Asymmetric dialdimine-containing polyurethane composition

FIELD: chemistry.

SUBSTANCE: present invention relates to a curable composition consisting of two components K1 and K2, which contain (a) at least one aromatic polyisocyanate P, which contains isocyanate groups, (b) at least one dialdimine A of formula , where X is a diamine residue DA with two primary amino groups after separating said two amino groups; and Y1 and Y2 are independently a univalent hydrocarbon residue with 1-12 C atoms; and Y3 is a univalent hydrocarbon residue which optionally has at least one heteroatom, particularly oxygen in form of an ether, a carbonyl or ester group, and (c) compounds which are reactive with respect to isocyanate groups, particularly water and/or polyols and/or polyamines, under the condition that at least one of the two primary amino groups of diamine DA is an aliphatic amino group, and that two primary amino groups of diamine DA differ from each other either by the number of hydrogen atoms at the carbon atoms (Cα), which are in the α-position to the corresponding amino group, at least one, or the number hydrogen atoms at the carbon atoms (Cβ), which are in the β-to the corresponding amino group, at least two. Described also is a curable composition obtained after reacting said composition with water, use of the disclosed compositions as an adhesive, a sealant, filling compound or coating, methods of gluing, sealing and coating using said curable composition, and an article which is glued, sealed or coated using said methods.

EFFECT: obtaining moisture-curable polyurethane compositions which are stable during storage, are characterised by long curing time before gluing and high rate of hardening and harden without bubbles.

23 cl, 10 tbl, 24 ex

 

The technical field

The invention relates to the field of vlagootverzhdaemykh polyurethane compositions and their use, in particular as elastic adhesives, sealants and coatings.

The level of technology

Vlagootverzhdaemykh compositions based on polyurethane polymers containing isocyanate groups, have long been used as elastic adhesives, sealants and coatings. Polyurethane polymers used, is usually synthesized from simple polyether polyols and polyisocyanates. These compositions, when cured with the help of liquid predisposed to the formation of bubbles due to release of carbon dioxide in the form of a gas that dissolves quickly enough or outstanding.

In order to reduce the formation of bubbles in the polyurethane composition can be added to the blocked amines, the so-called latent (hidden) hardeners, such as, for example, polyoxazolines, polyetilene or polyamidimide. However, because this may decrease the stability of the composition during storage.

From patent US 4469831 and US 4853454 known polyurethane compositions containing polyamideimide and as a consequence possessing good stability during storage.

From international application WO 2004/013200 known polyurethane compositions containing special polyol imine, which are also characterized by good storage stability and which otverzhdajutsja odorless.

Polyurethane compositions containing latent hardeners, in particular based on aromatic polyisocyanates, however, in most cases, have the disadvantage that their curing occurs very quickly, so it's too short a time before pasting" and therefore too short processing period. Moreover, when cured in most cases released volatile and strong-smelling products removal, in particular aldehydes or ketones, depending on the application interferes with or is at all desirable.

Summary of invention

The objective of the invention is to create vlagootverzhdaemykh polyurethane compositions which are stable during storage, are characterized by long waiting time before bonding and high curing speed and otverzhdajutsja without the formation of bubbles.

It has been unexpectedly found that compositions according to claim 1 of the formula of the invention solve this problem. These compositions contain a special asymmetric gialdini so that they are stable during storage, are characterized by long exposure times re the gluing and high curing speed and otverzhdajutsja without the formation of bubbles. In one preferred form of execution of these compositions are moreover characterized by the absence of odor, namely both before and during and after curing. The composition may be one-component or two-component and used as adhesives, sealants, potting mass or coatings. Especially preferred was their use as sealants.

Further object of the invention is a method of bonding according to claim 20 of the formula of the invention, the packing method according to item 21 of the claims and the method of coating according to article 22 of the claims.

In conclusion, the objects of this invention are curable composition according to item 16 of the claims, as well as products, bonded as described, sealed or covered by A.25 claims.

A preferred form of execution of the invention are objects of the dependent claims.

The embodiment of the invention

The object of this invention is a composition comprising

a) at least one aromatic polyisocyanate P containing isocyanate groups, and

b) at least one Valdimir And formula (I).

While X represents the residue of the diamine DA with two primary amino groups after the separation of these two amino groups. Further, Y1and Y2or independently from the other means, optional, monovalent hydrocarbon residue with 1 to 12 atoms, or Y1and Y2mean together divalent hydrocarbon residue with 4 to 20 atoms, which is part of an optionally substituted carbocyclic ring with 5 to 8, preferably 6, atoms C.

Further, Y3means monovalent hydrocarbon residue, which optionally contains at least one heteroatom, especially oxygen in the form of a simple ether, carbonyl or ester groups.

For the invention it is important that at least one of the two primary amino groups of the diamine DA is an aliphatic amino group, and two primary amino groups of the diamine DAdiffer from each other, or

the number of hydrogen atoms of carbon atoms (Cα)standing in α-position to the corresponding amino group by at least one,

or

the number of hydrogen atoms of carbon atoms (Cβ), standing in the β-position to the corresponding amino group by at least two.

The term "polymer" in this application on the one hand understand the totality of chemically uniform macromolecules, but differ in respect of degree of polymerization, molecular weight and chain length obtained by polyreactive (polymerization, polyaddition, polycondensation). On the other hand, the term "the emer" also includes derivatives of such a set of macromolecules from polyeucte, that is, compounds that are obtained through interactions, such as accession or the substitution of functional groups defined macromolecules and which may be chemically uniform or chemically diverse. Further, the term also includes so-called prepolymers, that is, reactive oligomeric prior adducts, functional groups which participate in the structure of macromolecules.

The term "polyurethane polymer" includes all polymers that are obtained by way of the so-called diisocyanate polyaddition. It also includes such polymers, which are almost or entirely free from urethane groups. Examples of polyurethane polymers are copolymers of polyethers and polyurethanes, polyesters and polyurethanes, polyethers and polyureas, polyurea, copolymers of polyesters, and polyureas, polyisocyanurates and polycarbamide.

The prefix "poly" in the names of substances, such as polyamidimide, polyisocyanate, polyol or polyamine in this application means substances which formally contain two or more functional groups present in its designation, on a molecule.

The term "aromatic isocyanate group" in this application means an isocyanate group, which is linked with aromatic atom C.

The term "p is Ruina amino group" in this application means the NH 2the group, which is associated with one organic residue, while the term "secondary amino group" means an NH-group, which is associated with two organic residues, which together can be part of a ring.

By "aliphatic amino group" means amino group, which is linked with aliphatic, cycloaliphatic or arylaliphatic balance. This is different from "aromatic amino group", which is directly linked to the aromatic or heteroaromatic residue, such as, for example, in aniline or 2-aminopyridine.

Under the "waiting time before bonding" in this application we understand the time during which the composition may be recycled, after isocyanate groups MDI come in contact with water.

The composition includes at least one aromatic polyisocyanate P containing isocyanate groups.

In the first form of the aromatic polyisocyanate P containing isocyanate groups is an aromatic polyurethane polymer PUP, containing isocyanate groups.

Suitable polyurethane polymerPUP, in particular, obtained by reaction of at least one polyol, at measure one aromatic polyisocyanate. This interaction may result from the fact polyol and a polyisocyanate in the standard way, for example, at a temperature of 50°C.-100°C., optionally using suitable catalysts, is brought to reaction with the polyisocyanate is metered so that its isocyanate groups in relation to the hydroxyl groups of the polyol are in stoichiometric excess. Preferably the polyisocyanate is metered so that the ratio of NCO/OH is 1.3-5, in particular 1.5 to 3. In this case, the ratio of NCO/OH see the number of isocyanate groups to the number of hydroxyl groups. Preferably, the polyurethane polymer PUP after interaction of all hydroxyl groups of the polyol content of free isocyanate groups remain in the amount of 0.5-15 wt%, preferably 0.5 to 10 wt%.

Optional polyurethane polymerThe PUP can be obtained by the joint use of plasticizers, and used plasticizers do not contain groups reactive toward isocyanates.

As polyols to obtain a polyurethane polymer PUP, for example, can be used the following commercially available polyols or mixtures thereof:

- Polyoxyalkylene, also called simple polyether polyols or simple oligopyrroles, which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2 - or 2,3-butilenica, oxetane (Oxetan), tetrahydrofuran or their mixtures is her possibly polymerized with the initiator molecules with two or more active hydrogen atoms such as, for example, water, ammonia or compounds with several OH or NH groups such as, for example, 1,2-ethanediol, 1,2 - and 1,3-propandiol, neopentylglycol, diethylene glycol, triethylene glycol, isomers of dipropyleneglycol and dipropyleneglycol, isomers of butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanol, 1,3 - and 1,4-cyclohexanedimethanol, bisphenol a, hydrogenated bisphenol a, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, glycerol, aniline, and also mixtures of the aforementioned compounds. Can be used as polyoxyalkylene characterized by a low degree of unsaturation (measured according to ASTM D-2849-69 and shown in milliequivalent unsaturation per gram of polyol (mEq/g)), obtained, for example, using the so-called catalysts double metal cyanide complex (DMC catalysts), and polyoxyalkylene with a high degree of unsaturation obtained, for example, with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alcoholate.

Especially appropriate are polyoxyalkylene or polyoxyalkylene, in particular polyoxypropylene or polyoxypropylene.

Particularly relevant are polyoxyalkylene the crystals and trioli with the degree of unsaturation lower than 0.02 mEq/g and with a molecular weight in the range from 1000 to 30,000 g/mol, and polyoxypropylene and-trioli with a molecular weight of from 400 to 8000 g/mol.

