and phenols which are substituted with long aliphatic chains.

EFFECT: obtaining blocked polyisocyanates which combine relatively low viscosity and low molecular weight with high functionality on isocyanate groups and high reactivity relative to binders used in coatings, as well as which are stable during storage with respect to increase in viscosity and are virtually colourless, which is especially important for systems which form transparent coatings.

9 cl, 6 ex, 5 tbl

 

The present invention relates to polyisocyanates, in particular containing biuret groups of the polyisocyanates or blocked containing biuret groups of the polyisocyanates.

The scope of the invention

Buritizal isocyanates are widely known. In U.S. patent No. 3903127 and No. 3976622 described a wide range of reagents for buritizal, including primary aliphatic amines. Published patent application Canada No. 2211025 describes the use of tertiary alcohols or a mixture of water and a tertiary alcohol to buritizal isocyanate. And, finally, in U.S. patent No. 4220749 describes the use of secondary monoamines as reagents for buritizal. In all three reference describes the use of hexamethylenediisocyanate as a source of isocyanate. In U.S. patent No. 4788262 is assumed that buritizal trimer of hexamethylenediisocyanate, but in the examples there is only a mixture of trimers and biletov (see also U.S. patent No. 6133397).

The use of polyisocyanates as curing agents for compositions forming the coating, it is also known, and preference is given to polyisocyanates, in particular, with functionality isocyanate groups of three and above. Published patent application U.S. No. 2003/0109664 describes obtaining polyisocyanates with a high degree of functionalization by which eoretical MDI, contains, which is a group. Among the described source of isocyanates is the trimer of hexamethylenediisocyanate. As a reagent for buritizal use water. The application indicates that, compared with isocyanates, which bioreserve tert-butanol or a mixture of tert-butanol and water containing isocyanate trimer, which bioreserve only water, have better color. The application is also often suggested that the isocyanate group in bioreserves the isocyanates can be blocked by spirits, kamiminami or oximes. Although described in the application bioreserve isocyanates have improved properties compared with the above bioreserve isocyanates, it would be desirable to improve the content of the gel and resistance to damage to the coatings obtained from these isocyanates.

Know a wide variety of blocking reagents (see, for example, "Blocked Isocyanates in Coatings," Potter and others, presented at the Water-Borne &Higher-Solids Coatings Symposium, New Orleans, February 1986). Among the described blocking reagents include i) phenol, Cresols and phenols, substituted long aliphatic chains (e.g., isononylphenol), (ii) amides (for example, ε-caprolactam), iii), oximes (for example, butanonoxime), (iv) compounds containing active methylene groups (for example, malonate and acetoacetate), and v) sodium bisulfite. Various blocking reagents are also described, for example, in U.S. patent No. 4324879, No. 4439593, No. 4495229. №4518522, №4667180, №5071937, №5705593, №5780541, №5849855, №6051675, №6060573, №6274693, №6368669 and no 6583216.

In recent time have been described as suitable blocking reagents such secondary amines as N-benzyl-tert-butylamine (published application for the European patent No. 1375549 corresponding to patent application U.S. serial number 10/459033 registered 10 June 2003) and 3-tert-butylamino-methylpropionate (application for United States patent serial number 10/874716 registered 23 June 2004).

Description of the invention

The present invention relates to containing biuret groups of the polyisocyanate having a functionality isocyanate groups of at least 4 and received by a process involving the interaction of the polyisocyanate adduct, which

a) derived from aliphatic and/or cycloaliphatic diisocyanate,

b) has an average functionality isocyanate groups of at least 2.5 and

b) which contains, which is the group

secondary monoamines when the ratio of isocyanate equivalents to amine equivalent of from about 4:1 to about 14:1 for the introduction of the named MDI biuret groups.

The invention relates also to containing biuret groups of the blocked p is diisocyanate, have a functionality isocyanate groups of at least 4, obtained by the method including

A) interaction of a polyisocyanate adduct, which

a) derived from aliphatic and/or cycloaliphatic diisocyanate,

b) has an average functionality isocyanate groups of at least 2.5 and

b) which contains, which is the group

secondary monoamines when the ratio of isocyanate equivalents to amine equivalent of from about 4:1 to about 14:1 for the introduction of the named MDI biuret groups and

B) interactions containing biuret groups MDI with a blocking reagent.

Suitable source polyisocyanates to obtain the appropriate present invention polyisocyanates are polyisocyanate adducts, which

a) derived from aliphatic and/or cycloaliphatic diisocyanates, in the preferred case of aliphatic diisocyanates and in the preferred case of 1,6-hexamethylenediisocyanate,

b) have an average functionality isocyanate groups of at least 2.5, in the preferred case, not less than 2.8 and in the preferred case, not less than 3.0, and

in), which contain groups.

