Polyaldimine-containing polyurethane composition

FIELD: polymer materials.

SUBSTANCE: invention relates to moisture-hardenable polyurethane compositions, namely to those containing at least one polyurethane prepolymer with isocyanate groups obtained from at least one polyisocyanate and at least one polyol. In addition to prepolymer, composition further contains at least one polyaldimine prepared from at least one polyamine with primary aliphatic amino groups and at least one aldehyde of general formula: wherein Y1 and Y2, independently from each other, represent alkyl, aryl, or arylalkyl group, which is optionally substituted, may contains heteroatoms and/or unsaturated fragments, or Y1 and Y2 together form carbocyclic or heterocyclic ring, which is composed of 5-8, preferably 6 atoms and optionally contains one or two unsaturated bonds; and R1 represents either linear or branched C11-C30-alkyl chain, optionally with at least one heteroatom, especially with at least one ether oxygen atom, or linear or branched C11-C30-alkyl chain with one or numerous unsaturated bonds, or R1 represents group or in which R2 represents linear, branched, or cyclic hydrocarbon chain with 2-16 carbon atoms, optionally incorporating at least one heteroatom, especially at least one ether oxygen atom, or linear, branched, or cyclic C2-C16-hydrocarbon chain with one or numerous unsaturated bonds; and R3 represents linear, branched, or cyclic hydrocarbon chain with 1-8 carbon atoms. Invention describes methods for preparing such compositions and polyaldimine. Compositions can be used as glues, sealing formulations, coatings, or floorings hardening without unpleasant smell and suitable to seal layers inside buildings or to join structural members in vehicle interiors.

EFFECT: extended assortment of hardenable liquid polymer compositions.

24 cl, 4 tbl, 14 ex

 

The technical field and prior art

The invention relates to polyurethane compositions comprising at least one polyurethane prepolymer and at least one polyamidimide that otverzhdajutsja without the unpleasant smell. Used for this polyamidimide obtained from polyamine with aliphatic primary amino groups (hereinafter referred to also repeatedly called "aliphatic polyamino") and special aldehyde.

Polyurethanes are used among other things as a one-component, cured under the action of moisture, elastic sealing compounds, adhesives and coatings. Usually they contain a polyurethane prepolymer having isocyanate groups derived from polyols and polyisocyanates, which is then mixed with other components and to use stored with the exclusion of moisture. These in themselves known systems have the disadvantage that the gas CO2formed by the reaction of isocyanate groups with water, can lead to the formation of bubbles in the cured product.

Polyamidimide in polyurethane chemistry known as hardeners, and are described, for example, in U.S. patent 3420800 and U.S. patent 3567692. Polyaluminum represent molecules with two or more aldimine group R-CH=N-R'. Polyurethane prepolymers containing isocyanate groups, and polyaluminum mo is ut to get a one-component products with good mechanical properties, which are sufficiently stable during storage and quickly otverzhdajutsja upon contact with water or moisture from the air. This polyamidimide hydrolyzed by water with formation of the corresponding aldehydes and polyamines, which then react with the isocyanate groups of the polyurethane prepolymer, and he cures without the release of CO2and thus, without the formation of bubbles.

Polyamidimide aliphatic polyamines and their use as hardeners for polyurethane is very well known. For example, they are described in U.S. patent 3932357.

Usually use polyamidimide relatively volatile aldehydes, which are known to be characterized by a particularly strong smell. So their use requires good ventilation or respiratory protection, especially if you also use an organic solvent. For the application in which you are working with a predominantly free from solvents and high viscosity products in thick layers, as, for example, in the case of elastic seals and kleivane, the smell of aldehyde released during the hydrolysis polyamidimide, is a particularly disturbing effect, as it lasts for long time. This is because, on the one hand, the complete curing curing under the action of moisture, polio Lanovoy composition, applied a thick layer, is relatively long, because the diffusion of water required for curing, through the already cured material inside slows to an increasing extent; and that, on the other hand, the aldehyde released during the curing reaction, slowly diffuses out through the dense layers formed curable material. The pollution caused by the volatilization of aldehyde after curing of the product, partly acceptable for some applications, for example, in the outer region of the buildings. But as the heavy smell of aldehyde can lead to headaches and nausea, these applications also occurs an increasing desire on systems without the smell. Specialist clear that the concept of "unscented" is difficult to define. Here and in the whole document should be understood as "not noticeable or slightly noticeable human individuals with a sense of olfaction (smell)".

In other, so-called smell-sensitive applications, on the contrary, this pollution is fundamentally not valid. Particularly sensitive to smell is to use indoors, such as sealing joints in buildings or bonding of structural elements in internal space vehicles. No smell in the estuaries and the is a necessary condition, namely, during and some time after using the product. When used in the interior of the vehicle relative to volatiles, volatile, for example, glue, proceed from the universal strict criteria. So, in the automotive industry is set to the appropriate limit value for the volatile components released from the glue, so-called "fogging" "Fogging" (measurement Method: see, for example, DIN 75201).

Still made various attempts to reduce the smell of systems containing aldimine.

In U.S. patent 4469831 described one-component polyurethane composition comprising a cured under the action of moisture 2,2-dimethyl-3-(isobutoxy)-propanolamine aliphatic polyamines. This composition is characterized by good storage stability, high curing speed and a seemingly low odor. However, the use is described of polyaluminum causes long existing pungent odor, which is not valid for smell-sensitive applications.

In U.S. patent 4853454 described, among other similar one-component polyurethane composition comprising a cured under the action of moisture substituted 2,2-dimethyl-propanolamine aliphatic polyamines. The aldehydes released during the hydrolysis described polyamidine is s, due to its high elasticity pair should ostensibly to promote the song with very little smell. However, when using the described polyaluminum also observed unpleasant tangible long time smell that makes these substances are unsuitable for smell-sensitive applications.

In U.S. patent 4720535 described one-component polyurethane composition comprising a cured under the action of moisture substituted 2,2-dimethylpropanolamine aromatic polyamines. The use is described of polyaluminum unusable due to applied aromatic polyamines. On the one hand, aromatic polyamine generally much more toxic than the aliphatic ones, and, on the other hand, polyamidimide aromatic polyamines are clearly less reactive as hardeners than those of aliphatic polyamines, both in terms of hydrolysis aldimine groups, and most of all in relation to the reaction of amino groups with isocyanate groups of the polyurethane prepolymer. In addition, the above aldehydes in most cases, also cause clearly noticeable, until the strong smell.

In U.S. patent 6136942 described one-component polyurethane composition comprising 3-phenyloxy-benzylidene aliphatic polyamines or similar compounds, which is to identify themselves with very little smell. The smell of aromatic aldehydes arising from the use of these polyaluminum, however, is clearly noticeable, and also invalid for smell-sensitive applications. In addition, the use of 3-phenoxybenzaldehyde and similar aromatic aldehydes may adversely affect the light-curable polyurethane composition.

In prior art is still not possible to use the advantages of one-component polyurethane compositions containing cured under the action of moisture polyamidimide aliphatic polyamines, as lack of education of bubbles during curing, high curing speed and good mechanical properties after curing for smell-sensitive applications.

Problem and solution

The objective of the invention is to develop a cured under the action of moisture one-component polyurethane compositions containing as a hardener, at least one polyamidimide aliphatic polyamines, cured without the unpleasant odor and, thus, among other things, suitable for smell-sensitive applications, such as sealing layers inside buildings or bonding of structural elements in internal prostranstvyennykh funds. Suitable composition, on the one hand, must be obtained by a simple method from commercially available raw materials, to have sufficient stability during storage and after application quickly enough to cure. The aldehyde released during the hydrolysis polyamidimide, should not cause any unpleasant smell and to have any negative impact on the cured polyurethane composition.

It has been unexpectedly found that the above conditions are best performed using a composition comprising at least one polyurethane prepolymer with isocyanate groups and at least one polyamidimide obtained from at least one polyamine with aliphatic primary amino groups and at least one aldehyde according to the formula given later.

Obtaining the aldehydes used for polyaluminum comes from commercially available raw materials, and amazingly just through the esterification of low volatile carboxylic acids, for example, long-chain fatty acids, with β-hydroxyaldehyde, in particular 3-hydroxypivalic aldehyde. The resulting aldehydes at room temperature are, depending on the carboxylic acids, solid or liquid. They can continue to be Atsa transformation with polyamines directly with the formation of the corresponding polyaluminum. All necessary reaction stage can be conducted without using a solvent, which composition does not leave any residue solvent, where they could cause undesirable odor and the formation of fog. As the carboxylic acid used to obtain the aldehydes themselves have little or no odor, the traces of them also do not cause any unpleasant smell, which makes unnecessary expensive treatment polyaluminum before using.