Also acceptable are the so-called "EO-terminated" (ending with ethylene oxide) polyoxypropyleneamine. Polyoxypropyleneamine are special Polyoxypropylenediamine that receive, for example, so that the net polyoxypropyleneamine, in particular polyoxypropylene and-trioli, after the reaction of polipropilenovaya next alkoxylated with ethylene oxide, and therefore are characterized by primary hydroxyl groups:

- Simple polyether polyols grafted styrolacrylonitrile, or acrylonitrilebutadiene.

- Complex polyether polyols, also called complex oligopyrroles obtained, for example, two or 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, t is Reptilia acid and hexahydrophthalic acid or a mixture of these acids, and complex polyether polyols from lactones, such as ε-caprolactone.

- Polycarbonatediol that are available through the interaction of the above used for the synthesis of complex polyether polyols and alcohols with diallylmalonate, dellcorporate or phosgene.

- Polyacrylate and polymethacrylamide.

- Polyhydroxybutyrate fats and oils, for example natural fats and oils, in particular castor oil; or (so-called oleochemical) polyols obtained by chemical modification of natural fats and oils, for example, a complex epoxypolyester or simple epoxypolyester obtained by epoxidation of unsaturated oils and subsequent disclosure of the cycle with carboxylic acids or alcohols, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils; or polyols obtained from natural fats and oils through a process of decomposition, such as alcoholysis or ozonolysis and subsequent chemical bonding, for example, by transesterification or dimerization obtained in this the image degradation products or derivatives thereof. Acceptable degradation products of natural fats and oils, in particular, are fatty acids and fatty alcohols, and esters of fatty acids, in particular methyl ester (FAME), which can be Modific is arranged, for example, by hydroformylation and hydrogenation to esters of fatty hydroxyacids.

- Poliglecaprone polyols, also called oligohydramnios, as, for example, polyhydroxyvalerate copolymers of ethylene - propylene, ethylene - butylene or ethylene - propylene - diene, which produces, for example, the company Kraton Polymers, or polyhydroxyvalerate copolymers of dienes as 1,3-butadiene or a mixture of dienes and vinyl monomers as styrene, Acrylonitrile or isobutylene, or polyhydroxybutyrate polybutadiene, as, for example, those which are obtained by copolymerization of 1,3-butadiene and allyl alcohol, and can also be gidrirovanny.

- Polyhydroxyvalerate copolymers of Acrylonitrile/butadiene, which can be obtained, for example, from epoxides or aminoalcohols and carboxyterminal copolymers of Acrylonitrile/butadiene copolymer (available commercially under the name Hycar®CTBN from Hanse Chemie).

These polyols preferably characterized by an average molecular weight 250-30000 g/mol, in particular 400-20000 g/mol, and preferably an average OH functionality in the range from 1.6 to 3.

In addition to these mentioned polyols to obtain a polyurethane polymerThe PUP can be used together with small quantities of low molecular weight two - or mn is gotany alcohols, such as, for example, 1,2-ethanediol, 1,2 - and 1,3-propandiol, neopentylglycol, diethylene glycol, triethylene glycol, isomers of dipropyleneglycol and dipropyleneglycol, isomers of butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanol, 1,3 - and 1,4-cyclohexanedimethanol, hydrogenated bisphenol a, dimer fatty alcohols, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol or mannitol, sugars such as sucrose, other polyhydric alcohols, low-molecular products alkoxysilane the above two - and polyhydric alcohols, and also mixtures of the aforementioned alcohols. Can also be used along with small amounts of polyols with an average OH functionality of more than 3, for example, sugar alcohols.

As polyisocyanates for the preparation of aromatic polyurethane polymerPUP, containing isocyanate groups, use aromatic polyisocyanates, in particular diisocyanates. As aromatic polyisocyanates are suitable, for example, 2,4 - and 2,6-toluylenediisocyanate and any mixtures of these isomers (TDI, TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any mixtures of these isomers (MDI, MDI), mixtures of MDI and MDI homologues (polymeric MDI or PMDI), 1,3 - and 1,4-delete the entry, 2,3,5,6-tetramethyl-1,4-diisocyanates, naphthalene-1,5-dietzia is at (NDI), 3,3'-dimethyl-4,4'-diisocyanatobutane (TODI, TODI, densityindependent (DADI, DADI), oligomers and polymers of the aforementioned isocyanates, and also any mixtures of the aforementioned isocyanates. Preferred are MDI and TDI.

Mentioned aromatic polyisocyanates are commercially available.

In the second form of the aromatic polyisocyanate P containing isocyanate groups is aromatic polyisocyanate PI. Aromatic polyisocyanate PI,in particular, is an aromatic diisocyanate, or a low molecular weight oligomer aromatic diisocyanate or a derivative of an aromatic diisocyanate, or any mixture of these isocyanates. As aromatic MDI PI is suitable, for example, 2,4 - and 2,6-toluylenediisocyanate and any mixtures of these isomers (TDI, TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any mixtures of these isomers (MDI, MDI), mixtures of MDI and MDI homologues (polymeric MDI or PMDI), 1,3 - and 1,4-delete the entry, 2,3,5,6-tetramethyl-1,4-diisocyanates, naphthalene-1,5-diisocyanate (NDI, NDI), 3,3'-dimethyl-4,4'-diisocyanatobutane (TODI, TODI), densityindependent (DADI, DADI), oligomers and polymers of the aforementioned isocyanates, and also any mixtures of the aforementioned isocyanates.

As MDI PIpreferred are liquid at room temperature, the MDI form (the so-called"modified MDI"), representing mixtures of MDI and MDI derivatives, such as MDI-carbodiimide, MDI-uretonimine or MDI urethanes, known, for example, under the trademarks Desmodur®CD, Desmodur®PF, Desmodur®PC (all from Bayer), Lupranat®MM 103 (from BASF), Isonate®M 143 (from Dow), Suprasec®2020, Suprasec®2388 (both from Huntsman), technical forms PMDI, for example, obtained under the trade names Desmodur®VL, VL 50, VL R 10, VL R 20 and Desmodur®VKS 20 F (all from Bayer), Lupranat® M 10 R, Lupranat® M 20 R (both from BASF), Isonate®M 309, Voranate®M 229, Voranate®M 580 (all from Dow), Suprasec®5025, Suprasec®2050, Suprasec®2487 (all from Huntsman); and technical forms of TDI oligomers, for example, Desmodur®IL (Bayer). The above-mentioned polyisocyanates are usually a mixture of substances with different degrees of oligomerization and/or chemical structure. Preferably they have an average NCO-functionality of from 2.1 to 4.0, and in particular, which contain, iminoimidazolidine, uretdione, urethane, biuret, allophanate, carbodiimide, uretonimine or oxidization group.

A third form of execution of the polyisocyanate P is a mixture consisting of at least one polyurethane polymer PUP and at least one MDI PI as described above.

As usual, the polyisocyanate P is present in amounts of 5-95 wt%. preferably in the amount of 10-90 wt%. calculated on the whole composition. In filled compositions, i.e. compositions which contain a filler, the polyisocyanate Pis present preferably in an amount of 5-60 wt%, in particular 10-50 wt%. calculated on the whole composition.

The composition contains in addition at least one aromatic MDI P,containing isocyanate groups, at least one Valdimir And formula (I).

Preferably Y1and Y2respectively denote a methyl group.

Preferably Y3means the residue of formula (II) or (III)

where R3means a hydrogen atom or an alkyl or arylalkyl group, in particular from 1 to 12 atoms, preferably a hydrogen atom;

R4means a hydrocarbon residue with 1-30, in particular 11-30, the atoms, which optionally contains a heteroatom; and

R5or

means a hydrogen atom,

or means linear or branched alkyl residue with 1-30, in particular 11-30, atoms, optionally with cyclic part and optionally with at least one heteroatom,

or means one or more times unsaturated, linear or branched hydrocarbon residue with 5 to 30 atoms With,

or means, optionally substituted, aromatic or heteroaromatic the ski 5 - or 6-membered cycle.

Particularly preferably, Y3means the residue of formula (III).

The dashed lines in the formulas in this application are, respectively, communication between the proxy and related to him the remainder of the molecule.

Valdimir And formula (I) obtained by the condensation reaction with elimination of water between at least one diamine DA of the formula (IV) and at least one aldehyde ALD of the formula (V). While the aldehyde ALD of the formula (V) used in relation to the amino groups of the diamine stoichiometrically or in a stoichiometric excess.

In formulas (IV) and (V) X, Y1, Y2and Y3have the already mentioned meanings.

For this invention it is essential that two primary amino groups of the diamine DAdiffer from each other or the number of hydrogen atoms of carbon atoms (Cα), standing in the α-position (= 1-position) to the corresponding amino group by at leastoneor the number of hydrogen atoms of carbon atoms (Cβ), standing in the β-position (= 2-position) to the corresponding amino group by at leasttwo.

Thus, the diamine DAcharacterized by different examples of the substituents at the α - or β-carbon atoms to the corresponding amino group. Such diamines characterized by different substituents in question is the application also referred to as "asymmetric". These different substituents lead to different reactivity of the two primary amino groups, in particular with respect to isocyanate groups.

Thus, the diamine DAin one form of execution is a sample of the substituents at the carbon atoms that are α-position to the primary amino groups.

Such diamines DAare, for example, 1,2-propandiamine, 2-methyl-1,2-propandiamine, 1,3-butanediamine, 1,3-diaminopentane (DAMP), 4-aminoacetanilide, 4-aminotetralin, 4-[(4-aminocyclohexane)methyl]aniline, 2-aminoethylamino, 2-aminotetralin, 2-[(4-aminocyclohexane)methyl]aniline and 4-[(2-aminocyclohexanol)methyl]aniline.

Thus, the diamine DA other form of execution is a sample of the substituents at the carbon atoms that are in β-position to the primary amino groups.