Iskhodye polyisocyanate adducts in the preferred case, have a content of isocyanate groups of from 10 to 25 is AC.%, in the preferred case from 12 to 25 wt.% and in the most preferred case from 15 to 25 wt.%, also in the preferred case, they have an upper limit of functionality isocyanate groups, equal to 8, in the preferred case, it is equal to 7 and in the most preferred case, it is equal to 6. The source material for the production of polyisocyanate Adayev in the preferred case contains at least 70 wt.%, in a more preferred case, at least 80 wt.% and in the most preferred case, at least 90 wt.% aliphatic diisocyanate, in the most preferred case, 1,6-hexamethylenediisocyanate.

Source polyisocyanate adducts containing which groups are known and they can be obtained in accordance with the materials of U.S. patent No. 4324879, and to familiarize yourself with them you should refer to this link. In the General case, in the present invention preference is given to these adducts as starting compounds. Suitable examples of such polyisocyanate adducts containing which groups are trimers derived from aliphatic and/or cycloaliphatic diisocyanates. Most preferred trimers of aliphatic diisocyanates, such as the trimer of 1,6-hexamethylenediisocyanate that sold under the trademark Desmodur N3390 manufactured by Bayer Polymers LLC.

<> In principle, to obtain the original polyisocyanate adduct can be used any aliphatic and/or cycloaliphatic diisocyanate. In a number of suitable diisocyanates include 1,6-hexamethylenediisocyanate, bis-cyclohexyldiamine, 1,4-cyclohexyldiamine, bis-(4-isocyanatophenyl)methane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate ("isotropy diisocyanate"), and the like, but the list is not limited.

For obtaining of the present invention, polyisocyanates containing biuret groups, the original polyisocyanate adducts react in the presence of secondary monoamine as a reagent for buritizal. Getting bioreserves isocyanates using secondary monoamines described in U.S. patent No. 4220749 presented here as a reference. In the General case of secondary amines have the General formula (R1)(R2)NH, where R1and R2may be the same or different, they represent an aliphatic hydrocarbon radical containing from one to twenty carbon atoms. Among the suitable specific secondary monoamines include dimethylamine, diethylamine, dipropylamine, dibutylamine, bis(2-ethylhexyl)amine. For the introduction of named polyisocyanate biuret groups of the isocyanate and amine react with respect to isocyanate is about equivalent to the amine equivalent of from about 4:1 to about 14:1. The reaction is carried out at a temperature of from about 0 to 140°C, in the preferred case from 60 to 160°C. in a more preferred case from 70 to 140°C.

The resulting polyisocyanate has a functionality isocyanate groups, which is in General equal to at least 4, in the preferred case, it is equal to at least 4.5 and in the preferred case, it is at least equal to 4.8, and the content of isocyanate groups therein is from about 8 to about 24 wt.%, in the preferred case from about 10 to about 22 wt.% in the preferred case from about 10 to about 20 wt.%, based on the weight of MDI. In the preferred case, the resulting polyisocyanates have maximum functionality isocyanate groups, equal to 10, in the preferred case, it is equal to 8 and in the most preferred case, it is equal to 7. To use products can be respectively distributed in the solvent.

The molecular weight of the product is calculated based on data obtained using gel permeation chromatography with polystyrene as standard. The resulting polyisocyanate containing biuret groups, in the General case is set srednetsenovoj molecular weight from about 500 to about 10,000, in the preferred case from about 500 to about 5500 and in most FAV is Cetelem case from about 500 to about 3000.

By using the appropriate invention of the method containing biuret groups of the polyisocyanate can be obtained by continuous or intermittent.

Obtained in this way products are, in particular, the fact that they combine a relatively low viscosity and low molecular weight, high functionality isocyanate groups and with high reactivity relative to that used in the coating binder, it called binders contain reactive isocyanate groups and are, for example, containing the hydroxyl group of the polyacrylates. Other advantages are that they are easy to obtain, the content of volatile isocyanates in them does not increase even during prolonged storage, since these compounds are stable and do not decompose into monomers, they contain standard isocyanate groups, which do not require additional controlled release, and the fact that these products are stable during storage in relation to increasing the viscosity, they are virtually devoid of color, which is especially important for systems forming a transparent coating.

In particular, we obtain in this way the products are suitable for use as curing agents in the compositions for the formation of coatings, in particular for pokr is carried out in the automotive industry. In this application, the products can be used unchanged, or they may be blocked by one of the usual blocking reagents. Such products are also included in the scope of claims of the present invention.

Typical blocking reagents include i) phenol, Cresols and phenols, substituted long aliphatic chains (e.g., isononylphenol), (ii) amides (for example, ε-caprolactam and δ-valerolactam), iii), oximes (for example, butanonoxime, formaldoxime, acetophenone oxime, benzophenone oxime, diethylhexyl and methyl ethyl ketone oxime), (iv) such hydrazones as methylethylketone, and v) pyrazoles such as dimethylpyrazol. Blocking reagents typically used in cases, when the composition for formation of the coating is in the same scope.