Unexpected and not obvious to a person is the fact that such polyamidimide have a high reactivity as curing agents for polyurethanes. The specialist would expect that they, due to their hydrophobic structure, poorly accessible for water required for hydrolysis aldimine groups, and that, therefore, their hydrolysis proceeds only slowly and incompletely. However, contrary to expectations described polyamidimide upon contact with moisture in polyurethane compositions react quickly and completely. Their reactivity is comparable to the reactivity significantly less hydrophobic polyaluminum, for example, described in U.S. patent 4469831.

Polyurethane compositions according to the invention are characterized by exceptional stability during storage. They very quickly otverzhdajutsja when contact is e with moisture without the unpleasant smell. The released aldehyde remains in utverzhdenii polyurethane compositions, where it does not exert any harmful effects on its properties. On the contrary, its hydrophobicity leads to the desired increase in hydrolytic stability utverzhdenii polyurethane composition.

The invention

This invention relates to compositions comprising at least one polyurethane prepolymerAndwith isocyanate groups derived from at least one MDI and at least one polyol, and at least one polyamidimideInobtained from at least one polyamineWithwith aliphatic primary amino groups and at least one aldehydeD.

Following receipt of these compositions, as well as getting polyamidimide.

Additionally describes the use of these compositions as adhesives, sealing compositions, coatings or flooring. The following describes a method of bonding, sealing or coating. In conclusion, of the product described, the surface of which could communicate, at least partially, with such a composition.

Detailed description of the invention

This invention relates to compositions comprising at least one polyurethane prepolymerAndwith isocyanate groups, obtained from, at m is re, one MDI and at least one polyol, and at least one polyamidimideInobtained from at least one polyamineWithwith aliphatic primary amino groups and at least one aldehydeDformula (I):

and Y1and Y2on the one hand, independently from each other represent an alkyl, aryl or arylalkyl group, which may possibly be substituted, may contain heteroatoms and may may contain unsaturated fragments. Preferably Y1= Y2= methyl.

On the other hand, Y1and Y2can be connected to each other with the formation of a carbocyclic or heterocyclic ring, which is characterized by a ring size of between 5 and 8, preferably 6, atoms, and possibly one or two simple unsaturated bonds.

The remainder R1denotes a linear or branched alkyl chain with 11 to 30 C atoms, possibly with at least one heteroatom, in particular with at least one oxygen-simple ester, or a linear or branched hydrocarbon chain with 11 to 30 C atoms, with one or multiple unsaturated bonds, or a residue of formula (II) or (III).

In formulas (II) and/or (III) R2the seat is no linear or branched, or cyclic alkyl chain with 2 to 16 C atoms, possibly with at least one heteroatom, in particular with at least one oxygen-simple ester, or a linear or branched, or cyclic hydrocarbon chain with 2 to 16 C atoms, with one or multiple unsaturated bonds, and R3denotes a linear or branched alkyl chain with 1 to 8 atoms C. Y1and Y2have the meanings indicated above, and the dotted line in formulas denote the space of connections.

The term "poly-" in "polyamidimide", "polyol", "polyisocyanate", "polyamine" understand molecules, which formally contain two or more appropriate functional groups.

The concept of "polyamine with aliphatic primary amino groups" in this document always refers to compounds which formally contain two or more NH2group associated with one aliphatic, cycloaliphatic or arylaliphatic balance. They differ from aromatic amines in which the amino groups directly linked to aromatic residue, such as, for example, in aniline or 2-aminopyridine.

Polyurethane prepolymerAndreceive from at least one MDI and at least one polyol. This transformation can be carried out due to the fact that the reaction between the polyol and polii asianata carried out in the usual way, for example, at a temperature of from 50 to 100aboutWith, if necessary using suitable catalysts, the polyisocyanate is metered so that its isocyanate groups in relation to the hydroxyl groups of the polyol are in stoichiometric excess. Excess MDI are chosen so that the resulting polyurethane prepolymerAndafter transformation of all hydroxyl groups of the polyol content of free isocyanate groups remains from 0.1 to 15 wt.%, preferably 0.5 to 5 wt.%, in the calculation for the entire polyurethane prepolymerA.Inif necessary, the polyurethane prepolymerAndcan be obtained by using a solvent or plasticizer, and solvent used or the plasticizer does not contain any reactive groups with respect to isocyanates.

As polyols to obtain a polyurethane prepolymerAndcan be used, for example, the following commercially available polyols or any mixtures thereof:

- Polyoxyalkylene, also called simple polyether polyols, which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2 - or 2,3-butilenica, tetrahydrofuran or mixtures thereof, possibly polymerized with the initiator molecules with two or more active hydrogen atoms, as, n is the sample, water, ammonia or compounds with several OH - or NH-groups, such as 1,2-ethanediol, 1,2 - and 1,3-propandiol, neopentylglycol, diethylene glycol, triethylene glycol, the isomeric dipropyleneglycol and dipropyleneglycol, isomeric butandiol, pentandiol, hexandiol, heptanediol, octanediol, nonanediol, decanediol, undemandingly, 1,3 - and 1,4-cyclohexanedimethanol, bisphenol a, hydrogenated bisphenol a, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, glycerol, aniline, and mixtures of these compounds. Can be used as polyoxyalkylene, which are characterized by a low degree of unsaturation (measured according to ASTM D-2849-69 and shown in milliequivalent unsaturation per gram of polyol (IEC/g)), obtained, for example, by using so-called double metallocyanide complexes, catalysts (DMC catalysts), and polyoxyalkylene with a higher degree of unsaturation obtained, for example, with the aid of anionic catalysts as NaOH, KOH or alkali metal alcoholate.

Particularly suitable are polyoxyalkylene or polyoxyalkylene, especially polyoxypropylene or polyoxypropylene.

Particularly suitable are polyoxyalkylene or polyoxyalkylene with the degree of unsaturation lower than 0.02 IEC/g and with a molecular weight in the range from 1000 to 3000 g/mol, and polyoxypropylene and-trioli with a molecular weight of from 400 to 8000 g/mol. By "molecular weight" or "molar weight" in this document always understand the average molecular weight of Mn.

Also particularly suitable are the so-called polyoxypropylene or trioli with the blocking end ethyleneoxide (EO) groups. The latter are special Polyoxypropylenediamine that receive, for example, so that the net polyoxypropyleneamine after polipropilenovaya alkoxylated with ethylene oxide, and due to this have primary hydroxyl groups.

- Hydroxyquinoline polybutadienes.

- Complex polyether polyols obtained, for example, of the two, is a trivalent alcohols such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propandiol, dipropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols, with organic dicarboxylic acids or their anhydrides or esters, such as, for example, succinic acid, glutaric acid, adipic acid, cork acid, sabotinova acid, dodecadienol acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acids is or mixtures of the aforementioned acids, and complex polyether polyols from lactones such as, for example, ε-caprolacton.

- Polycarbonatediol, which are accessible through a transformation, for example, mentioned above, used for the formation of complex polyether polyols - alcohols with diallylmalonate, dellcorporate or phosgene.

- Polyacrylate and polymethacrylamide.

These polyols are characterized by an average molecular weight from 250 to 30,000 g/mol and an average functionality of Oh-groups in the range from 1.6 to 3.

In addition to these mentioned polyols to obtain a polyurethane prepolymerAndcan be used low molecular weight two - or polyhydric alcohols such as, for example, 1,2-ethanediol, 1,2 - and 1,3-propandiol, neopentylglycol, diethylene glycol, triethylene glycol, the isomeric dipropyleneglycol and dipropyleneglycol, isomeric butandiol, pentandiol, hexandiol, heptanediol, octanediol, nonanediol, decanediol, undemandingly, 1,3 - and 1,4-cyclohexanedimethanol, hydrogenated bisphenol a, dimeric fatty alcohols, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols and other polyols, low molecular weight alkoxysilane products of the above two - and polyhydric alcohols, and also mixtures of the aforementioned of spirits.