Such diamines DAare, for example, 2,2,4-trimethylhexamethylenediamine (TMD), 1,5-diamino-2-butyl-2-ethylpentane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= ISOPHORONEDIAMINE = ACCESSORIES>) and 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA).

The diamine DAit is characterized by two primary groups, of which at least one is aliphatic. The second amino group may be aliphatic or aromatic amino group.

Not considered diamines DAformula (IV) diamines, amino groups which differ from others who ha exclusively for one hydrogen atom of carbon atoms (C β), standing in the β-position to the corresponding amino group. An example of such a diamine, which is not a diamine DA,is 2-methylpentylamine (= 1,5-diamino-2-methylpentan = MPMD). Also not considered diamines DAformula (IV) diamines, amino groups which differ from each other solely by the number of hydrogen atoms of carbon atoms (Cγorδ)standing inγorδ-position to the corresponding amino group. In all these cases, various examples of the substituents at diamines do not show different or are only insignificantly different reactivity of the amino groups, in particular with respect to isocyanate groups.

Preferably the diamine DAformula (IV) selected from the group comprising 1,3-diaminopentane (DAMP), 1,5-diamino-2-butyl-2-ethylpentane, 2,2,4-trimethylhexamethylenediamine (TMD) and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= ISOPHORONEDIAMINE = ACCESSORIES>).

The aldehyde ALD is used to obtain daldinia And formula (I), characterized by formula (V) and is a tertiary aliphatic or tertiary cycloaliphatic aldehyde. As aldehyde ALD is suitable, for example, pavlinovic aldehyde (= 2,2-dimethylpropyl), 2,2-dimethylbutyl, 2,2-diethylbutyl, 1-methylcyclohexanecarboxylic, 1-methylcyclohexanecarboxylic; a simple ester of 2-hydroxy-2-methyl is of ravenala and alcohols, such as propanol, isopropanol, butanol and 2-ethylhexanol; esters of 2-formyl-2-methylpropionic acid or 3-formyl-3-methylmalonic acid and alcohols such as propanol, isopropanol, butanol and 2-ethylhexanol; esters of 2-hydroxy-2-methylpropanal and carboxylic acids, such as butyric acid, somalina acid and 2-ethylhexanoate acid; and described as being particularly suitable ethers and esters of 2,2-disubstituted 3-hydroxypropane-butanole or analogous higher aldehydes, particular 2,2-dimethyl-3-hydroxypropyl.

Especially appropriate aldehydes ALD of the formula (V) in one form of execution are aldehydes ALD1 of the formula (VI), namely aldehydes ALD of the formula (V) with residue Y3formula (II).

In the formula (VI) Y1and Y2accordingly, preferably means methyl group and R3preferably means hydrogen atom.

Aldehydes ALD1 of the formula (VI) are ethers, aliphatic, arylaliphatic or cycloaliphatic 2,2-disubstituted 3-hydroxyaldehyde with alcohols or phenols of the formula R4-OH, such as, for example, fatty alcohols or phenols. Acceptable 2,2-disubstituted 3-hydroxyaldehyde with his side are obtained alcalinity reactions, in particular cross-alcalinity Rea is produced, between primary or secondary aliphatic aldehydes, in particular formaldehyde, and secondary aliphatic, secondary arylaliphatic or secondary cycloaliphatic aldehydes, such as, for example, Isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleramide aldehyde, 2-ethylcaproic aldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionic aldehyde, 2-phenylpropionic aldehyde (hydrotroilite) or diphenylacetaldehyde. Examples of suitable 2,2-disubstituted 3-hydroxyaldehyde are 2,2-dimethyl-3-hydroxypropyl, 2-hydroxymethyl-2-methylbutanal, 2-hydroxymethyl-2-ethylbutanal, 2-hydroxymethyl-2-methylpentanol, 2-hydroxymethyl-2-ethylhexanal, 1-hydroxypolycarboxylic, 1-hydroxypolycarboxylic, 1-hydroxymethyl-cyclohex-3-enecarboxylate, 2-hydroxymethyl-2-methyl-3-phenylpropanal, 3-hydroxy-2-methyl-2-phenylpropanal and 3-hydroxy-2,2-diphenylpropyl.

As examples of such aldehydes ALD1 of the formula (VI) must be named 2,2-dimethyl-3-(2-ethylhexyloxy)propanal, 2,2-dimethyl-3-eurosiberian, 2,2-dimethyl-3-stearothermophilis, 3 cyclohexyloxy-2,2-dimethylpropyl and 2,2-dimethyl-3-phenoxypropanol.

Especially appropriate aldehydesALD form is s (V) in the following form execution are aldehydes ALD2 of the formula (VII), that is, the aldehydes ALD of the formula (V) with residue Y3formula (III).

In the formula (VII) Y1and Y2accordingly, preferably means methyl group and R3preferably means hydrogen atom.

Aldehydes ALD2 of the formula (VII) are esters of the above-described 2,2-disubstituted 3-hydroxyaldehyde with acceptable carboxylic acids.

Examples of suitable carboxylic acids are aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, somalina acid, valeric acid, hexanoic acid, 2-atelophobia acid, enanthic acid, Caprylic acid, pelargonia acid, capric acid, undecanoate acid, lauric acid, tridecanoate acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachnid acid; once unsaturated aliphatic carboxylic acids, such as palmitoleic acid, oleic acid, erucic acid; multiply unsaturated aliphatic carboxylic acids, such as linoleic acid, linolenic acid, aleocharinae acid, arachidonic acid; cycloaliphatic carboxylic acid, t is the cue as cyclohexanecarbonyl acid; arylaliphatic carboxylic acids such as phenylacetic acid; aromatic carboxylic acids such as benzoic acid, naphthoic acid, tolarova acid, anisic acid; isomers of these acids; mixtures of fatty acids from industrial saponification of natural oils and fats such as rapeseed oil, sunflower oil, linseed oil, olive oil, coconut oil, palm kernels and oil palm; as well as complex monoalkylamines and monoacrylate esters of dicarboxylic acids, which get a simple esterification of dicarboxylic acids such as 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-trioxadecyl dicarboxylic acid and similar derivatives of polyethylene glycol, alcohols such as methanol, ethanol, propanol, butanol, and higher homologs and isomers of these alcohols.

Preferred aldehydes ALD2 of the formula (VII) are 3-benzoyloxy-2,2-dimethylpropyl, 3 cyclohexyloxy-2,2-dimethylpropyl, 2,2-dimethyl-3-(2-ethylhexyloxy)propanal, 2,2-dimethyl-3-euroluxe-propanal, 2,2-dimethyl-3-myristoylated OPANAL, 2,2-dimethyl-3-palmitoylation, 2,2-dimethyl-3-stearamidopropyl, as well as similar esters of other 2,2-disubstituted 3-hydroxyaldehyde.

In one particularly preferred form of execution of R5selected from the group comprising phenyl, cyclohexyl, 2-ethylhexyl and C11-With13-With15- and17is an alkyl group.

As the aldehyde of formula (VII) in most cases, the preferred 2,2-dimethyl-3-neurological.

In one preferred method of obtaining aldehyde ALD2 of the formula (VII) 2,2-disubstituted 3-hydroxyaldehyde, for example, 2,2-dimethyl-3-hydroxypropyl, which, for example, can be obtained from formaldehyde (or paraformaldehyde) and isobutyrate, optionally in situ, is subjected to the interaction with the carboxylic acid to the formation of the corresponding ether complex. This esterification can occur without the use of solvent by known methods, for example described in the publication Houben-Weyl, “Methods der organischen Chemie”, Vol. VIII, Seiten 516-528.

Aldehydes ALD2 of the formula (VII) in comparison with aldehydes ALD1 of the formula (VI) are preferable due to their simple way of getting.

In one particularly preferred form of execution of the aldehyde ALD of the formula (V) is nephrosis. The term "Neponset" substance understand the substance that smells so that DL is most human individuals is not determined by the sense of smell, that is undetectable by the nose.

Neponese aldehyde ALD of the formula (V), on the one hand, means aldehyde ALD1 of the formula (VI)where the remainder R4means a hydrocarbon residue with 11-30 atoms, optionally containing a heteroatom.

On the other hand, neponese aldehyde ALD of the formula (V), in particular, means aldehyde ALD2 of the formula (VII)where the remainder R5means or a linear or branched alkyl group with 11-30 atoms, optionally with cyclic part, and optionally with at least one heteroatom, in particular with at least one ether oxygen, or singly or multiply unsaturated linear or branched hydrocarbon chain with 11-30 atoms C.

Examples nephroma aldehydes ALD2 of the formula (VII) are the products of esterification of the above mentioned 2,2-disubstituted 3-hydroxyaldehyde with carboxylic acids, such as lauric acid, tridecanoate acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachnid acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, aleocharinae acid, arachidonic acid, and also mixtures of fatty acids from technical processes saponification of natural Mac is l and fats, such as rapeseed oil, sunflower oil, linseed oil, olive oil, coconut oil, palm kernels and oil palm.

Preferred neponosima aldehydes of the formula (VII) are 2,2-dimethyl-3-neurological, 2,2-dimethyl-3-myristoylation, 2,2-dimethyl-3-palmitoylation and 2,2-dimethyl-3-stearamidopropyl. Especially preferred is 2,2-dimethyl-3-neurological.

Guldimann And formula (I) is characteristic that in the absence of water, they do not react with isocyanates. In particular, this means that their residues X, Y1, Y2and Y3no groups which are reactive toward isocyanate groups. In particular X, Y1, Y2and Y3do not contain hydroxyl groups that do not contain primary or secondary amino groups, do not contain mercaptopropyl and do not contain other groups with active hydrogen.