Relevant to the present invention a composition for the formation of coatings in General contain a film-forming binder, which comprises reacting with isocyanate oligomer or polymer or dispersed gel-like polymer and above the locked or unlocked, containing biuret groups polyisocyanate curing agent.

Relevant to the present invention a composition for the formation of coatings in the preferred case are liquid one-component or two-component composition for the education of coating with an organic solvent or with water. Although in the preferred case, the compositions are liquid compositions for coating, they can be included in the powder compositions for the formation of coatings.

In particular, relevant to the present invention a composition for coating can be used for coating on the external surface of enclosures of cars or trucks. Depending on its use the present composition can form a coating that is durable, fast cure, has excellent adhesion with respect to the substrates coated with earlier coating, effectively forming intermolecular cross-links and perfectly resists corrosive chemical environments, resistant to weather conditions and retains a shiny appearance for a long time.

If the present composition is used in the coating obtained by using a solvent, the above-described polyisocyanates containing biuret groups, best suited to their introduction into the composition rapidly curable compositions for transparent coatings with a solvent with a low content of volatile organic compounds and high solids content to obtain a transparent or colored coatings for cars and g is Uzbekov. Enable compact, with high degree of functionalization, containing biuret groups polyisocyanate curing reagent with a low viscosity leads to an increase in the speed of curing of the coating and to improve performance, to more efficient formation of cross-linking, to improve resistance to aggressive chemical environments and weather factors and compositions with a low content of volatile organic compounds, since these biuret have a high degree of functionalization on the isocyanate groups and do not form a material with a high molecular weight and high viscosity, which would require additional dilution solvents for coating with the spray and the associated increase in the content of volatile organic compounds in composition.

As mentioned above, forming the coating composition is most suitable for use as a transparent coating in the automotive industry for finishing and repaints, but the coating can be painted with conventional pigments and used as a single layer or a base layer or substrate such as, for example, primer or sealer. These coatings can also be used not only in avtomobilestroenie is, for example, they may find application in industry or in architecture.

A particular advantage of the present invention isocyanates (both blocked and non-blocked) is that obtained on the basis of their coverage better otverzhdajutsja that shows an increased content of the gel at a lower temperature curing in comparison with similar products derived from bioreserves isocyanates for which as bioresidues reagent water was used.

In the following examples all parts and percentages are by mass, unless otherwise noted, we used hereinafter enumerated materials.

DESMO 800 - Desmophen 800 - polyester with a content of hydroxyl groups of 8.8%, 100% solids, a viscosity of about 170000 SP, supplied by the company Voeg MaterialScience.

CGL - CGL-052 L2 - light shielding means, which represents a sterically hindered amine based gidrauxilirovannogo functional triazine, supplied by Ciba Specialty Chemicals in the form of a 60% solids in PM acetate (acetate nanometrology ether of propylene glycol).

T-12 - Dabco T-12 - dilaurate dibutylamine, supplied by Air Products.

T-928 - Tinuvin 928 - absorber of UV radiation on the basis of hydroxyphenyltriazine, supplied by Ciba Specialty Chemicals.

BYK-370 - 25%solution of the solid is of exist, representing dimethylpolysiloxane modified hydroxyl and ester, Funktsionalnyi groups in xylene/cyclohexanone/2-Phenoxyethanol/nafta(75:7:7:1), supplied by Byk-Chemie, designed for wetting of the substrate.

n-VA/PMA/EUR - mix 4:5:6 n-butyl acetate (CAS# 123-86-4), RM acetate (CAS# 108-65-6, also known as acetate nanometrology ether propylene glycol) and Ektapro EEP production Eastman (CAS# 763-69-9, also known as ethyl-3-ethoxypropionate).

Examples

In the following examples, examples 1, 3 and 5 are examples of the comparison.

Polyiso 1. In a round bottom flask with a volume of 5 l equipped with a stirrer, a device for introducing nitrogen, a thermocouple and a heater, load 2500 parts (12,88 equivalent) MDI Desmodur N-3300 (free trimer solvent hexane diisocyanate with a content of isocyanate groups of about 22 wt.% and with a viscosity of about 2500 MPa·s, supplied by Bayer MaterialScience), 700 parts of butyl acetate, 5 parts of dietilfosfat as a catalyst and 297 parts (2.30 equivalent) of N,N-dibutylamine and stirred until homogenization. The reaction mixture for one hour, heated at 65°C, then half an hour at 90°C. after five hours at 120°C and, finally, two hours at 140°C. after the time of heating, the reaction mixture was cooled to room temperature. Sod is neigh isocyanate 10.5 wt.% (according to theory should be 10.0%). The viscosity at 25°C. equal to 1980 SP. The functionality of the product is equal to about six isocyanate groups on the molecule.