To obtain a polyurethane prepolymerAnduse the commercially available polyisocyanates. As examples could be mentioned the following polyisocyanates, best known in polyurethane chemistry:

2,4 - and 2,6-toluenediisocyanate (TDI) and any mixture of its isomers, 4,4'-diphenylmethanediisocyanate (MDI), isomers position diphenylmethanediisocyanate, 1,3 - and 1,4-delete the entry, 2,3,5,6-tetramethyl-1,4-diisocyanatobutane, 1,6-hexamethylenediisocyanate (HDI), 2-methylpentanediol-1,5-diisocyanate, 2,2,4 - and 2,4,4-trimethyl-1,6-hexamethylenediisocyanate (TMDI), 1,12-dodecyltrimethoxysilane, cyclohexane-1,3 - and -1,4-diisocyanate and any mixture of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (= isophorondiisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethanediisocyanate (HMDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), m - and p-xylylenediisocyanate (XDI), 1,3 - and 1,4-tetramethylcyclopentadiene (TMXDI), 1,3 - and 1,4-bis-(isocyanatomethyl)-cyclohexane, and also oligomers and polymers of the aforementioned isocyanates, and also any mixtures of the aforementioned isocyanates. Especially preferred are MDI, TDI, HDI and IPDI.

PolyamidimideIncan be obtained from at least one polyamineWithwith aliphatic primary amino groups and at least one aldehydeDthrough the condensation reaction with elimination of water. Such condensation reaction is best known and is described, for example, in Houben-Weyl, "Methods der organischen Chemie", Vol. XI/2, page 73 f. AldehydeDused in relation to the primary amino groups polyamineWithstoichiometrically or in a stoichiometric excess.

As polyaminesWithwith aliphatic primary amino groups to obtain polyamidimideInmean polyamine known in polyurethane chemistry, which are used among others for a two-component polyurethanes. As examples can be mentioned the following: aliphatic polyamine as Ethylenediamine, 1,2 - and 1,3-propandiamine, 2-methyl-1,2-propandiamine, 2,2-dimethyl-1,3-propandiamine, 1,3 - and 1,4-butanediamine, 1,3 - and 1,5-pentanediamine, 1,6-hexanediamine, 2,2,4 - and 2,4,4-trimethylhexamethylenediamine and mixtures thereof, 1,7-heptadien, 1,8-octanediamine, 4-aminomethyl-1,8-octanediamine, 1,9-enantiomer, 1,10-decontamin, 1,11-undecanedioic, 1,12-dodecandioic, methyl-bis-(3-aminopropyl)amine, 1,5-diamino-2-methylpentane (MPMD), 1,3-diaminopentane (DAMP), 2,5-dimethyl-1,6-hexamethylenediamine were, cycloaliphatic polyamine as 1,2-, 1,3 - and 1,4-diaminocyclohexane, bis-(4-aminocyclohexane)-methane, bis-(4-amino-3-methylcyclohexyl)-methane, bis-(4-amino-3-ethylcyclohexyl)-methane, bis-(4-amino-3,5-dimethylcyclohexyl)-methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (=ISOPHORONEDIAMINE or ACCESSORIES>), 2 - and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3 - and 1,4-bis-(aminomethyl)cyclohexane, 1-cyclohexylamino-3-aminopropane, 2,5(2,6)-bis-(aminomethyl)-bizik what about[2.2.1]heptane (NBDA, received Mitsui Chemicals), 3(4),8(9)-bis-(aminomethyl)-tricyclo[5.2.1.02,6]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5.5]undecane, 1,3 - and 1,4-xylylenediamine, aliphatic polyamine containing ether groups as bis-(2-aminoethylamide) simple ether, 4,7-dioctadecyl-1,10-diamine, 4,9-dioxadodecane-1,12-diamine and higher oligomers, polyoxyalkylene-polyamine with theoretically two or three amino groups, for example, commercially available under the name Jeffamine® (produced by Huntsman Chemicals), as well as mixtures of the aforementioned polyamines.

The preferred polyamines are 1,6-hexamethylenediamine were, MPMD, DAMP, 2,2,4 - and 2,4,4-trimethylhexamethylenediamine, 4-aminomethyl-1,8-octanediamine, ACCESSORIES>, 1,3 - and 1,4-xylylenediamine, 1,3 - and 1,4-bis-(aminomethyl)cyclohexane, bis-(4-aminocyclohexane)-methane, bis-(4-amino-3-methylcyclohexyl)-methane, 3(4),8(9)-bis-(aminomethyl)-tricyclo[5.2.1.02,6]decane, 1,2-, 1,3 - and 1,4-diaminocyclohexane, polyoxyalkylene-polyamine with theoretically two or three amino groups, especially Jeffamine®EDR-148, Jeffamine®D-230, Jeffamine®D-400 and Jeffamine®T-403, and in particular mixtures of two or more of the aforementioned polyamines.

To obtain polyamidimideInuse at least one aldehydeDformula (I):

In prefer enom method of obtaining aldehyde Dcome out β-Hydroxyaldehyde according to the formula (IV), which can be obtained, for example, from formaldehyde (or paraformaldehyde, or oligomeric forms of formaldehyde, as 1,3,5-trioxane) and aldehyde according to formula (V) in the cross-aldol condensation, if necessary, in situ.

Y1and Y2in formulas (IV) and (V) have already described the value.

β-Hydroxyaldehyde according to the formula (IV) is subjected to transformation with the carboxylic acid to the corresponding ether complex, namely: or fatty acid with long chain R1-COOH to the corresponding fatty acid ester; and/or with complex monoalkyl ether dicarboxylic acid HOOC-R2-COOR3to aldehydeDwith the residue of formula (III); and/or dicarboxylic acid HOOC-R2-COOH to aldehydeDin this case, get a dialdehyde, with the residue of formula (II). Formula (II) and (III) and R1, R2and R3have the previously described meaning. This esterification can be carried out without using a solvent by known methods described, for example, in Houben-Weyl, "Methods der organischen Chemie", Vol. VIII, Seiten, 516-528.

In the case of dicarboxylic acids have the mixture of aldehydesDwith the remnants of the formula (II) and formula (III), if, for example, the first part of the carboxyl groups atrificial β-GI is oxyaldehydes according to the formula (IV), and then the remaining carboxyl group atrificial alkilany alcohol (R3-OH). This mixture can then be directly used to obtain polyamidimideB.

Preferred aldehydes of the formula (V) to interact with formaldehyde to β-hydroxyaldehyde formula (IV) are the following: Isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleramide aldehyde, 2-ethylcaproic aldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde and diphenylacetaldehyde. Particularly preferred Isobutyraldehyde.

Preferred β-hydroxyaldehyde according to the formula (IV) are products of the interaction of formaldehyde with the above-mentioned aldehydes of the formula (V), named as preferred. Particularly preferred is 3-hydroxypivalic aldehyde.

As suitable carboxylic acids for esterification with β-hydroxyaldehyde according to the formula (IV) can be mentioned, for example, the following: lauric acid, tridecanoate acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachnid acid, palmitoleic acid, oleine the traveler acid, erucic acid, linoleic acid, linolenic acid, aleocharinae acid, arachidonic acid, succinic acid, glutaric acid, adipic acid, Emelyanova acid, cork acid, azelaic acid, sabotinova acid, 1,12-dodecadienol acid, maleic acid, fumaric acid, hexahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalate acid, 3,6,9-trioxaundecanoate acid and similar derivatives of polyethylene glycol, dehydrated ricinoleic acid, and fatty acids of technical processes saponification of natural oils and fats such as, for example, rapboe oil, sunflower oil, linseed oil, olive oil, coconut oil oil palm kernels and palm oil.

Preferred are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, succinic acid, adipic acid, azelaic acid and sabotinova acid and technical mixtures of fatty acids containing these acids.

By turning at least one polyamineWithwith aliphatic primary amino groups with at least one aldehydeDare formed, for example, polyamidimide schematic formulas (VI) and (VII)

and n denotes 2, 3 or 4, and Q must be a balance polyamineWithwith aliphatic primary amino groups after removal of all primary amino groups; and

and m denotes an integer from 0 to 10, and Q in the same molecule is the same or different, and depending on the circumstances, there must be a balance polyamineWithwith aliphatic primary amino groups after removal of all primary amino groups. The remains of the Y1, Y2, R1and R2in formulas (VI) and (VII) have already described the value.