Then Guldimann And formula (I) is characteristic that their aldimine group may not be subject to tautomerism to enamine groups, as they are as substituents in α-position to the atom aldimine groups do not contain hydrogen. Due to this property they form together with aromatic polyisocyanates P containing isocyanate groups, particularly stable during storage, that is fairly consistent about the wearing of viscosity, of the mixture.

Gialdini Andwhich were obtained on the basis ofnephroma aldehydes described above, are particularly preferred forms of execution are neponosima. Such nephroma gialdini especially preferred. For many applications no smell is a big advantage or a mandatory condition, particularly in enclosed spaces, such as inside buildings or vehicles and in extensive use, as, for example, in the coating of the floor.

Gialdini And under suitable conditions, in particular with the exclusion of moisture, stable during storage. When the access of moisture them aldimine group through an intermediate stage formally be either hydrolyzed to amino groups, and is released appropriate to be used to obtain daldinia And aldehyde ALD of the formula (V). Since this hydrolysis reaction is reversible and the chemical balance clearly shifted towards aldimine, in the absence of groups reactive towards amines, hydrolyses only part aldimine groups.

In the presence of isocyanate groups, the equilibrium of the hydrolysis shifts, as gidrolizuacy aldimine groups with isocyanate groups react irreversibly with the formation of urea groups. The reaction of the isocyanate groups with gidrolizuemye aldimine groups should not inevitably occur is to build through free amino groups. Of course, it is also possible reaction with the intermediate stages of hydrolysis. A valid example is that gidrolizuacy elimina group in the form of polyamines directly reacts with the isocyanate group.

Valdimir Andin the composition preferably is present in a stoichiometric excess, stoichiometric or stoichiometric insufficient quantity per isocyanate group. Preferably Valdimir Andformula (I)is present in the composition in such amounts that the ratio between the number aldimine groups and the number of isocyanate groups is 0.1 to 1.1, in particular of 0.15 to 1.0, particularly preferably from 0.2 to 0.9.

As daldinia And can also be used mixtures of different valdemiro And.In particular, there can be used mixtures of different valdemiro And who receive based on mixtures of different diamines DAformula (IV) and/ormixtures of different aldehydes ALDformula (V).

It is also possible that in addition to at least daldinia And in the composition can contain other polyamidimide. For example, it is possible to expose the interaction of the diamine DA of the formula (IV) with a mixture containing the aldehyde ALDand dialdehyde. It is also possible to use a mixture of aldehydes, which in addition to aldehyde ALDcontains on the other aldehydes.

The composition may in addition to at least one aromatic polyisocyanate P, characterized by isocyanate groups, and at least one valdemiro Andformula (I) contain other AIDS and additives.

The composition reacts with water or moisture and consequently sewn. If there is enough water to expose the interaction of most or all of the isocyanate groups is formed of the cured composition, which is characterized by excellent mechanical properties. Therefore, the composition can be called "vlagootverzhdaemykh".

The composition may be in the form of one-component compositions or in the form of two-component composition. One-component compositions have the advantage that they are applied without mixing process, while the two-component compositions have the advantage that they quickly harden and as components may contain substances, which, together with the isocyanates are not stable when stored.

In one form of the composition exists in the form of a one-component composition.

As aromatic MDI P, characterized by isocyanate groups, in one-component compositions, the preferred polyurethane polymer PUP, described above.

The quality is TBE auxiliary substances and additives for the one-component compositions are suitable, for example, the following substances:

- plasticizers, for example esters of carboxylic acids, such as phthalates, for example, dioctylphthalate, diisononylphthalate or diisodecylphthalate, adipate, for example, dioctyladipate, azelate and Sabatini, organic esters of phosphoric and sulfonic acids or polybutene;

- solvents;

inorganic and organic fillers, for example ground or precipitated calcium carbonates, which optionally coated with stearates, soot, in particular industrial soot obtained (hereinafter referred to as "soot"), barite (BaSO4also called heavy spar), kaolin, alumina, aluminum hydroxide, silicic acid, in particular finely dispersed silicic acids from pyrolysis processes, PVC powder or hollow beads;

fiber, for example, polyethylene;

- pigments, for example titanium dioxide or iron oxides;

- catalysts that accelerate the hydrolysis aldimine groups, in particular acid or compounds gidrolizuemye to acids, for example organic carboxylic acids such as benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic anhydrides of carboxylic acids, such as phthalic anhydride or hexahydrophthalic anhydride, complex Silovye esters of organic carboxylic acids, organic sulfonic acids, so is e as methanesulfonate acid, pair-toluensulfonate acid or 4-dodecylbenzenesulfonic acid, or other organic or inorganic acids;

- catalysts that accelerate the reaction of isocyanate groups with water, in particular metal compounds, for example tin compounds such as dibutylaminoethanol, dibutyltindilaurate, dibutyltindilaurate, dibutyltindilaurate, dioctyladipate, dibutyltindilaurate and oxide dibutylamine, tin(II)carboxylates; stanekzai, such as lauristons, bismuth compounds such as bismuth(III)-octoate, bismuth(III)-neodecanoate or bismuth(III)-oxidati; and also tertiary amines, for example, a simple 2,2'-demoralization ester and other derivatives simple Martinovich esters;

- rheology modifiers such as, for example, thickeners or means for thixotropy, for example, compounds of urea, polyamide waxes, bentonites or pyrogenic silicic acids;

reactive diluents and suturing, for example, Monomeric polyisocyanates such as MDI, TDI, mixtures of MDI and MDI homologues (polymeric MDI or PMDI), and oligomers of these polyisocyanates, in particular in the form of isocyanurates, carbodiimides, uretonimine, Burlov, allophanate or iminoimidazolidine, adducts of Monomeric polyisocyanates with short-chain polyols, and also dehydrated adipic acid and on the other dihydrazide, and blocked amines in the form of aldimines, ketimines, oxazolidines or enamines;

driers, for example, molecular sieves, calcium oxide, highly reactive isocyanates such as para-totalitarian, ester orthomorphisms acid, alkoxysilane, such as tetraethoxysilane, organoalkoxysilanes, such as VINYLTRIMETHOXYSILANE and organoalkoxysilanes characterized by the functional group in the α-position to a silanol group;

- adhesion promoters, in particular organoalkoxysilanes, such as, for example, epoxysilane, vinylsilane, (meth)acrylicana, isocyanatobenzene, carbonatation, S-(alkylsulphonyl)mercaptoethane and eliminazione, and also oligomeric forms of these silanes;

- stabilizers against heat, light and UV radiation;

- retardants;

- surfactants, for example, suturing, to contribute to spreading, means to support ventilation, or antispyware;

- biocides, such as, for example, algaecides, fungicides or substances that slow the growth of fungi.

You should take into account the fact that such additives do not cause harm to the stability of the composition during storage. This means that these additives during storage may not significantly affect the reaction, leading to the stitching as hydrolysis aldimine groups or crosslinking isocyanate groups. In the lastnosti, this means that all these additives must not contain all or most may contain only traces of water. So, perhaps you certain supplements before adulteration in composition to dry chemically or physically.

Preferably one-component composition, in addition to at least one MDI P and at least one daldinia And formula (I) contains at least one catalyst. The catalyst, in particular, is one of these acids, such as benzoic acid or salicylic acid, or one of the above-mentioned metal compounds, or one of the above-mentioned tertiary amines. In particular, we are talking about the catalyst, which accelerates the hydrolysis aldimine groups, preferably on acid. Also preferably completely, if you mix different catalysts or different types of catalysts.

One-component composition preferably receive and store with the exclusion of moisture. Suitable impermeable packaging or device, such as, for example, barrel, bag, or cartouche, it is characterized by exceptional stability during storage. The concept of "stable storage" and "storage stability" in connection with the composition in this application has a value such that the viscosity of the composition at a given temperature nanesenii when suitable storage in the period of time is not increased or the maximum increase in the extent the composition may be recycled specified method.

If one-component composition is in contact with moisture or water, aldimine group daldinia And begin to either hydrolyzed. Isocyanate groups present in the composition, then react with gidrolizuemye aldimine groups, and allocates at least one aldehyde ALD of the formula (V). Isocyanate groups that are against aldimine groups in excess to react directly with water. As a result of these reactions, the composition crosslinks and finally solidifies with the formation of solid material. The reaction of isocyanate groups with gidrolizuemye aldimine groups when this does not have to pass through the free amino group; possible reactions with intermediate stages of hydrolysis reactions. A possible example is that gidrolizuacy aldimine group in the form of polyamines directly react with isocyanate groups.

The water necessary for the curing reaction may or separate from the air (humidity, atmospheric moisture), or the composition can be brought into contact with components containing water, for example, by spraying, or in the composition when applied can be added to components containing water, in particular by adding it.

The composition of the foundations of the om cures without bubbles, in particular at high speed curing.

On the curing rate can be influenced by the type and amount of one or more optionally present catalysts using temperature prevailing during curing, and by humidity or the amount of added water.

If in the composition adds the components of a water-containing curing composition is much faster compared to curing solely under the action of humidity. For this case, a longer "dwell time before pasting" compositions described here is particularly great advantage. This way we obtain a composition, which is suitable for practice time before bonding very quickly otverzhdajutsja.

The following form of the composition is in the form of two-component composition. Two-component composition consists of component K1 and a component K2, which are stored separately from each other and are mixed with one another only shortly before use.

In one form of the two-component composition aromatic polyisocyanate P containing isocyanate groups, and Valdimir And formula (I) are part of the first component K1,and the second component K2 contains compounds reactive toward sociality groups, in particular water and/or polyols and/or polyamine.

In another form of implementation of two-component composition aromatic polyisocyanate P containing isocyanate groups, is part of the first component K1,whilethe second component K2 contains Valdimir And formulas (I)and compounds reactive towards isocyanate groups, in particular water and/or polyols, and/or polyamine.