Polyiso 2. In a round bottom flask with a volume of 5 l equipped with a stirrer, a device for introducing nitrogen, a thermocouple and a heater, load 2550 parts (13,14 equivalent) MDI Desmodur N-3300, 450 parts of butyl acetate, 0,128 parts of dietilfosfat as a catalyst and 16,60 parts (0.92 equivalent) of distilled water and stirred until homogenization. The reaction mixture for one hour, heated at 65°C., then 0.5 hour at 90°C, then half an hour at 120°C and, finally, seven hours at 140°C. after the time of heating, the reaction mixture was cooled to room temperature. The content of the isocyanate is 14,52 wt.% (on theory must be 14,16%). The viscosity at 25°C. equal to 6800 SP. The functionality of the product is equal to about six isocyanate groups on the molecule.

Blocked From 1. In a round bottom flask with a volume of 2 l equipped with a stirrer, a device for introducing nitrogen, a thermocouple, a heater and a dropping funnel, download 321 part (0.80 equivalent) Polyiso 1 and 245,8 parts of butyl acetate and stirred until homogenization. Separate parts alternately for 30 minutes was added to 83 parts (0.86 equivalent) dimethylpyrazole and of 211.5 parts of butyl acetate.

The temperature rises to 35°C. a heater and increase the the temperature to 70°C. After heating at 70°C for four hours isocyanate group in the infrared spectrum are not detected. The viscosity at 20°C is equal to 226 SP. Density is equal to 0.85 g/ml Calculated equivalent weight equal to about 1077.

Locked Out 2. Carry out the transformation by analogy with getting locked Out 1, except that take 303,8 parts (0.76 equivalent) Polyiso 1, 93,2 part (1,92 equivalent) of ε-caprolactam and 175,5 parts of butyl acetate. ε-Caprolactam take instead of dimethylpyrazole that was used to get blocked From 1. The viscosity at 25°C is equal to 294 SP. Density is 0,859 g/ml Calculated equivalent weight equal to 554.

Locked Out 3. For this isocyanate blocking reagent is ethyl ketone oxime. The transformation carried out by analogy with getting locked Out 1 except that take 301,3 parts (0.75 equivalent) of Polyiso 1, 67,1 part (0.77 equivalent) of methyl ethyl ketone oxime and 206 parts of butyl acetate. The viscosity at 25°C. equal to 177 SP. Density is 0,822 g/ml Calculated equivalent weight equal to 750.

Locked Out 4. In a round bottom flask with a volume of 2 l equipped with a stirrer, a device for introducing nitrogen, a thermocouple, a heater and a dropping funnel, download 418 parts (1.70 equivalent) Polyiso 2 and 100.6 parts of butyl acetate. These substances are mixed until homogenization. Separate the parts alternately for 30 minutes add 195,8 parts (2.04 equivalent) dimethylpyrazole and 208,4 parts of butyl acetate. The temperature rises to 35°C. a heater and raise the temperature to 62°C. After heating at 62°C for two and a half hours isocyanate group in the infrared spectrum are not detected. The viscosity at 20°C is equal to 110 SP. Density is 0,824 g/ml Calculated equivalent weight equal to 466.

Locked Out of 5. Carry out the transformation by analogy with getting locked Out 4, except that they take 462,8 parts (1.60 equivalent) Polyiso 2, 217,3 part (1,92 equivalent) of ε-caprolactam and 384,0 parts of butyl acetate. The viscosity at 25°C is equal to 333 SP. Density is 0,861 g/ml Calculated equivalent weight equal to 554.

Locked Out of 6. Carry out the transformation by analogy with getting locked Out 4, except that they take 491,7 parts (1.70 equivalent) Polyiso 2, 177,7 parts (2.04 equivalent) of methyl ethyl ketone oxime and 372,6 parts of butyl acetate. The viscosity at 25°C is equal to 302 SP. Density is 0.82 g/ml Calculated equivalent weight equal to 511.

In the following next, table 1 shows the investigated compositions for the formation of coatings, and in tables 2-5 shows the acquired data. Compositions are applied using spray gun type Binks 95 to the formation of wet film thickness of about 0.1 mm After drying for 15 minutes panel utverjdayut in the selected temperature range.

Next track is no enumeration of the tests.

Experience resistance to methyl ethyl ketone in a reciprocating motion. The semicircular head of the hammer weight of about 900 g cover with several layers of cotton swabs. Tampons impregnated with methyl ethyl ketone. Hammer set at a 90° angle to the surface and move it back and forth over the surface Dina about 10 cm Tampons again impregnated with methyl ethyl ketone after every twenty-five double movements. Experience continue to breach the integrity of the coating or to achieve the 200 series of moves. Fix double the number of movements required for the integrity of the coating.

The content of the gel. Separated from the coating film is weighed and placed on a grid of stainless wire. Then 7 hours immersed in boiling acetone to extract all of the extracted material. After that, the coating film weighed again to determine and record the total mass of the remaining solids.