If obtaining polyamidimideBuse dialdehydeDwith the residue of formula (II), it is preferable to use, or in a mixture with monoallelicDnamely, in such proportions that for polyamidimide formula (VII) for m receive the average value in the range from 1 to 10; or metered so that there is an excess of the aldehyde groups in relation to the amino groups in obtaining polyamidimideBand the excess aldehyde pick up so that polyamidimide formula (VII) for m also get the average value in the range from 1 to 10. Both methods receive the mixture of oligomeric polyaluminum viscosity, well fit for use.

As polyamidimideIncan also be used a mixture of R is slichnih of polyaluminum, in particular also mixtures of different polyaluminum obtained with different polyaminesWithwith primary aliphatic amino groups, subjected to transformation with different or the same aldehydesDin particular also mixtures of polyaluminum obtained using polyamines with different number of primary aliphatic amino groups, i.e. different values of n.

Polyurethane prepolymerAand polyamidimideBmix with each other, and polyamidimideBdosed in amounts of from 0.1 to 1.1 equivalents aldimine groups to the equivalent of isocyanate groups of the polyurethane prepolymerA. Extras can be added catalyst for hydrolysis polyamidimide, for example, organic carboxylic acid, benzoic acid or salicylic acid, organic carboxylic acid anhydride as the anhydride of phthalic acid or anhydride hexahydrophthalic acid complex silloway ester of organic carboxylic acids, organic sulfonic acid, p-toluensulfonate, or another organic or inorganic acid, or mixtures of the aforementioned acids.

As additional components in the described polyurethane compositions may be present, among others, the following auxiliary substances and additives, well known in the production is of poliuretano.

Plasticizers, for example esters of organic carboxylic acids or their anhydrides, phthalates, such as dioctylphthalate or diisodecylphthalate, adipinate, as, for example, dioctyladipate, Sabatini, organic esters of phosphoric and sulfonic acids, polybutene and others that do not react with isocyanate compounds; solvents; inorganic and organic fillers, such as ground or precipitated calcium carbonates, which, if necessary, coated with stearates, carbon black, kaolin, aluminum oxide, silicic acid and PVC powder; fiber, for example, polyethylene; pigments; catalysts for example, ORGANOTIN compounds as dibutyltindilaurate, dibutyltindilaurate, or other conventional in polyurethane chemistry catalysts for the reaction of isocyanate groups; rheology modifiers such as thickeners, for example, compounds of urea, polyamide waxes, bentonites or pyrogenic silicic acid; adhesion promoters, in particular silanes as epoxysilane, vinylsilane, isocyanatobenzene and aminosilane subjected to transformation with aldehydes to eliminationof; dehumidifiers as, for example, p-totalitarian and other reactive isocyanates, esters orthomorphisms acid, calcium oxide or molecular sieves; stabilizers against the of EPLA, light and UV radiation; flame retardants; surface-active substances such as, for example, wetting means, means to support spreading, helping to remove air or defoamers; fungicides or substances which inhibit the growth of fungi, and other substances commonly used in the manufacture of polyurethanes.

Described polyurethane composition to receive and keep with the exclusion of moisture. The compositions are stable during storage, i.e. they can in suitable packaging or device (Anordnung), as, for example, in a barrel, bag or charging the liner before applying be storedwithin a few months up to a year or more, without losing fitness. When using polyurethane compositions come in contact with moisture, after which polyamidimideBhydrolyzed to aldehydesDand polyaminesCand polyamineWithreact with the polyurethane prepolymerAcontaining isocyanate groups, and he thus cures. Or the water necessary for the reaction, can be derived from the air (humidity), or polyurethane composition can be brought into contact with components containing water, for example by spreading, for example, a smoothing agent, by sprayingor through the exchange method, or the component containing water, the can is to be added to the polyurethane composition, for example, in the form of a water-containing paste, which may be blended with, for example, staticthe mixer.

If polyamidimideBuse in fault, i.e. the ratio aldimine groups to isocyanate groups is selected below the stoichiometric excess isocyanate groups react with available water.

The reaction of the polyurethane prepolymerAcontaining isocyanate groups, with gidrolizuyutza polyaluminumBnot necessarily must pass through polyamineWith. Of course it is also possible reaction with the intermediate stages of hydrolysis polyamidimideBto polyamine C. for Example, it is possible that hydrolisis polyamidimideBin the form of polyamines directly reacts with the polyurethane prepolymerAndcontaining isocyanate groups.

As a result, the polyurethane composition is cured in the above reactions.

Described polyurethane composition in the cured state has exceptional mechanical properties. It is characterized by high elongation and high tensile strength tensile, module of elasticity, which can consistently be installed by variations of components used, as, for example, polyols, polyisocyanates and polyamine in a wide region on the basis of the response to the values of the corresponding application.

AldehydesDthat hatshepsuts from polyamidimideBwhen hydrolysis, are different in that they due to their high vapor pressure remain in utverzhdenii polyurethane compositions, and that they do not cause any unpleasant smell. In the case of fatty acids with long chain hydrophobic balance of fatty acids causes reduced water flow in utverzhdennuyu polyurethane composition that increases the resistance of polyurethane material with respect to hydrolysis. Furthermore, the hydrophobic residue of a fatty acid with a long lasting contact with water allows good protection against leaching of aldehydesDfrom utverzhdenii polyurethane composition. The presence of these aldehydes in utverzhdenii polyurethane composition does not cause any deterioration of light resistance of the polyurethane material, as it is observed in the presence of low volatile aromatic aldehydes.

Described polyurethane composition suitable as sealant compositions of all kinds, for example, for sealing joints in building construction, as adhesives for bonding various substrates, for example, for bonding of structural parts in the manufacture of automobiles, railway rolling stock, ships or other industrial products, and the quality is as coatings or flooring for different types on different bases (substrates).

It is especially suitable for applications that are sensitive to smell, such as sealing layers inside buildings and bonding of structural parts in the interior of the vehicle. As coatings are preferred protective coating, sealing (Versiegelungen), protective layers and undercoat layers. Among decks are particularly preferred can be called flooring. These decks get typical pouring reactive composition on the base and leveling it, where it solidifies with the formation of flooring. For example, these flooring are used for offices, some residential areas, hospitals, schools, warehouses, garages and other private or industrial applications. Such use is so vast space that even when used in outdoor area can lead to complications in the work from the point of view of hygiene and/or gas. Further, the majority of flooring is used indoors. So smell for flooring is a very big problem.

The polyurethane composition at least partially in contact with the surface of any substrate. It is preferable for uniform contact in the form of a sealing compound or adhesive, coating or flooring, and they are the NGOs in the areas requiring the use of the compounds for bonding or sealing, or should be protected basis. It is necessary that the substrate or the contact product before contact should be subjected to physical and/or chemical pre-treatment, for example, by grinding, sand blasting machine, cleaning brush or the like, or treatment with cleaners, solvents, adhesion promoters, solvents adhesion promoters or primer layer, or coating compounds that promote adhesion (Haftbrücke) or sealant.

Examples

All percentage data refer to weight percent unless otherwise specified).

Used polyamine:

Alpha, omega-Polyoxypropylenediamine (Jeffamine®D-230, Huntsman): total content of primary amines>97%; the content of amine = by 8.22 mmol NH2/year

1,3-xylylenediamine (MXDA); Mitsubishi Gas Chemical: content MXDA>99%; the content of amine = 14,56 mmol NH2/year

1,6-hexamethylenediamine were (HDA): contents HDA>99,0%; the content of amine = 17,21 mmol NH2/year

1,5-diamino-2-methylpentane (MPMD; DuPont): content MPMD>98,5%; the content of amine = 17.11 per bbl mmol NH2/year

Used polyols:

Acclaim®4200 N (Bayer): linear polipropilenovaya with theoretical functionality of the IT-group 2, the average molecular weight of about 4000, OH-the number of about 28 mg KOH/g, unsaturation OK. 0,005 IEC/year

Acclaim®12200 (Bayer): linear polipropilenovaya with theoretical functionality of the IT-group 2, the average molecular weight of about 12000, OH-number of about 11 mg KOH/g, an unsaturation OK. 0,005 IEC/year

Caradol®MD34-02 (Shell): nonlinear polypropyleneoxide-polietilenoksidnye, with ethylenoxide terminal groups, with theoretical functionality of the IT-group 3, the average molecular weight of about 4900, OH-number of about 35 mg KOH/g, an unsaturation OK 0.08 IEC/year

Description of test methods:

The viscosity was measured at 20aboutWith chicascoyote.com viscometer Fa. Haake (PK100/VT-500).