Preferably component K2 contains at least one Valdimir And formulas (I) and water.

Preferably component K2 contains at least one Valdimir And formulas (I) and at least one polyol, and in the composition preferably is 0.3 to 1 equivalent aldimine groups to equivalents of hydroxyl groups.

Particularly preferably, the component K2 contains at least one Valdimir And formula (I)at least one polyol and water, and in the composition preferably is 0.3 to 1 equivalent aldimine groups to equivalents of hydroxyl groups of polyol and water per aldimine group is preferably present in the ratio below the stoichiometric.

In both the above forms of implementation of two-component composition acceptable polyols are the same as those commercially available polyols, which have already been mentioned as when adnych to obtain a polyurethane polymer PUP, and those of low molecular weight two - or polyhydric alcohols which have been previously mentioned as suitable for joint use in obtaining a polyurethane polymer PUP.If the component K2 contains water, preferably, if the maximum amount of water is determined such that it is necessary for hydrolysis daldinia And- and, optionally, possibly another latent hardener. In addition, both components can contain other auxiliary substances and additives, which have already been mentioned for the one-component composition. However, in the case of component K2 optionally other auxiliary substances and additives. In particular, such auxiliary substances and additives that are not suitable for storage together with aromatic isocyanate groups, or suitable only for short-term storage. In particular catalysts, such as described below:

compounds of zinc, manganese, iron, chromium, cobalt, copper, Nickel, molybdenum, lead, cadmium, mercury, antimony, vanadium, titanium, zirconium, or potassium, zinc(II)acetate, zinc(II)2-ethylhexanoate, zinc(II)-laurate, zinc(II)oleate, zinc(II)naphthenate, zinc(II)acetylacetonate, zinc(II)-salicylate, manganese(II)2-ethylhexanoate, iron(III)-2-ethylhexanoate, iron(III)acetylacetonate, chromium(III)2-ethylhexanoate, cobalt(II)naphthenate, cobalt(II)-2-e is Elecsnet, copper(II)2-ethylhexanoate, Nickel(II)naphthenate, finalstate-neodecanoate, lead(II)acetate, lead(II)2-ethylhexanoate, lead(II)-neodecanoate, lead(II)-acetylacetonate, aluminum lactate, aluminum oleate, aluminum(III)-acetylacetonate, diisopropoxide-bis-(ethylacetoacetate), dilutability-bis-(ethylacetoacetate), dilutability-bis-(acetylacetonate), potassium acetate, octoate potassium; tertiary amines such as triethylamine, tributylamine, N-ethyldiethanolamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine and their higher homologues, N,N,N',N'-tetramethylpropylenediamine, pentamethyldiethylenetriamine and their higher homologues, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis(dimethylamino)methane, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N,N-dimethylhexylamine, bis-(N,N-diethylaminoethyl)adipate, N,N-dimethyl-2-phenylethylamine, Tris-(3-dimethylaminopropyl)amine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), N-methylmorpholine, N-ethylmorpholine, N-cocomotion, N,N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethylacrylate, bis-(dimethylaminoethyl)piperazine, 1,3,5-Tris-(dimethylaminopropyl)hexahydrotriazine, bis-(2-dimethylaminoethoxy) (simple) ether; astrometricheskie compounds such as 4-dimethylaminopyridine, N-Mei, N-vinylimidazole or 2-dimethylimidazole; amidine and guanidine, such as 1,1,3,3-tetramethylguanidine; tertiary amines containing active hydrogen atoms, such as triethanolamine, triisopropanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, 3-(dimethylamino)propertiesproperty, bis-(3-(dimethylamino)propyl)isopropanolamine, bis-(3-dimethylaminopropyl)amine, 3-(dimethylamino)proprotein, Mannich bases, such as 2,4,6-Tris-(dimethylaminomethyl)phenol or 2,4,6-Tris-(3-(dimethylamino)propylaminoethyl)phenol, N-hydroxypropylamino N-(3-aminopropyl)imidazole, as well as products alkoxysilane and polyalkoxysiloxanes of these compounds, for example, dimethylaminoethoxide; organic ammonium compounds, such as benzyltrimethylammonium or alkoxysilane tertiary amines; the so-called catalysts "slow motion", which is a modification of a known metal or amine catalysts, such as the interaction products of tertiary amines and carboxylic acids or phenols, for example, from 1,4-diazabicyclo[2.2.2]octane or DBU and formic acid or acetic acid; and combinations of these compounds, in particular metal compounds and tertiary amines.

Preferably component K2 does not contain isocyanate groups.

If the composition contains other blocked amines, in particular aldimine, cetim the us, oxazolidine or enamines, they may be part of component K1and/orK2. As aldimine especially acceptable are other aldimine, such as Valdimir And that derived from other amines according to the formula (IV), and/or based on other aldehydes, according to the formula (V). All these blocked amines tend hydrolysis to free amino groups, which react quickly with the available isocyanate groups.

Getting the two components K1 and K2 independently from each other, at least for the component K1 with the exclusion of moisture. The two components K1 and K2 separately are stable during storage, i.e. each of them can be stored in suitable packaging or device, such as a barrel, tin container, bag, bucket, or cartouche, before using them for several months up to a year or more, without changing their respective properties at the scale required for their use.

The ratio between the two components K1 and K2 are preferably chosen so that the groups of components K1 and K2, reactive towards isocyanate groups, are suitable relation to the isocyanate groups of component K1. In the two-component composition before curing is suitable, there are 0.1 to 1.1, preferably from 0.5 to 0.95, and the TOC is built preferably 0.6 to 0.95 equivalents group amount reactive toward isocyanates, in the equivalent of isocyanate groups, and aldimine group and, optionally present other blocked amino group is referred to the groups reactive toward isocyanates, and the water is not taken into account groups reactive toward isocyanates. Excess isocyanate groups react preferentially directly with water, for example, with air moisture.

Before or during application of two-component composition both components are mixed with each other in a suitable way. Mixing can be done continuously or intermittently. The mixed composition during mixing or at the end of the mixing is applied, and its lead in contact with the surface of a solid body, with optional use of certain auxiliary means. This should draw attention to the fact that the mixing of components K1 and K2 and the use was not too much time, because this can cause problems, such as slow or full adhesion to a solid surface. The maximum period of time during which the mixed composition should be used, means both "sustainability"and "waiting time before bonding". Often the waiting time before bonding is" defined as the time during which the viscosity of the mixed composition is doubled.

After mixing of the components K1 and K2 starts curing. Deletemin And formula (I) is either hydrolyzed already described manner and to react with isocyanate groups, as soon as he comes in contact with water. Or water was already present in the mixed composition, because that was the ingredient component K2or because it was added to the composition before or during the mixing of the two components K1 and K2-,orwater was diffusional in the mixed composition in the form of moisture in the air. In the latter case, the reaction occurs valdemone And with isocyanate groups from outside to inside, in parallel with the penetration of moisture air in the composition. As indicated above, the reaction of the isocyanate groups with gidrolizuemye aldimine groups need not necessarily be carried out through free amino groups, but may also be effected through an intermediate stage of hydrolysis. In the same way released reactive group other latent hardeners, optionally present in the composition. Next, after mixing of the components K1 and K2with isocyanate groups react with compounds reactive towards isocyanate groups, optionally present in the composition, in particular polyols and polyamine. From ydachnie isocyanate groups, in particular, react directly with water. As a result of these reactions mixed composition crosslinks and finally cures to a solid material.

The composition is mainly cures without bubbles, in particular at high speed curing.

On the curing rate can influence the type and amount of one or more optionally present catalysts, the temperature prevailing during curing, as well as the humidity or the amount of water introduced with the componentK2.

As in one-component and two-component form of execution described composition, on the one hand, has a long waiting time before bonding, and on the other hand, high speed curing. The combination of long exposure times before pasting and fast curing for the many one-component and two-component compositions is highly desirable.

Using a one-component composition is often simple if after the application is still some time to give the composition a desired shape, before he formed the crust of hardened material on the surface. For example, the sealant is still quite a long time after application should be able to be polished; the adhesive should be able obodno to move, in order to accurately align the joined parts; coating or lining must be aligned or, for example, powdered rubber crumb, sand or colored plates. But then the composition should quickly be cured to it as quickly as possible could be loaded and/or that it was not covered with dust.

The use of two-component composition also is often rather simple, if it is characterized by a prolonged waiting time before bonding, as during the time before pasting another should be carried out as the process of mixing and applying the composition, and optionally the required stage subsequent processing, for example, to give the composition the desired form. For example, two-component flooring, which is mixed in portions and then pour on the base and polished, must be a long time before gluing, so that the application could be neat, without time pressure. But then the composition should quickly be cured to it as quickly as possible could be loaded. For flooring is often necessary condition for flooring at the latest the next day after application in General overdise so that it could be designed for the load that could be carried out further work.

In the case of onecompany is based composition as a measure of time before pasting usually determine the time of formation of a crust. Under the "time of the formation of a crust" at the same time understand the period of time that occurs between the coating composition and the formation of a crust of hardened material on the surface of the composition. As a measure of the speed of curing one-component compositions, cured from the outer part to the inner, usually establish so-called full curing. Under this measure, for example, the thickness of the cured layer, which was formed under certain conditions after a specified period of time in the deposited composition; or measure the time that is necessary to the composition, a layer of given thickness, under certain conditions, fully hardened.

In the case of two-component composition as a measure of time before bonding can be determined period of time, during which after mixing both components occurs, for example, a certain increase of viscosity (for example, double gain), or the composition is characterized by a non-adhesive surface. As a measure of the speed of curing two-component compositions can be installed, for example, increase of hardness, for example, shore hardness, over time.