Determination of the hardness of the decay time of the oscillations of the pendulum. Glass panels coated is placed in the device Koenig to determine hardness by means of the pendulum and record the number of oscillations of the pendulum as long as the angle of deviation is so small. All coatings compared to the hardness of glass (172-185 fluctuations).

Experience with scratching and abrasion. The experience is performed on the device Atla AATCC crockmeter, model CM-5. Filled with wool swab (Atlas 14-9956-00) placed directly on the acrylic finger. Then the panel with the coating applied cleaner Bon Ami and remove the excess. The panel with the floor ten times Scrabble reciprocating movements, then the panel is washed and dried. Resistance to abrasion is defined as the percentage saving Shine on 20 sites with the dimension perpendicular to the position of the scratch direction.

Table 1
Example123456
Locked Out415263
Locked Out, parts of the mass393,57476,36412,13477,65428,79497,1
Desmo 800, parts of the mass155,72the level of 121.8 of 148.6118,38142,57122,03
T-12, parts of the mass3,923,983,9644a 3.9
CGL, parts of the mass6,536,636,66,666,666,44
T-928, parts of the mass39,1939,7639,5939,9539,9838,95
Byk-370, parts of the mass29,0429,4629,3329,629,634
n-VA/PMA/ear, parts of the mass201.63163.8197.88169.58194.86156.39

Table 2
Example123456
The curing temperature, °C, dual movements
113Sticky791030
118Sticky963925
120
12125
1241281176265
12725
1301728310584
13275
13514714216476
138144
143 163
1465
15125
15727
163191
168170

Table 3
Example1 23456
The curing temperature, °C gel
1138379,1to 25.330
11889,690,6for 91.325
120
12128
12499,39491,7 65
12771
1309996,996,384
132of 89.1
13599,798,4of 97.876
138100
143100
146Sticky
1510,3
15773,3
163100
168100

The curing temperature, °C hardness
Table 4
Example123456
1137712
118916102
120
121Sticky
1247532195
127 Sticky
13074583036
13231
13576546624
13852
14387
146L is PCI
151Sticky
1576
163100
16879

Table 5
Example123*456
The curing temperature, °C, the formation of scratches
79,5
90
100
110
113Sticky9613of 92.7
11858,293,2of 97.81,8
120
12489,488,410095,7
13090,7to 91.199,5100
135br93.191100100
146Sticky
151Sticky
157 17,6
16388
16882
* The composition was not investigated

1. The blocked polyisocyanate containing biuret groups and having a functionality isocyanate groups of at least 4 and not more than 10 obtained by the method including
A) interaction of a polyisocyanate adduct, which
(a) is obtained from 1,6-hexamethylenediisocyanate,
b) has an average functionality isocyanate groups is not less than 2.5 and not more than 8, and
b) which contains, which is the group
secondary monoamines formula
(R1)(R2)NH,
where R1and R2may be the same or different, yet they represent alkyl radicals containing from one to twenty carbon atoms,
when the ratio of isocyanate equivalents to amine equivalent from the example is about 4:1 to about 14:1 for the introduction of the named MDI biuret groups and
B) interactions containing biuret groups MDI with a blocking reagent which is selected from the group consisting of phenol, cresol, replaced by a long aliphatic chain phenols, amides, oximo, hydrazones and pyrazoles.

2. The polyisocyanate according to claim 1, where the above adduct has an average functionality isocyanate groups is not less than 2.8.

3. The polyisocyanate according to claim 2, where the above adduct has an average functionality isocyanate groups of not less than 3.0 and not more than 6.

4. The polyisocyanate according to claim 1, where the above adduct contains from 10 to 25 wt.% isocyanate groups.

5. The polyisocyanate according to claim 1, where the named monoamin is dibutylamine.

6. The polyisocyanate according to claim 1, where the mentioned blocking reagent selected from the group consisting of dimethylpyrazole, ε-caprolactam and methyl ethyl ketone oxime.

7. The polyisocyanate according to claim 1, where the mentioned blocking reagent includes dimethylpyrazol.

8. The polyisocyanate according to claim 1, where the mentioned blocking reagent comprises ε-caprolactam.

9. The polyisocyanate according to claim 1, where the mentioned blocking agent includes methyl ethyl ketone oxime.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to blocked polyisocyanates, applied for obtaining binding agents for lacquers, paints and elastomers in form of systems of hot drying for application of coatings on substratum from wood, metals, mineral substances, products from concrete, textile, glass or plastics, as well as hardener for polyol components. Blocked polyisocyanates have general formula (I): Polyisocyanates are obtained by interaction of polyisocyanates of general formula (II) with secondary amines of general formula (III) and hydrophilising means D-H, where D represents residue of cationic, anionic and/or non-ionic hydrophilising means.