During the formation of the film (time to extinction tack-free) was determined at 23aboutC and 50% relative humidity.

Tensile strength tensile elongation at break and E-modulus was determined at 0.5-5% elongation in the film, cured for 7 days at 23aboutC and 50% relative humidity according to DIN EN 53504 (stretch speed: 200 mm/min).

The bubbles were evaluated qualitatively based on the number of bubbles that are formed during the curing of the films used for mechanical testing (if 23aboutC and 50% relative humidity).

The smell was evaluated in cast films through smell nose on distance and 10 cm, the first time directly before use of the composition, and the second time through the 7 days after that song, utverzhdenii at the 23aboutC and 50% relative humidity.

Obtaining polyurethane prepolymers

Polyurethane prepolymer PP1

259 g of polyol Acclaim®4200 N, 517 g of polyol Caradol®MD34-02, 124 g of 4,4'-etilendiamindisuktsinatov (MDI; Desmodur®44 MC L, Bayer) and 100 g of diisodecylphthalate was subjected to transformation by a known method at 80aboutWithto the polyurethane prepolymer with terminal NCO groups. The reaction product had a content of free isocyanate groups, a certain space-analytically, 2,30% (based on the polyurethane prepolymer, and a viscosity at 20aboutWith56 PA × s.

Polyurethane prepolymer PP2

845 g of polyol Acclaim®4200 N and 115 g of 4,4'-methylene-diphenyldiisocyanate (MDI; Desmodur®44 MC L, Bayer) were subjected to transformation by a known method at 80aboutWithto the polyurethane prepolymer with terminal NCO groups. The reaction product had a content of free isocyanate groups, a certain space-analytically, 1,96%, and a viscosity at 20about37 PA × s.

Polyurethane prepolymer PP3

937 g of polyol Acclaim®4200 N, 57 g tripropyleneglycol and 285 g of 4,4'-etilendiamindisuktsinatov (MDI; Desmodur®44 MC L, Bayer) under the Yergali transformation by a known method at 80 aboutWithto the polyurethane prepolymer with terminal NCO groups. The reaction product had a content of free isocyanate groups, a certain space-analytically, 3,76%, and a viscosity at 20aboutWith 58 PA × s.

Polyurethane prepolymer PP4

1515 g of polyol Acclaim®12200 and 82 g of isophoronediisocyanate (IPDI; Verstanat®IPDI, Degussa) were subjected to transformation by a known method at 100aboutWithto the polyurethane prepolymer with terminal NCO groups. The reaction product had a content of free isocyanate groups, a certain space-analytically, 0,93%, and a viscosity at 20aboutWith 45 PA × s.

Getting polyaluminum

Polyamidimide PA1

In a round bottom flask with reflux condenser and water separator (Dean Stark) downloaded 40,5 g of formaldehyde (37% in water, free from methanol), 36,0 g Isobutyraldehyde, 100.0 g of lauric acid and 1.0 g of 4-toluenesulfonic acid, and placed in a nitrogen atmosphere. The mixture was heated on an oil bath with vigorous stirring, after which started to separate water. After 4 hours the temperature in the bath was raised to 170aboutWith, and the apparatus was evacuated using a water-jet pump, until the end of allocating water. Gathered, in General, about 35 ml of distillate in the separator. The reaction mixture was cooled, and the counter drops added to 48.6 g of Jeffamine®D-230. P the following this volatile components are completely banished. The reaction product thus obtained, a liquid at room temperature, and was characterized by a content aldimine determined as the amine content, 2,17 mmol NH2/g and a viscosity at 20aboutWith 700 MPa × s.

Polyamidimide PA2

As described for polyamidimide PA1, 42.8 g of formaldehyde (37% in water, free from methanol), 38.0 g of Isobutyraldehyde, 150,0 g of stearic acid and 1.0 g of 4-toluenesulfonic acid were subjected to transformation in the allocation of approximately 37 ml of water, and the reaction mixture is formed at the same time, mixed with 57,0 g Jeffamine®D-230. After removal of volatile components obtained reaction product, creamy at room temperature characterized by the content aldimine determined as the amine content, of 1.93 mmol NH2/year

Polyamidimide PA3

In a round bottom flask with reflux condenser, thermometer, and water separator (Dean Stark) was downloaded and 11.0 g of paraformaldehyde, 40,0 g 2-methylvaleramide aldehyde, 64,0 g of lauric acid and 0.5 g of 4-toluenesulfonic acid, and placed in a nitrogen atmosphere. The mixture was heated on an oil bath with vigorous stirring to 100aboutWith up to a noticeable decrease in the rate of reverse flow. After that was off the back of the refrigerator, the temperature in the bath was increased to 130aboutWith, after which he began to receive water. After 30 minutes the temperature in the ban is raised to 170 aboutWith, and within 90 minutes of the apparatus was evacuated using a water-jet pump. Gathered, in General, about 14 ml of distillate in the separator. The reaction mixture is then subjected to fractional distillation in a high vacuum. To 30.0 g thus obtained aldehyde (2-methyl-2-propyl-3-oxopropionate), then the counter drops) was added 7.6 g HDA. After separation of the volatile components at 80aboutWith under a water-jet vacuum pump received a colorless liquid at room temperature, the reaction product is completely odorless, and is characterized by a content aldimine determined as the amine content, of 2.72 mmol NH2/, IR: 2955, 2922, 2852, 1737 (C=O), 1667 (C=N), 1466, 1419, 1376, 1343, 1233, 1162, 1112, 1070, 1021, 1008, 939, 885, 863, 740, 722.

Polyamidimide PA4

As described for polyamidimide PA1, a 60.2 g of formaldehyde (37% in water, free from methanol), 53,5 g Isobutyraldehyde, 100.0 g sabatinovka acid and 1.0 g of 4-toluenesulfonic acid were subjected to transformation in the allocation of approximately 52 ml of water. The reaction mixture, the resultant was cooled, was added 19 g of n-butanol, stirred 30 minutes and again heated, and then again began to receive water. After one hour the temperature in the bath was raised to 170aboutWith, and the apparatus was evacuated using a water-jet pump, until the end of allocating water. Gathered, in General, about 57 ml (52 ml + 5 is l) of distilled water in the separator. The reaction mixture was cooled and added 72,0 g Jeffamine®D-230. After removal of the volatile components of the received liquid at room temperature, the reaction product is characterized by the content aldimine determined as the amine content, 2.49 mmol NH2/g and a viscosity at 20aboutWith 6700 MPa × s.

Polyamidimide PA5

As described for polyamidimide PA1, 40,5 g of formaldehyde (37% in water, free from methanol), 36,0 g Isobutyraldehyde, 100.0 g of lauric acid and 1.0 g of 4-toluenesulfonic acid were subjected to transformation in the allocation of 35 ml of water, and the reaction mixture is formed at the same time, mixed with 26,0 g MXDA. After removal of the volatile components of the received liquid at room temperature, the reaction product is characterized by the content aldimine determined as the amine content, of 2.33 mmol NH2/year

Polyamidimide PA6

As described for polyamidimide PA1, 22,3 g of paraformaldehyde, 53,5 g Isobutyraldehyde, a 49.5 g of lauric acid, 50.0 g sabatinovka acid and 1.0 g of 4-toluenesulfonic acid were subjected to transformation in the allocation of a total of 14 ml of water, and the reaction mixture is formed at the same time, mixed with 33,0 g MPMD. After removal of volatile components obtained reaction product, liquid at room temperature, characterized by a content aldimine determined as the amine content, of 3.05 mmol NH2 /g and a viscosity at 20aboutWith 13000 MPa × s.

Polyamidimide PA7

In a round bottom flask with a thermometer and a water separator (Dean Stark) downloaded 51,0 g 3-hydroxypivalic aldehyde (dimeric form), 100.0 g of lauric acid and 1.0 g of 4-toluenesulfonic acid, and placed in a nitrogen atmosphere. The mixture was heated on an oil bath with vigorous stirring, after which he began to receive water. After 4 hours the temperature in the bath was raised to 170aboutWith, and the apparatus was evacuated using a water-jet pump until water excretion. Gathered, in General, about 9 ml of distilled water in the separator. The reaction mixture was cooled and counter drops added to 48.6 g of Jeffamine®D-230. Then volatile components were completely off. The reaction product thus obtained, a liquid at room temperature, and was characterized by a content aldimine determined as the amine content, 2,19 mmol NH2/g and a viscosity at 20aboutWith700 MPa × s.