Only due to the composition according to the invention can be realized in a single composition combined with each other a long time what I excerpts before gluing and high speed curing.

The effect of long time exposure before gluing at high speeds curing clearly define, as shown by the following examples. The basis for this were until now not been studied in detail. But you can assume that the effect can be described asymmetry valdemone And formula (I) or originating from the diamine DA of the formula (IV). When the water first react exclusively reactive aldimine group daldinia And,or a reactive amino groups of the diamine DA, with isocyanate groups MDI P. However, this still does not lead to crosslinking of the composition, but only to a small increase in the viscosity, which probably limits the waiting time before bonding. Only when reactive aldimine group, or amino group, significantly consumed, begin to react slow aldimine group, or amino group, with the following isocyanate groups, which now directly leads to crosslinking of the composition and greatly accelerates the cure.

As already described, Valdimir Andformula (I) is based on a special asymmetric diamines DA of the formula (IV) and tertiary aldehydes ALD of the formula (V). The different reactivity of the two amino groups in the diamine DA, based on different substances transferred directly to Valdimir of the diamine DA,in which both aldimine groups also exhibit different reactivity. In the special case daldinia And there is a difference of reactivity in aldimine groups caused by tertiary, and therefore sterically strained, the structure of the aldehyde ALD underlying aldimine groups, presumably even more enhanced because of steric busy aldehyde residue further limits the availability aldimine groups - in particular, if they exist in polyhydrocarbons form as polymyalgia group - and therefore disproportionately reduces reactivity slow aldimine groups compared with the same quick aldimine groups.

Thanks to the use of preferably nephroma of valdemiro And, it is also possible first of all to get any of the songs before, during and after curing do not smell. This property is a great advantage compared with the prior art and significantly extends the use of these compositions.

The described compositions are particularly suitable as one - and two-component adhesives, sealants, potting mass or floor coverings, in particular floor coverings. In particular they are suitable as elastic adhesives, elastic sealants, elastic sealing mass or elastic coating. Especially preferably, they are used to is the amount of elastic sealants, as the use of special valdemiro And in dry condition attached particular plastic-elastic properties.

In particular, the described composition suitable as plastic-elastic sealant for sealing joints of all kinds, in particular joints in buildings. The so-called expansion joints are joints that are located in suitable places and in suitable spaces of buildings to smooth movement between the parts of hard building materials such as concrete, stone, resin and metal. Such transfers occur on the one hand, due to vibration and, on the other hand, due to changes in temperature. In cold solid materials are reduced, so that the seams become wider, and in the heat they expand, causing the joints to become denser. The sealant, which should long to seal these seams, must be plastic-elastic properties, so that when tension and compression in the seam if possible, less power is transferred to the substrate, and thereby it has been possible lesser load. Under the plastic-elastic properties in the present description see high elongation and a low voltage value when stretching, and a good opportunity to return to its original position). The concept of "tension tensile" oznake the voltage, which acts in the material in the stretched condition.

Particularly low values of tensile stress in dry condition characterized by the composition of sealants, which contain at least one Valdimir And, in which X in the formula (I) means the remainder of the diamine DA selected from the group consisting of TMD, and accessories > 1,5-diamino-2-butyl-2-ethylpentane.

The following aspect of the invention concerns a method of bonding a substrate S1 to a substrate S2. This method involves the following stages:

i) applying the above-described composition on a substrate S1;

ii) contacting the applied composition with a substrate S2 within the exposure time before the bonding composition;

or

i') applying the above-described composition on a substrate S1 and a substrate S2;

ii') contacting the applied compositions with each other during the exposure time before the bonding composition;

moreover, the substrate S2 consists of the same or different material as compared with the substrate S1.

In addition, the invention relates to a method of sealing comprising the stage of:

i) applying the above composition between a substrate S1 and a substrate S2, so that the composition is in contact with the substrate S1 and the substrate S2;

moreover, the substrate S2 consists of the same or different material as compared with the substrate S1.

Period, in which method plot the value is between the substrate S1 and a substrate S2, the specialist is called a "seam". Usually the composition is extruded from a cartouche in pre-treated joints and then polished manually, often the tool, soapy water, for example, a spatula or your finger processor, soapy water, conduct applied on top of the sealant to become smooth and dense surface, with just a little deeper inside. Because the processor is often first smoothes the applied sealant, if it fills large areas of the seams between applying and smoothing the sealant may be a long time, for example, up to one hour. But in order to provide accurate anti-aliasing, it is necessary that the surface of the sealant at this time has not yet formed a crust from the cured material. Therefore sealants with a short waiting time before bonding to processors sealants are undesirable. Despite this, it is important that the sealant after a long time before gluing quickly utverjdala and formed a non-adhesive surface, as for the sticky uncured surface of the sealant is great danger of contamination, such as dust and sand. On the other hand, the sealant composition in dry condition shall have a maximum plastic-elastic properties. E. and requirements described composition could be performed.

Finally, the invention relates to a method of coating a substrate S1, which includes stage

i') applying a composition according to any one of claims 1-16 of claims on a substrate S1 within the exposure time before the bonding composition.

For all these methods, the substrate S1 and/or S2 can be represented by a large number of materials. In particular, they are inorganic substrates such as glass, glass ceramic, concrete, construction, cement, brick, tile, gypsum or natural stone such as granite or marble; metals or alloys such as aluminum, steel, non-ferrous metal, galvanized metals; organic substrates such as wood, polymers, such as PVC, polycarbonate, emission spectra obtained for pure, polyethylene, polypropylene, complex, polyester, epoxy resin, polyurethane (PUR); substrates with a coating, such as a metal or alloy with powder coating or paint or varnish, particular automotive top coat varnish.

In all these methods, the substrate S1 and/or the substrate S2 before gluing or sealing or coating can be pre-treated, in particular a primer layer or the composition of the adhesion promoter. Pre-treatment of this kind in particular includes a method of physical and/or chemical cleaning and activation, such as, for example, grinding, sandblasting clicks the processing, cleaning brush, treatment by corona discharge, the treatment with plasma processing, flame, surface etching and the like, or treatment with cleaners or solvents, or the application of the adhesion promoter, the solution of the adhesion promoter or primer layer.

Of these described methods for the bonding, sealing or coating is formed product.

This product is essentially a structure, in particular the construction of the ground or underground, or industrial product, or a consumer product, such as, in particular, window, machine for household or vehicle, in particular a water or land vehicle, preferably a car, bus, truck, train or ship, or structural element of the vehicle.

EXAMPLES

Description methods

Infrared spectra were measured on the instrument FT-IR 1600 from Perkin-Elmer (horizontal ATR measuring cell with ZnSe crystal), and substances applied in film form, undiluted. The absorption bands are given in wave numbers (cm-1) (measurement range: 4000-650 cm-1).

Spectra1H-NMR was measured in the spectrometer type Bruker DPX-300 when 300,13 MHz; chemical shifts δ are given in ppm (ppm) relative to tetramethylsilane (TMS). The interaction constant J are given in Hz. Authentic is and pseudopeziza interactions do not distinguish.

Viscosity was measured on controlled viscometer type cone - plate Physica UM (cone diameter 20 mm, cone angle 1°, the distance from the vertex of the cone to the plate of 0.05 mm, shear rate 10-1000-1).

The content of amines in the received valdemone, i.e. the content of the blocked amino groups in the form aldimine groups was determined by titrimetric (0.1 n HClO4in glacial acetic acid, crystal violet) and always resulted in mmol N/g

a) Obtaining valdemiro

Valdimir a-1

In a round bottom flask under nitrogen atmosphere were placed 55,0 g (to 0.19 mol), distilled 2,2-dimethyl-3-euroelections. With vigorous stirring of the dropping funnel was slowly added 15.6 g (0.18 mol N) 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= ISOPHORONEDIAMINE, ACCESSORIES>; Vestamin® IPD, Degussa; the content of amine 11,68 mmol N/g), and the mixture was heated and became thicker. Then volatile components were released to the vacuum (10 mbar, 80°C). Output: 67,1 g clear, colorless oil with an amine content by 2.73 mmol N/g and a viscosity of 190 MPa∙s at 20°C.

IR: 2952, 2922, 2852, 2819 shortened, 1738 (C=O), 1666 (C=N), 1464, 1418, 1394, 1378, 1364, 1350, 1298, 1248, 1236 shortened, 1158, 1112, 1048, 1020, 1000, 938, 928, 910, 894, 868, 772, 722.

1H-NMR (CDCl3, 300 K): δ to 7.59 and EUR 7.57 (2×s, total 1H, CH=N ([isomer]), 7,47 (s, 1H, CH=N), and 4,03 4,01 (2×s, 2×2H, C(CH3)2-CH2-O), 3,37 (m, 1H, N-CHCy), is 3.08 (DD, 2H, J≈11,1 N-CH 2-CCy), is 2.30 (t, 4H, J≈7,5, OC(O)-CH2-CH2), to 1.61 (m, 4H, OC(O)-CH2-CH2), 1,60-0,85 (m, 65H, rest of CH).

Valdimir a-2

In a round bottom flask under nitrogen atmosphere were placed 55,0 g (to 0.19 mol), distilled 2,2-dimethyl-3-euroelections. With vigorous stirring of the dropping funnel was slowly added 9.4 g (0.18 mol N) 1,3-diaminopentane (DAMP; Dytek®EP Diamine, Invista; the content of amine 19,42 mmol N/g), and the mixture was heated and became thicker. Then volatile components were released to the vacuum (10 mbar, 80°C). Output: 60,9 g transparent, light-yellow oil with an amine content 3,01 mmol N/g and a viscosity of 50 MPa∙s at 20°C.