EFFECT: obtaining of polyisocyanates, which have lower temperature of hardening or temperature of hot drying, due to which compositions of materials, which contain such polyisocyanate, are more stable in storing at room temperature and more stable at high temperatures of hot drying.

14 cl, 1 tbl, 15 ex

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

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: aqueous polyurethane dispersion composition contains polyurethane with carbodiimide and/or carboxyl groups, and polyurethane dispersion adhesive which contains polyurethane with carbodiimide and/or carboxyl groups. The polyurethanes are polyester-polyurethane elastomers. The aqueous polyurethane dispersion composition and polyurethane dispersion adhesive also contain at least one carbodiimide which contains at least one carbodiimide group. The aqueous polyurethane dispersion composition and polyurethane dispersion adhesive react with each other through a polyaddition reaction when heated to 50°C or higher. A polymeric film having an undercoating is obtained by depositing and drying the single-component aqueous polyurethane dispersion composition on a polymeric film. A composite is obtained by reacting the polymeric film having an undercoating with a substrate on which polyurethane dispersion adhesive is deposited and dried. The composite can be produced industrially and can be especially used in interior finishing, preferably of a component built into a transportation vehicle or can be used in the furniture industry.

EFFECT: high reliability of the composition.

5 cl, 3 tbl

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to aromatic polyurethane polyols used as components of priming compositions. Invention describes the priming composition comprising aromatic polyurethane polyol including product of reaction: (a) at least one diol component among number of α,β-diols, α,γ-diols and their mixtures; (b) at least one triisocyanate; (c) at least one diisocyanate wherein at least one isocyanate is aromatic one, and molecular mass or aromatic polyurethane polyol is 3000 Da, not above, and a cross-linking agent also. Prepared aromatic polyurethane polyol shows viscosity value by Brookfield at the level 8260 centipoises, OH-number 192.6 KOH/g and the dispersity (Mn/Mw) at the level 3.0. Priming compositions prepared by using indicated aromatic polyurethane polyol are useful in finishing large means of transportation, for example, trains, trucks, buses and airplanes, in particular, in vehicle body works. Also, invention relates methods for applying priming compositions on support comprising applying indicated compositions, and to a method for finishing car in repairs comprising applying the indicated priming composition.

EFFECT: improved and valuable properties of composition.

11 cl, 5 tbl, 12 ex

FIELD: chemical industry; methods of production of a thermosetting elastomers.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of production of a thermosetting polyurethane elastomer and also to the elastomer produced according to the given method. The invention presents the method of production of the polyurethane elastomer having a total apparent density exceeding 150 kg/m3 and providing for an interaction of polyisocyanate and a reactive to isocyanate composition not necessarily at presence of water, according to which the reaction conduct at an isocyanate index of 85-120. At that the polyisocyanate component is composed of: al) 80-100 mass % of diphenylmethanediisocyanate containing at least 40 mass % of 4.4'- diphenylmethanediisocyanate and-or a derivative of the indicated diphenylmethanediisocyanate, which (the derivative) is a may be a liquid at the temperature of 25°C and has NCO value of no less than 20 mass % and a2) 20 mass % of the other polyisocyanate; the reactive to isocyanate composition b) consists of b1) 80-100 mass % of a simple polyol polyester having an average nominal functionality - 2-8, average reactive equivalent weight of 750-5000, an average molecular mass of 2000-12000, the share of oxyethylene - 60-90 mass % and the share of the primary hydroxyl groups of 70-100 mass % calculated for the total number of the primary and the secondary hydroxyl groups in polyol; b2) a reactive to isocyanate extender of the chain in such a quantity, that the ratio of the rigid block makes less than 0.45; and b3) - 20-0 mass % of one or more of other reactive to isocyanate composition excluding water. At that the amount of the polyol of 61) and the reactive to isocyanate composition 63) is calculated from the total amount of the indicated polyol 61) and the composition 63). The invention presents also description of the thermosetting elastomer produced according to the indicated method.

EFFECT: the invention ensures production of a thermosetting polyurethane elastomer.

10 cl, 2 ex

The invention relates to a light-resistant, elastomeric, polyurethane moulded products

FIELD: chemistry.

SUBSTANCE: method of producing biuret and cyanuric acid through thermal decomposition of urea involves cooling the product of thermal decomposition of urea in order to settle crystals which are then dissolved in an aqueous alkaline solution and cooled to obtain high-purity biuret, and after neutralising the filtered mother solution with acid, cyanuric acid crystals are settled to obtain a suspension of cyanuric acid crystals which is then filtered to separate the crystals and washed. The invention also relates to devices for realising the given methods.

EFFECT: development of a cheap and simple method of producing biuret and high-purity cyanuric acid.

19 cl, 2 ex, 1 dwg

FIELD: chemical industry; methods and the devices for production of the biuret.