Polyamidimide PA8

In a round bottom flask was loaded 100.0 g Jeffamine®D-230. With good cooling and vigorous stirring was added from the counter drops of 75.0 g of Isobutyraldehyde. After 12 hours stirring drove volatile components. Thus obtained reaction product, liquid at room temperature, and was characterized by a content aldimine, ODA is defined as the amine content, to 5.66 mmol NH2/year

Polyamidimide PA9

In a round bottom flask was loaded 62,0 g Jeffamine®D-230. With good cooling and vigorous stirring was added from the counter drops to 89.5 g of 2,2-dimethyl-3-isobutylacetophenone. After 10 minutes stirring drove volatile components. Thus obtained reaction product, liquid at room temperature, and was characterized by a content aldimine determined as the amine content, 3.58 mmol NH2/year

Polyamidimide PA10

As described for polyamidimide PA9 were subjected to transformation of 45.0 g MXDA with 115,0 g of 2,2-dimethyl-3-isobutylacetophenone. Thus obtained reaction product, liquid at room temperature, and was characterized by a content aldimine determined as the amine content, 4,43 mmol NH2/year

Examples 1-4 (according to the invention) and examples 5-7 (comparative)

Table 1 polyurethane prepolymers and polyamidimide homogeneous mixed in the ratio of NH2/NCO (i.e. equivalents aldimine groups to equivalents of isocyanate groups of the polyurethane prepolymer) 0,5/1,0. To the mixture was added benzoic acid (200 mg/100 g of the polyurethane prepolymer), again homogeneous mixed and immediately Packed up in sealed tubes, and kept them for 15 hours at 60aboutC. Then the portion of the mixture was poured on sheet metal, pokr is th PTFE (PTFE) (dry film thickness about 2 mm), was utverjdali within 7 days at 23aboutC and 50% relative humidity, and then measured the mechanical properties utverzhdenii film. With the remaining contents of the tubes were determined stability during storage by measuring the viscosity before and after storage for 7 days at 60aboutC. the Results are given in table 1.

Table 1
Example12345

cf.*
6

cf.*
7

cf.*
Polyurethane prepolymerPP1PP1PP1PP1PP1PP1PP1
PolyamidimidePA1PA2PA3PA4PA8PA9-
Viscosity before storage (PA x s)506655701204856
The viscosity after storage (PA x s)59795881-

jelly
5861
During the formation of film (min)353832/td> 452529>600
BubblesnonoNonoNoNovery

strong.
Ultimate tensile strength (MPa)1,31,22,01,11,21,2Nism.
Elongation (%)150160160130140150Nism.
E-module 0.5 to 5% (MPa)1,71,59,01,72,12,0Nism.
The smell when you usenonononovery

strong.
Strong.no
The smell in 7 daysnonoNoNoweakstrong.no
(nism = immeasurably); cf.* = comparative

The results show that the compositions of examples 1-4 according to the invention are stable during storage, are characterized by a good reaction pic is the institutional capacity (film forming) and otverzhdajutsja without bubbles. However, they neither using nor later do not emit an unpleasant odor, and in dry condition characterized by good mechanical properties. Comparative example 5 is made according to the prior art, is not stable during storage and is characterized by a strong smell. Comparative example 6 made according to U.S. patent 4469831 in respect of stability during storage, reactivity, blistering and mechanical properties is equivalent to examples 1-4; however, in this example, during curing, and after a long time manifests itself clearly noticeable odor. Comparative example 7, is made entirely without aldimine, in conclusion can be odorless, but is characterized by a lack of reactivity (long education film) and a strong tendency to form bubbles.

Examples 8-9 (according to the invention) and example 10 (comparative)

Compositions of various polyurethane prepolymers and polyaluminum received and tested as described in example 1 (used the ratio of NH2/NCO = 0,7:1,0).

The polyurethane prepolymers and polyamidimide, and the results are given in table 2.

Table 2
P is the iMER 8910

compare.
Polyurethane prepolymerPP2PP2PP2
PolyamidimidePA5PA6PA10
Viscosity before storage (PA x s)323634
The viscosity after storage (PA x s)374338
During the formation of film (min)405040
BubblesNoNono
Ultimate tensile strength (MPa)9,13,0*7,5
Elongation (%)1300>13001300
E-module 0.5 to 5% (MPa)3,60,84,5
The smell when you useNoNostrong
The smell in 7 daysNoNostrong
*the value at the maximum elongation (1300%)

The results show that the compositions of examples 8-9 according to the invention are stable during storage, features resultsa good reactivity (film forming) and otverzhdajutsja without bubbles. However, they neither using nor later do not emit an unpleasant odor, and in dry condition characterized by good mechanical properties. The latter depends strongly on the used polyamidimide (or from the underlying polyamine), as clearly show the differences between the two examples. Comparative example 10, made according to U.S. patent 4469831 in respect of stability during storage, reactivity, blistering and mechanical properties is equivalent to the examples 8-9; however, in this example, during curing, and after a long time manifests itself clearly noticeable odor.

Examples 11-12 (according to the invention) and example 13 (comparative)

Compositions of various polyurethane prepolymers and polyaluminum received and tested as described in example 1 (used the ratio of NH2/NCO = 0.5 to 1.0 second).

38
Table 3
Example111213

compare.
Polyurethane prepolymerPP3PP3PP3
PolyamidimidePA7PA5PA9
Viscosity before storage (PA × s)3140
The viscosity after storage (PA × s)374444
During the formation of film (min)1008580
BubblesNoNoNo
Ultimate tensile strength (MPa)6,27,67,5
Elongation (%)860900700
E-module 0.5 to 5% (MPa)1,75,02,4
The smell when you useNoNoStrong
The smell in 7 daysNoNostrong

The polyurethane prepolymers and polyamidimide, and the results are given in table 3.

The results show that the compositions of examples 11-12 according to the invention are stable during storage, are characterized by good reactivity (film forming) and otverzhdajutsja without bubbles. However, they neither using nor later do not emit an unpleasant odor, and in dry condition characterized by good mechanical properties. The last C is hanging from used polyamidimide (or from the underlying polyamine), what is clearly seen when comparing test data for both examples. Comparative example 13, is made to U.S. patent 4469831 in respect of stability during storage, reactivity, blistering and mechanical properties is equivalent to the examples 11-12; however, in this example, during curing, and after a long time manifests itself clearly noticeable odor.

Example 14 (according to the invention) and example 15 (comparative)

Compositions of various polyurethane prepolymers and polyaluminum received and tested as described in example 1 (used the ratio of NH2/NCO = 0,9:1,0). The polyurethane prepolymers and polyamidimide, and the results are given in table 4.

Table 4
Example1415

compare.
Polyurethane prepolymerPP4PP4
PolyamidimidePA4PA10
Viscosity before storage (PA × s)3738
The viscosity after storage (PA × s)4241
During the formation of film (min)240 220
BubblesNoNo
The smell when you useNoStrong
The smell in 7 daysNoStrong

The results show that the composition of example 14 according to the invention is stable upon storage, it has good reactivity (film forming) and cures without bubbles. While it is neither using nor later does not emit an unpleasant odor. Comparative example 15, made according to U.S. patent 4469831 in respect of stability during storage, reactivity, blistering and mechanical properties is equal; however, in this example, during and after curing is manifested clearly noticeable odor.

1. The composition is intended for adhesive, sealing compound, coating or flooring that contains at least one polyurethane prepolymer And isocyanate groups derived from at least one MDI and at least one polyol;

and at least one polyamidimide received from at least one polyamine With aliphatic primary amino groups

and at least one aldehyde D formula:

and Y1and Y2or, independently of one another, denote alkyl, aryl or arylalkyl group which may be substituted, may contain heteroatoms and may contain unsaturated fragments,

or Y1and Y2connected to each other with the formation of a carbocyclic or heterocyclic ring, which is characterized by a ring size of between 5 and 8, preferably 6, atoms, and possibly one or two simple unsaturated bonds;

and R1or denotes a linear or branched alkyl chain with 11 to 30 C atoms, possibly with at least one heteroatom, in particular with at least one oxygen-simple ester, or a linear or branched hydrocarbon chain with 11 to 30 C atoms, with one or multiple unsaturated bonds,

or does

or does

and R2denotes a linear or branched, or cyclic alkyl chain with 2 to 16 C atoms, possibly with at least one heteroatom, in particular with at least one oxygen-simple ester, or a linear or branched, or cyclic hydrocarbon chain with 2 to 16 and the ohms, with one or multiple unsaturated bonds,

R3denotes a linear or branched alkyl chain with 1 to 8 atoms C.