IR: 2955 shortened, 2922, 2868 shortened, 2852, 1737 (C=O), 1666 (C=N), 1466, 1419, 1394, 1373, 1346, 1300, 1248, 1233, 1159, 1112, 1057, 1019, 1000, 935, 884, 769 broadened, 722.

Valdimir a-3

In a round bottom flask under nitrogen atmosphere were placed 50.0 g (0.18 mol), distilled 2,2-dimethyl-3-euroelections. With vigorous stirring of the dropping funnel was slowly added to 15.8 g (0,17 mol N) of 1,5-diamino-2-butyl-2-ethylpentane (amine content 10,52 mmol N/g), and the mixture was heated and became thicker. Then volatile components were released to the vacuum (10 mbar, 80°C). Output: 62,6 g transparent, almost colorless oil with an amine content of 2.64 mmol N/g and a viscosity of 100 MPa∙s at 20°C.

IR: 2951, 2922, 2871 shortened, 2852, 2831 shortened, 1738 (C=O), 1669 (C=N), 1463, 1418, 1393, 1375, 131, 1302, 1248, 1234, 1159, 1112, 1019, 999, 935, 874 shortened, 848 shortened, 777, 722.

ValdimirA-4

In a round bottom flask under nitrogen atmosphere were placed 79,4 g (0.28 mol), distilled 2,2-dimethyl-3-euroelections. With vigorous stirring of the dropping funnel was slowly added to 20.0 g (0.25 mol N) 2,2(4),4-trimethylhexamethylenediamine (Vestamin® TMD, Degussa; the content of amine 12,64 mmol N/g), and the mixture was heated and became thicker. Then volatile components were released to the vacuum (10 mbar, 80°C). Output: 94,4 g transparent, light-yellow oil with an amine content of 2.66 mmol N/g and a viscosity of 63 MPa∙s at 20°C.

IR: 2954, 2920, 2852, 2822 shortened, 1737 (C=O), 1668 (C=N), 1466, 1418, 1392 shortened, 1374, 1365, 1348, 1301 shortened, 1248, 1234, 1158, 1112, 1020, 999, 932, 867, 722.

Valdimir A-5

In a round bottom flask under nitrogen atmosphere were placed 24,3 g (85 mmol), distilled 2,2-dimethyl-3-euroelections. With vigorous stirring of the dropping funnel was slowly added 5.0 g (81 mmol N) 4-aminomethylpyridine (=4-aminobenzoylamino; the content of amine 16,24 mmol N/g), and the mixture was heated and slightly thickened. Then volatile components were released to the vacuum (10 mbar, 80°C). Output: 27,6 g transparent, light-yellow oil with an amine content of 2.93 mmol N/g and a viscosity of 125 MPa∙s at 20°C.

Valdimir A-6(comparative)

In a round bottom flask under nitrogen atmosphere were placed 60,0 g (0.21 mol) pereg the data 2,2-dimethyl-3-euroelections. With vigorous stirring of the dropping funnel was slowly added to 11.8 g (0.20 mol of N) of 1,5-diamino-2-methylpentane (MPMD; Dytek®A, Invista; the content of amine 17,04 mmol N/g), and the mixture was heated and became thicker. Then volatile components were released to the vacuum (10 mbar, 80°C). The output is 68.2 g of a transparent, light yellow oil with an amine content to 2.94 mmol N/g and a viscosity of 53 MPa∙s at 20°C.

Valdimir a-7(comparative)

In a round bottom flask under nitrogen atmosphere were placed for 80.9 g (0.27 mol), distilled 2,2-dimethyl-3-euroelections. With vigorous stirring of the dropping funnel was slowly added to 25.2 g (0.26 mol N) 3(4),8(9)-bis-(aminomethyl)tricyclo[5.2.1.02,6]decane (TCD-diamine, Celanese; the content of amine 10,23 mmol N/g), and the mixture was heated and became thicker. Then volatile components were released to the vacuum (10 mbar, 80°C). Output: 100,8 g transparent, almost colorless oil with an amine content of 2.56 mmol N/g

Valdimir a-8(comparative)

In a round bottom flask under nitrogen atmosphere were placed of 74.3 g (0.26 mol), distilled 2,2-dimethyl-3-euroelections. With vigorous stirring of the dropping funnel was slowly added 30.0 g (0.25 mol N) simple polyetherdiamine (Polyoxypropylenediamine with an average molecular weight of about 240 g/mol; Jeffamine®D-230, Huntsman; amine content 8,29 mmol N/g), and the mixture was heated the camping and became thicker. Then volatile components were released to the vacuum (10 mbar, 80°C). Output: of 99.5 g of a transparent, light yellow oil with an amine content of 2.50 mmol N/g

ValdimirA-9 (comparative)

In a round bottom flask under nitrogen atmosphere were placed of 50.9 g (0.18 mol), distilled 2,2-dimethyl-3-euroelections. With vigorous stirring of the heated dropping funnel was slowly added 10.0 g (0,17 mol N) 1,6-hexamethylenediamine (BASF; the content of amine 17,04 mmol N/g), and the mixture was heated and became thicker. Then volatile components were released to the vacuum (10 mbar, 80°C). Output: 57,7 g transparent, light-yellow oil with an amine content to 2.94 mmol N/g

b) Obtaining compositions

Examples 1-5 and comparative examples 6-8

For each example the corresponding components according to table 1 were weighed in predetermined weight parts without pre-drying in a polypropylene jar with a screw-top jar and mixed by means of a centrifugal mixer (SpeedMixerTMDAC 150, FlackTek Inc.; 1 min at 2500 rpm./min), the mixture was immediately loaded into the varnished inside aluminum tube and sealed it closed.

The polyurethane polymer PUP-1 was prepared as follows.

1300 g of polyoxypropylene (Acclaim®4200 N, Bayer; OH number 28.5 mg KOH/g) 2600 g Polyoxypropylenediamine (Caradol®MD34-02, Shell; OH number of 35.0 mg KOH/g), 600 g of 4,4-etilendiamindisuktsinatov (MDI; Desmodur®44 MC L, Bayer) and 500 g of diisodecylphthalate (DIDP; Palatinol®Z, BASF) were subjected to interaction at 80°C. until the NCO-terminated polyurethane polymer with a content of free isocyanate groups 2,05% weight. and viscosity of 31.6 PA∙s at 20°C.

The ratio between isocyanate groups and aldimine groups in all examples was 1.0/0,70.

Table 1
The composition of examples 1-5 and comparative examples 6-8
Example123456 Ms.7 Ms.8 Ms.
PUR-polymer PUP-150,050,050,050,050,050,050,050,0
ValdimirA-1,
6,26
A-2
5,67
A-3,
6,47
A-4
6.42 per
A-5
of 5.82
A-6,
of 5.81
A-7
to 6.67
A-8,
6,84
The acid catalystand0,10,10,10,10,10,10,10,1

andSalicylic acid (5% weight. in dioctyladipate).

Thus obtained composition was tested for stability in storage, waiting time before bonding and curing rate.

The storage stability was determined from the change in viscosity during heat aging. This composition was kept in a sealed tube in an oven at 60°C, and measured the viscosity at 20°C for the first time after 12 hours and again after 7 days of incubation.The storage stability is given in percentage increment of the second value of viscosity in relation to the first.

As a measure for the exposure time before gluing used during the formation of the crust (without glue, “tack-free”). To measure the time of crust formation small part of the composition to room temperature, sustained pri°C for 2 hours, applied with a layer thickness of about 2 mm to cardboard and at 23°C and 50% relative air humidity was determined by time up until when lightly disturbing the surface of the composition by means of a pipette of LDPE on the pipette for the first time there was no more residue.

As a measure of the speed of curing used the time to complete curing of the composition. Time to complete curing of the composition was found that the composition in the form of a film with a thickness of 5 mm was filled in in the form of PTFE, and kept under normal conditions and by periodically lifts the edges of the film was determined by the number of days that you want to film from the first time were able to break away from the mold without residue.

The results are given in table 2.

Table 2
Properties of examples 1-5 and comparative examples 6-8
Example123456 Ms.7 Ms.8 Ms.
Viscosity after 12 hand22,827,1 21,719,723,822,423,120,5
Viscosity after 7 daysand27,030,625,023,226,426,227,725,2
The increase in viscosityb18%13%15%18%11%17%20%23%
The time of crust formation (min)70150906560404545
Full curing (days)2,53332,52,52,52,5/td>
andIn PA∙s, keeping at 60°C.
b(viscosity after 7 days/viscosity after 12 h) × 100%.

Examples 9-10 and comparative example 11

For each example the corresponding components according to table 3 were weighed in predetermined weight parts without pre-drying in a polypropylene jar with a screw-top jar and mixed by means of a centrifugal mixer (SpeedMixerTMDAC 150, FlackTek Inc.; 1 min at 2500 rpm./min), the mixture was immediately loaded into the varnished inside aluminum tube and sealed it closed.

The polyurethane polymer PUP-2 was prepared as follows:

180 g of polyoxypropylene (Acclaim®4200 N, Bayer; OH number 28.5 mg KOH/g), 50 g polyoxypropylene (Acclaim®6300, Bayer; OH number of 28.0 mg KOH/g) and 21 g of toluylene diisocyanate (TDI; Desmodur®T 80 P, Bayer) were subjected to interaction at 80°C. until the NCO-terminated polyurethane polymer with a content of free isocyanate groups 1,89% weight. and viscosity of 13.8 PA∙s at 20°C.

The ratio between isocyanate groups and aldimine groups in all examples was 1.0/0,70.

Table 3
The composition of examples 9-10 and comparative example 11
Example91011 (comparative)
The polyurethane polymer PUP-250,050,050,0
ValdimirA-1,
5,77
A-2
5,23
A-8,
of 6.31
The acid catalystand0,10,10,1
andSalicylic acid (5% weight. in dioctyladipate).