SUBSTANCE: the invention is pertaining to the method of production of biuret and to the device for its realization. The process includes production in the pyrolysis furnace of the biuret and ammonia by the carbamide pyrolysis, purification of the gained biuret in the reactor of the recrystallization, production of the salt of the monohalogenbiuret metal by interaction of the biuret with the compound of the hypohalogen metal or with halogen and the base in the first reactor. Interaction in the second reactor of the produced biuret metal salt with ammonia, including the ammonia produced during the pyrolysis process of carbamide at the molar ratio of the salt of the monohalogenbiuret metal and the total amount of the ammonia making 1:1-1:1000. The separated excess of the ammonia extracted from biuret in the ammonia evaporator is sent to the ammonia concentrator. At that the ammonia concentrator is intended for concentration of the excess of the ammonia and the ammonia produced in the pyrolysis furnace and for delivery of the concentrated ammonia in the second reactor. The technical result of the invention is the development of the economically profitable continuous process with high efficiency and utilization of the easily accessible source product, reduction of the quantity of the by-products.

EFFECT: the invention ensures the development of the economically profitable continuous process with high efficiency and utilization of the easily accessible source product, reduction of the quantity of the by-products.

14 cl, 62 ex, 12 tbl

The invention relates to new chemical compound 1,5-bis-(2-hydroxyethyl)-biuret, or diethanolamine, and method thereof

FIELD: chemical industry; methods and the devices for production of the biuret.

SUBSTANCE: the invention is pertaining to the method of production of biuret and to the device for its realization. The process includes production in the pyrolysis furnace of the biuret and ammonia by the carbamide pyrolysis, purification of the gained biuret in the reactor of the recrystallization, production of the salt of the monohalogenbiuret metal by interaction of the biuret with the compound of the hypohalogen metal or with halogen and the base in the first reactor. Interaction in the second reactor of the produced biuret metal salt with ammonia, including the ammonia produced during the pyrolysis process of carbamide at the molar ratio of the salt of the monohalogenbiuret metal and the total amount of the ammonia making 1:1-1:1000. The separated excess of the ammonia extracted from biuret in the ammonia evaporator is sent to the ammonia concentrator. At that the ammonia concentrator is intended for concentration of the excess of the ammonia and the ammonia produced in the pyrolysis furnace and for delivery of the concentrated ammonia in the second reactor. The technical result of the invention is the development of the economically profitable continuous process with high efficiency and utilization of the easily accessible source product, reduction of the quantity of the by-products.

EFFECT: the invention ensures the development of the economically profitable continuous process with high efficiency and utilization of the easily accessible source product, reduction of the quantity of the by-products.

14 cl, 62 ex, 12 tbl

FIELD: chemistry.

SUBSTANCE: method of producing biuret and cyanuric acid through thermal decomposition of urea involves cooling the product of thermal decomposition of urea in order to settle crystals which are then dissolved in an aqueous alkaline solution and cooled to obtain high-purity biuret, and after neutralising the filtered mother solution with acid, cyanuric acid crystals are settled to obtain a suspension of cyanuric acid crystals which is then filtered to separate the crystals and washed. The invention also relates to devices for realising the given methods.

EFFECT: development of a cheap and simple method of producing biuret and high-purity cyanuric acid.

19 cl, 2 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: polyisocyanate contains biuret groups, has functionality on isocyanate groups of not less than 4 and not more than 10 and is obtained using a method which includes (A) reaction of a polyisocyanate adduct with a secondary monoamine of formula (R1)(R2)NH, with the ratio of the isocyanate equivalent to the amine equivalent ranging from approximately 4:1 to approximately 14:1 to introduce biuret groups into said polyisocyanate, and (B) reaction of the polyisocyanate containing biuret groups with a blocking reagent. The polyisocyanate adduct (a) is obtained from 1,6-hexamethylenediisocyanate, (b) has average functionality on isocyanate groups of not less than 2.5 and not more than 8, and (c) contains isocyanurate groups. The blocking reagent is selected from a group comprising phenol, cresol, amides, oximes, hydrazones, pyrazoles and phenols which are substituted with long aliphatic chains.

EFFECT: obtaining blocked polyisocyanates which combine relatively low viscosity and low molecular weight with high functionality on isocyanate groups and high reactivity relative to binders used in coatings, as well as which are stable during storage with respect to increase in viscosity and are virtually colourless, which is especially important for systems which form transparent coatings.

9 cl, 6 ex, 5 tbl

FIELD: chemistry.

SUBSTANCE: described is a polymerisable iodonium salt containing a positively charged iodine atom bonded with two aryl rings and a negatively charged counter-ion and at least one substitute containing a urethane and/or urea group, which is bonded with at least one of said aryl rings, wherein said substitute contains at least one functional group capable of cationic or radical polymerisation. Described also is a polyvinyl alcohol acetal copolymer containing at least one functional group, which is capable of cationic or radical polymerissation, preferably vinyl ether, alkoxy-methylacrylamide or alkoxy-methacrylamide. The invention also describes polymer binder for coating an offset printing plate from the polyvinyl alcohol acetal family, cellulose ether family and binder based on monomers, each containing at least one functional group capable of cationic or radical polymerisation. Described also is an offset printing plate coating solution containing said polymerisable iodonium salt, said polyvinyl alcohol acetal copolymer and said binder.