2. The composition according to claim 1, characterized in that Y1=Y2=methyl.

3. The composition according to claim 1, characterized in that the polyurethane prepolymer And is characterized by a content of free isocyanate groups is from 0.1 to 15 wt.%, preferably 0.1 to 5 wt.%, in the calculation for the entire polyurethane prepolymer.

4. The composition according to claim 1, characterized in that the polyisocyanate to obtain a polyurethane prepolymer And is a diisocyanate, in particular selected from the group consisting of 4,4/-diphenylmethanediisocyanate, 2,4 - and 2,6-toluylene diisocyanate, 1,6-hexamethylenediisocyanate and isophoronediisocyanate.

5. The composition according to claim 1, characterized in that the polyol to obtain a polyurethane prepolymer And is characterized by an average functionality of Oh-groups from 1.6 to 3.

6. The composition according to claim 5, characterized in that the polyol is polyoxyethyleneglycol, especially with the degree of unsaturation <0.02 IEC/g and molecular weight Mn1000-30000 g/mol.

7. The composition according to claim 6, characterized in that the polyol is a polyol obtained by means of DMC catalysis (double metallocyanide complexes).

8. The composition according to claim 5, characterized in that the polyol is polyoxyalkylene, in particular the molecular weight M n400-8000 g/mol.

9. The composition according to claim 8, characterized in that the polyol is polyoxypropyleneglycol, or polyoxypropyleneglycol with the blocking end EO groups.

10. Composition according to one of claims 1 to 9, characterized in that for obtaining polyaniline used In the aldehyde D in the stoichiometric ratio or in stoichiometric excess with respect to the primary amino groups polyamine C.

11. Composition according to one of claims 1 to 9, characterized in that the polyurethane prepolymer a and polyamidimide At present in a ratio of 0.1 to 1.1 equivalent aldimine groups to the equivalent of isocyanate groups.

12. Composition according to one of claims 1 to 9, characterized in that the polyamine With an aliphatic primary amine groups selected from the group comprising 1,6-hexamethylenediamine were, 1,5-diamino-2-methylpentane, 1,3-diaminopentane, 2,2,4 - and 2,4,4-trimethyl-hexamethylenediamine were, 4-aminomethyl-1,8-octanediamine, ISOPHORONEDIAMINE, 1,3 - and 1,4-xylylenediamine, 1,3 - and 1,4-bis-(aminomethyl)-cyclohexane, bis-(4-aminocyclohexane)-methane, bis-(4-amino-3-methylcyclohexyl)-methane, 3(4),8(9)-bis-(aminomethyl)-tricyclo[5.2.1.02,6]decane, 1,2-, 1,3 - and 1,4-diaminocyclohexane, polyoxyalkylene-polyamine with theoretically two or three amino groups, especially Jeffamine®EDR-148, Jeffamine®D-230, Jeffamine®D-400 and Jeffamine®T-403, and, in particular, mixtures of the Vuh or more of the aforementioned polyamines.

13. Composition according to one of claims 1 to 9, characterized in that the aldehyde D used to obtain polyamidimide, obtained by the esterification reaction β-hydroxyaldehyde with carboxylic acid, in particular without the use of solvent, and β-hydroxyaldehyde obtained, possibly in situ, formaldehyde, or paraformaldehyde, or oligomeric forms of formaldehyde, and the second aldehyde, and this second aldehyde selected from the group comprising Isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleramide aldehyde, 2-ethylcaproic aldehyde, cyclopentanecarboxaldehyde cyclohexanecarboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde, diphenylacetaldehyde, preferably Isobutyraldehyde.

14. The composition according to item 13, wherein the aldehyde D used to obtain polyamidimide, obtained by the esterification reaction of 3-hydroxypivalic aldehyde obtained, possibly in situ, of formaldehyde or paraformaldehyde and Isobutyraldehyde, with a carboxylic acid, in particular without the use of solvent.

15. The composition according to 14, characterized in that the carboxylic acid used to obtain the aldehyde D selected from the group comprising lauric acid, myristic acid, palmitinovoj the acid, stearic acid, oleic acid, linoleic acid, linolenic acid, succinic acid, adipic acid, azelaic acid and sabotinova acid.

16. The method of obtaining the composition according to one of claims 1 to 15, comprising a step for polyamidimide through the interaction of the aldehyde with the amine.

17. The method according to clause 16, including the additional step for aldehyde D from carboxylic acid and β-hydroxyaldehyde, especially without the use of solvent, and β-hydroxyaldehyde get, perhaps, in situ, of formaldehyde or paraformaldehyde, or oligomeric forms of formaldehyde, and the second aldehyde.

18. The method according to clause 16, including the additional step for aldehyde D from carboxylic acid and 3-hydroxypivalic aldehyde, and Isobutyraldehyde, especially without the use of solvent, and 3-hydroxypivalic aldehyde get, perhaps, in situ, of formaldehyde or paraformaldehyde.

19. The use of a composition according to one of claims 1 to 15 as an adhesive, sealing compound, coating or flooring.

20. Method of bonding, characterized in that it includes a step of contacting with a composition according to one of claims 1 to 15.

21. Method of sealing, characterized in that it includes a step of contacting with a composition according to one of claims 1 to 15.

22. The method applied what I cover, characterized in that it includes a step of contacting with a composition according to one of claims 1 to 15.

23. The method according to claim 20, characterized in that it comprises the additional step of curing in air.

24. The method according to claim 20, characterized in that it further includes a step of contacting with a component containing water, or adulteration.



 

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SUBSTANCE: method involves placing gluing layer material between parts of textile material; providing hot pressing and cooling, with gluing material being preliminarily processed with flux of CO2-laser radiation having intensity of 350 W and radiation density of 5.3 W/cm2 during 40-45 s. Method allows glued connection strength to be increased by 1.5-2 times.

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29 cl, 3 tbl, 13 ex

FIELD: construction industry; methods of connection of the details made out of the from-foaming self-hardening mixtures.

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1 dwg

FIELD: rubber industry.

SUBSTANCE: invention relates to methods for glue-assisted attaching rubber plates to metallic surfaces, including curvilinear ones, and can be used in ship building, mechanical engineering, construction, and chemical engineering. Task of the present invention resides in improvement of coating quality, increase in plate attachment strength, and increased reliability of sealing of gaps between plates. For that, prior to applying glue composition, metallic surface is mechanically treated and mounting surface of rubber plates and their ends are chemically modified.

EFFECT: reduced laboriousness of operation and increased adhesion strength with sealed gaps between rubber plates.

FIELD: protective coatings.

SUBSTANCE: invention relates to methods for protecting metallic surfaces of geophysical instruments for exploring wells against combined action of generated acoustic field, drilling mud components, and formation fluids causing rapid wear of well instrument body. Gluing of protective polyurethane coating to cleaned and degreased metallic surface is effected by a way wherein glue composition based on triphenylmethanetriisocyanate in organic solvent is preliminarily applied onto surface as a layer with thickness 0.5-5 μm, preferably 1-3 μm, after which applied film is aged for 15-30 min at 100°C or for 12-18 h at 20-25°C and relative air humidity 30 to 98% and then protective coating based on lacquer polyurethane and/or poured polyurethane composition is deposited and hardened by a known method.

EFFECT: improved quality of received acoustic signal.

4 cl, 1 tbl, 3 ex

FIELD: connection of wood materials by separate application of hardening adhesive composition and gel-containing composition.

SUBSTANCE: proposed method includes several stages: (a) delivery of at least two parts of wood material; (b) separate application of adhesive composition (A) containing hardening resin and composition (B) containing gel-forming agent on surface of at least one or at least two parts; (c) connection of two parts forming stack with (A) and (B) compositions between parts; (d)preliminary molding of stack at temperature below required hardening temperature of thermosetting adhesive composition without hardening of resin; (e) hot molding of stack at temperature above temperature at preliminary molding or above required temperature of hardening of applied thermosetting composition at hardening of resin.