EFFECT: high quality of high-resolution image when the offset printing plate is used repeatedly.

17 cl, 25 dwg, 21 ex

FIELD: chemistry.

SUBSTANCE: polyisocyanate contains biuret groups, has functionality on isocyanate groups of not less than 4 and not more than 10 and is obtained using a method which includes (A) reaction of a polyisocyanate adduct with a secondary monoamine of formula (R1)(R2)NH, with the ratio of the isocyanate equivalent to the amine equivalent ranging from approximately 4:1 to approximately 14:1 to introduce biuret groups into said polyisocyanate, and (B) reaction of the polyisocyanate containing biuret groups with a blocking reagent. The polyisocyanate adduct (a) is obtained from 1,6-hexamethylenediisocyanate, (b) has average functionality on isocyanate groups of not less than 2.5 and not more than 8, and (c) contains isocyanurate groups. The blocking reagent is selected from a group comprising phenol, cresol, amides, oximes, hydrazones, pyrazoles and phenols which are substituted with long aliphatic chains.

EFFECT: obtaining blocked polyisocyanates which combine relatively low viscosity and low molecular weight with high functionality on isocyanate groups and high reactivity relative to binders used in coatings, as well as which are stable during storage with respect to increase in viscosity and are virtually colourless, which is especially important for systems which form transparent coatings.

9 cl, 6 ex, 5 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing a polyurethane elastomer, involving reaction of a reaction mixture via reaction injection moulding, where the reaction mixture contains: (A) a polyisocyanate component, (B) an isocyanate-reactive component, in the presence of (C) a catalyst composition and, if needed, (D) one or more ultraviolet stabilisers and, if needed, (E) one or more pigments, wherein the relative amount of (A) and (B) is such that the isocyanate index ranges from approximately 100 to approximately 120. Component (A) contains: (I) allophanate-modified polyisocyanate having content of NCO groups ranging from approximately 15 to approximately 35 wt %, and containing a reaction product: (1) (cyclo)aliphatic polyisocyanate having content of NCO groups ranging from approximately 25 to approximately 60 wt %, with (2) organic alcohol selected from a group comprising aliphatic alcohols containing 1-36 carbon atoms, cycloaliphatic alcohols containing 5-24 carbon atoms, and aromatic alcohols containing approximately 7-12 carbon atoms, in which the alcohol group is not bonded directly to the aromatic carbon atom; or (II) a prepolymer of allophanate-modified polyisocyanate, where the prepolymer has content of NCO groups from approximately 10 to approximately 35 wt %, and contains a reaction product: (1) allophanate-modified polyisocyanate having content of NCO groups from approximately 15 to approximately 35 wt %, which is a reaction product: (a) (cyclo)aliphatic polyisocyanate having content of NCO groups from approximately 25 to approximately 60 wt %, and (b) organic alcohol selected from a group comprising aliphatic alcohols containing 1-36 carbon atoms, cycloaliphatic alcohols containing 5-24 carbon atoms, and aromatic alcohols containing approximately 7-12 carbon atoms, in which the alcohol group is not bonded directly to the aromatic carbon atom; with (2) an isocyanate-reactive component having functionality from approximately 2 to approximately 6 and molecular weight from approximately 60 to approximately 4000. Component (B) contains: (1) from approximately 70 to approximately 90 wt % per 100 wt % (B) one or more polyetherpolyols with low saturation, having functionality from approximately 2 to approximately 8, molecular weight from approximately 2000 to approximately 8000 and containing a maximum of 0.01 meq/g unsaturation, (2) from approximately 10 to approximately 30 wt % per 100 wt % (B) one or more organic compounds having molecular weight from approximately 60 to approximately 150, having hydroxyl functionality of approximately 2 and not containing primary, secondary and/or tertiary amine groups, and (3) from approximately 0 to approximately 5 wt % per 100 wt % (B) one or more organic compounds having molecular weight from approximately 200 to approximately 500, having functionality from 3 to 4 and containing amine-initiated polyetherpolyol. The catalyst composition (C) contains: (1) one or more catalyst of formula: , where: m is a whole number from 3 to 8, and n is a whole number from 3 to 8, and (2) at least one tin-based catalyst. The invention also describes the polyurethane elastomer itself, containing the reaction product of the above-mentioned components.

EFFECT: improved hardening and simple catalysis without the need for a lead-based catalyst, as well as obtaining elastomers with better flexural modulus and better weather resistance.

18 cl, 2 ex, 2 tbl

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