EFFECT: improved cold adhesion.

20 cl, 2 tbl, 2 ex

FIELD: connection of wood materials by separate application of hardening adhesive composition and gel-containing composition.

SUBSTANCE: proposed method includes several stages: (a) delivery of at least two parts of wood material; (b) separate application of adhesive composition (A) containing hardening resin and composition (B) containing gel-forming agent on surface of at least one or at least two parts; (c) connection of two parts forming stack with (A) and (B) compositions between parts; (d)preliminary molding of stack at temperature below required hardening temperature of thermosetting adhesive composition without hardening of resin; (e) hot molding of stack at temperature above temperature at preliminary molding or above required temperature of hardening of applied thermosetting composition at hardening of resin.

EFFECT: improved cold adhesion.

20 cl, 2 tbl, 2 ex

FIELD: bonding materials on base of wood.

SUBSTANCE: proposed method includes hardening amino resin by means of hardening composition containing acid and phenol resin. Proposed method makes it possible to obtain quickly hardened and waterproof adhesive joint.

EFFECT: possibility of obtaining quickly hardened waterproof joint.

42 cl,, 4 tbl, 4 ex

Glue composition // 2265636

FIELD: adhesives.

SUBSTANCE: invention relates to preparation of glue for use generally in operations wherein two surfaces are to be tightly connected with each other in glazing industry and, in particular, when fixing vehicle windshields and/or windows, and/or other vehicle parts, which could require replacement such as, but not limiting to, vehicle panels; as well as to a method for using glue when mounting and/or replacing vehicle windshields and/or other vehicle as well as building transparencies. Glue composition comprises adhesive with thermally expanding microcapsules which act as, dispersed therein, pressure-caused adhesion activators. Microcapsules are heat activated and release at least one expandable volatile substance enclosed in microcapsule shell.

EFFECT: enabled replacement of transparencies with minimum possible damages using economically advantageous procedure.

31 cl

FIELD: wood working industry.

SUBSTANCE: method comprises setting the ends of the timber to be glued in the die filled with synthetic material and pressing. The ends of the timber to be glued is rolled by means of rolls until the timber fibers are produced. The fibers are washed up to remove fine wood particles. The fibers are brought together in the die, and the die is filled with synthetic material composed of 70% of wood fibers and 30% of synthetic material. The mass is pressed under the pressure 100 Mpa during no less than 5 min at a temperature of 75-100°C.

EFFECT: expanded functional capability and reliability.

6 dwg, 1 tbl

FIELD: building materials.

SUBSTANCE: invention relates to a hardening composition used in building industry. The composition comprising a polymer with two or more thiol groups per a molecule, compound with two or more isocyanate groups per a molecule, carbon black and calcium carbonate involves additionally a filling agent wherein silicic acid or silicate is the main component or organic filling agent wherein ground powdered carbon as the main component. The composition shows satisfactory stability in storing the basic compound and the hardening capacity even after storing the basic compound and, except for, it forms the hardened join with sufficient rupture strength limit, hardness and properties of barrier for gas. The composition comprises a hydrocarbon plasticizer and an organometallic compound preferably that provides highly effective hardening properties in combination with higher mechanical strength and properties of barrier for gas. Proposed hardening composition can be used as sealing material in manufacturing isolating glasses, frames, windows for transportation means, glues and covers.

EFFECT: improved and valuable technical properties of composition.

9 cl, 12 tbl, 11 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer compositions including at least one polyurethane prepolymer A with isocyanate terminal groups obtained from at least one polyisocyanate with at least one polyol A1 and, if necessary, with at least one polyol A2. wherein A1 is linear polyoxyalkylenepolyol with unsaturation degree ,less than 0.04 m-equ/g; A2 is polyol, which is present in amount 0-30%, preferably 0-20%, in particular 0-10% based on total amount A1+A2; and at least one polyaldimine B. Composition is a mixture of polyurethane prepolymer A with polyaldimine B. In absence of moisture, such compositions are stable on storage. When being applied, such compositions are brought into contact with moisture, after which polyaldimines are hydrolyzed into aldehydes and polyamines, and polyamines react with polyurethane prepolymer containing isocyanate groups. Products obtained from such composition possess very wide spectrum of properties, including tensile strength varying within a range from 1 to 20 MPa and ultimate elongation above 1000%. Composition may be used as glue, hermetic, coating, or facing.

EFFECT: expanded possibilities of polyurethanes.

3 cl, 7 tbl, 34 ex

FIELD: composite materials.

SUBSTANCE: in particular, invention relates to employment of polyisocyanates compositions as binders for composites containing lignocellulose fibers such as oriented wood chipboard.

EFFECT: improved performance characteristics regarding detachment of product as compared to conventional polyisocyanates employed for binding lignocellulose material.

11 cl, 7 tbl, 8 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polyurethane-polyol compositions comprising product of reaction of a polyol and Herbert alcohol, the two containing In average 12 carbon atoms. Preferred polyols are α,β-diols and α,β-diols. Polyurethane-polyol compositions exhibit very low viscosity and are particularly suitable in coating compositions with very low content of volatile organics. Hardened coating obtained from claimed compositions ensure high resistance to cracking and can be applied on various substrates such as metal, plastic, wood, glass, ceramics.

EFFECT: increased strength of coatings on a variety of substrates.

5 cl, 3 tbl

FIELD: coating compositions.

SUBSTANCE: invention relates to composition used for coating applying and comprising polyisocyanate compound, hydroxyl-functional film-forming polymer and nonvolatile branched monoatomic alcohol wherein the aliphatic branched monoatomic alcohol is preferable but long-chain nonvolatile branched monoatomic alcohols are more preferable. This provides preparing compositions for applying coatings that possess the improved indices of fluidity and can be used for preparing coatings with the improved appearance and without the negative effect on other properties. Also, invention relates to the multiple composition fir applying coatings. The multicomponent composition for applying coatings represents the bicomponent composition for applying coatings preferably that comprises the polyisocyanate component in addition to hydroxyl-functional film-forming polymer comprising nonvolatile branched monoatomic alcohol also. Also, invention relates to a method for car finishing comprising applying compositions for applying coating on car and to a method for preparing the multilayer coating.

EFFECT: valuable properties of composition.

30 cl, 1 tbl, 2 ex

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: 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: protective coatings.

SUBSTANCE: invention relates to methods for protecting metallic surfaces of geophysical instruments for exploring wells against combined action of generated acoustic field, drilling mud components, and formation fluids causing rapid wear of well instrument body. Gluing of protective polyurethane coating to cleaned and degreased metallic surface is effected by a way wherein glue composition based on triphenylmethanetriisocyanate in organic solvent is preliminarily applied onto surface as a layer with thickness 0.5-5 μm, preferably 1-3 μm, after which applied film is aged for 15-30 min at 100°C or for 12-18 h at 20-25°C and relative air humidity 30 to 98% and then protective coating based on lacquer polyurethane and/or poured polyurethane composition is deposited and hardened by a known method.

EFFECT: improved quality of received acoustic signal.

4 cl, 1 tbl, 3 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

FIELD: protective coatings.

SUBSTANCE: invention provides coating composition comprising first compound containing at least one bicyclo-ortho-ester functional group, second compound containing at least two isocyanate groups, and third compound containing at least one thiol group.

EFFECT: enlarged assortment of coatings.

19 cl, 10 tbl, 30 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer compositions including at least one polyurethane prepolymer A with isocyanate terminal groups obtained from at least one polyisocyanate with at least one polyol A1 and, if necessary, with at least one polyol A2. wherein A1 is linear polyoxyalkylenepolyol with unsaturation degree ,less than 0.04 m-equ/g; A2 is polyol, which is present in amount 0-30%, preferably 0-20%, in particular 0-10% based on total amount A1+A2; and at least one polyaldimine B. Composition is a mixture of polyurethane prepolymer A with polyaldimine B. In absence of moisture, such compositions are stable on storage. When being applied, such compositions are brought into contact with moisture, after which polyaldimines are hydrolyzed into aldehydes and polyamines, and polyamines react with polyurethane prepolymer containing isocyanate groups. Products obtained from such composition possess very wide spectrum of properties, including tensile strength varying within a range from 1 to 20 MPa and ultimate elongation above 1000%. Composition may be used as glue, hermetic, coating, or facing.

EFFECT: expanded possibilities of polyurethanes.

3 cl, 7 tbl, 34 ex

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