Thus obtained composition was tested for stability in storage, waiting time before bonding (crust formation) and the curing speed (full cure), as described in example 1.

The results are given in table 4.

Table 4
Properties of examples 9, 10 and comparative example 11
Example91011 (comparative)
Viscosity after 1 h (PA∙s) and12,813,0to 12.0
Viscosity after 7 days (PA∙s)andthe 15.6the 15.614,0
The increase in viscosityb22%20%17%
The time of crust formation (min)13029570
Full curing (days)43,53
andMaintaining at 60°C.
b(viscosity after 7 days/viscosity after 12 h) × 100%

Examples 12-15 and comparative examples 16-18:

One-component elastic adhesives

For each example the corresponding components according to table 5 were processed in the specified weight parts without pre-drying in a vacuum mixer with the exclusion of moisture until a homogeneous paste, it immediately downloaded in lacquered inside aluminum cartouche, cartouche tightly closed.

The polyurethane polymer PUP-3 was prepared as follows.

3560 g polyoxypropylene the Ola (Acclaim ®4200 N, Bayer; OH number of 28.1 mg KOH/g), 1000 g polyoxypropylene (Acclaim®6300, Bayer; OH number of 28.0 mg KOH/g) and 440 g of toluylene diisocyanate (TDI; Desmodur®T 80 P, Bayer) were subjected to interaction at 80°C. until the NCO-terminated polyurethane polymer with a titrimetric specific content of free isocyanate groups 2,19% weight. and a viscosity of 10 PA∙s at 20°C.

The thickener was prepared as follows:

In a vacuum mixer was downloaded 3000 g diisodecylphthalate (DIDP; Palatinol®Z, BASF) and 480 g of 4,4'-etilendiamindisuktsinatov (MDI; Desmodur®44 MC L, Bayer) and a little heated. Then with vigorous stirring slowly bury 270 g monomethylamine. The resulting paste was then mixed under vacuum and cooled for one hour.

The ratio between isocyanate groups and aldimine groups in all examples was 1.0/0,67.

Table 5
Song one-component elastic adhesives of examples 12-15 and comparative examples 16-18
Example1213141516 Ms.17 Ms.18 Ms.
PUR-polymer PUP-324,024,024,024,024,024,024,0
ValdimirA-1,
of 3.07
A-2
2,78
A-3,
3,18
A-4
3,15
A-6,
2,85
A-7
with 3.27
A-8,
3,36
The plasticizerand1,932,221,821,853,151,731,64
Chalk38,038,038,038,038,038,038,0
Thickener28,028,028,028,028,028,028,0
Dio is led titanium 4,54,54,54,54,54,54,5
Epoxysilaneb0,20,20,20,20,20,20,2
The acid catalystwith0,30,30,30,30,30,30,3
andDiisodecylphthalate (DIDP; Palatinol®Z, BASF).
b3-glycidoxypropyltrimethoxysilane (Dynasylan®GLYEO, Degussa).
cSalicylic acid (5% weight. in dioctyladipate).

Thus obtained one-component elastic adhesives were tested on consumer characteristics, waiting time before bonding, curing rate and mechanical properties after curing.

As a measure of consumer properties used sustainability and hood thread. To determine the stability of the adhesive through kartochnogo PI is tolet through triangular nozzle was applied in the form of horizontal triangle "caterpillar" with a base diameter of 8 mm and a height (distance of the vertices of the triangle from the base) 20 mm on the upright piece of cardboard. After 5 minutes, measure distance down the top, i.e. moved from the initial position in the center of the triangular "caterpillars". As "very good" has been evaluated, if the top were completely or approximately in the same position as "good"if top is positioned between the center and the end of the base. Hood yarns was determined qualitatively, the fact that a little glue through kartochnogo gun inflicted on a piece of cardboard attached to the wall, kartochnye gun at the end of the application was quickly pulled from the applied adhesive and the measured length of thread are left behind in the place of the cliff.

As a measure for the exposure time before gluing used during the formation of the crust (without glue). The time of the formation of a crustwas determined as described in example 1.

As a measure of the speed of curing used the time to complete curing of the adhesive. Time to complete curing was determined that the adhesive through kartochnogo gun through a round tip (hole 10 mm) was applied in the form of a horizontal loose cone with a length of about 50 mm and a thickness in the centre of 30 mm on a piece of cardboard attached to the wall, were left for 7 days under normal conditions, then vertically cut in the center and measured the thickness of the layer of the cured adhesive, using a scale.

To determine the mechanical properties of the pic is E. curing was measured And the shore hardness, the tensile strength, elongation at break and stress at tensile at 100%. And the shore Hardness of the tested specimens cured for 14 days in normal conditions, was determined according to DIN 53505. For testing the following mechanical properties of the adhesive 2 hours after receipt by the press extruded to a film thickness of about 2 mm, the film was utverjdali within 14 days in normal conditions and tested according to DIN EN 53504 on the tensile strength, elongation at break and stress at the 100% modulus (stretch speed: 200 mm/min)

All adhesives were completely overidealize without bubbles.

The results are given in table 6.

Table 6
The elastic properties of the adhesives of examples 12-15 and comparative examples 16-18
Example1213141516 Ms.17 Ms.18 Ms.
ResistanceVery goodVery goodVery good Very goodVery goodVery goodGood
Hood filament (cm)108451044
The time of crust formation (min)105280180100556065
Full cure (mm)988811104
A-shore Hardness38423431393731
Tensile strength (MPa)2,12,11,42,11,91,8
Elongation at break (%)1350107010101040114013101040
Voltage when the 100% modulus (MPa)1,001,460,931,011,391,04the 1.44

Example 19 and comparative examples 20 and 21

One-component elastic sealant

For each example the corresponding components according to table 7 were processed within the prescribed weight parts without pre-drying in a vacuum mixer with the exclusion of moisture until a homogeneous paste, it immediately downloaded in lacquered inside aluminum cartouche, cartouche tightly closed.

The polyurethane polymer PUP-4 was prepared as follows.

1190 g polyoxypropylene-diol (Acclaim®4200 N, Bayer; OH number of 28.1 mg KOH/g), 620 g Polyoxypropylenediamine (Caradol®MD34-02,Shell; OH number of 35.0 mg KOH/g) and 190 g of 2,4-toluylene diisocyanate (Scuranate® T-100, Lyondell) were subjected to interaction at 80°C. until the NCO-terminated polyurethane polymer with a titrimetric specific content of free isocyanate groups 2,32% weight. and a viscosity of 5 PA∙s at 20°C. the Thickener was obtained as described in example 12.

The ratio between isocyanate groups and aldimine groups in all examples was 1.0/0,67.

Table 7
Song one-component elastic sealant of example 19 and comparative examples 20 and 21
Example1920 Comparison.21 Cf.
The polyurethane polymer PUP-424,024,024,0
ValdimirA-1,
3,26
A-7
3,47
A-8,
of 3.56
The plasticizerand1,741,53the 1.44
Chalk38,038,038,0
Thickener28,028,028,0
Titanium dioxide4,54,54,5
Epoxysilaneb0,20,20,2
The acid catalystwith0,30,30,3
andDiisodecylphthalate (DIDP; Palatinol®Z, BASF).
b3-glycidoxypropyltrimethoxysilane (Dynasylan®GLYEO, Degussa).
cSalicylic acid (5% weight. in dioctyladipate).

Thus obtained one-component elastic sealant was tested on consumer properties (stability, extractor threads), the waiting time before bonding (crust formation), the curing speed (full cure) and mechanical properties after curing (a-shore hardness, tensile strength, elongation at break and stress at tensile at 100%) were tested as described in example 12.

Next sealants qualitatively tested for adhesion. It was thus that pushed big is alcam on cured shore a sample, after one or three days after application, and after this was established, how long the sample when lifting hands remained glued to your thumb. Thus the adhesiveness was evaluated as "high" (sample remains glued for more than 3 seconds), medium (sample remains glued 1-2 seconds) and "no" (sample remains glued less than 1 second).

All sealants were overidealize completely without bubbles.

The results are given in table 8.

Table 8
Properties of one-component elastic sealant of example 19 and comparative examples 20 and 21
Example1920 Comparison.21 Cf.
ResistanceVery goodVery goodVery good
Hood filament (cm)548
The time of crust formation (min)2509570
Full resp is redeye (mm) 873
A-shore Hardness303223
Tensile strength (MPa)2,02,01,4
Elongation (%)118011501200
Voltage when the 100% modulus (MPa)0,350,420,34
Adhesion after 1 daysmallsmallhigh
Stickiness in 3 daysnonoaverage

Examples 22, 23 and comparative example 24

Two-component elastic adhesives

For all examples, the component K1 was prepared as follows:

In a planetary mixer under nitrogen atmosphere were mixed until a homogeneous paste 200 g of partially cardiomediastinal 4,4'-etilendiamindisuktsinatov (Desmodur®CD, Bayer; the content is the W NCO = 29.5% of weight) with 280 g of polyurethane polymer PUP-1 and 20 g of a hydrophobic pyrogenic silicic acid (Aerosil ®R972, Degussa) and loaded in the cartouche.

Then the component K2 according to table 9 were weighed in predetermined weight parts without pre-drying in polypropylene cartouche and mixed until a homogeneous paste by means of a centrifugal mixer (SpeedMixerTMDAC 150, FlackTek Inc.; 2 min at 3000 rpm./min). To this was added are shown in table 9 weight parts of the component K1and immediately mixed (30 sec at 3000 rpm./min). The polyurethane polymer PUP-1 was obtained as described in example 1. The thickener was obtained as described in example 12.

The ratio between the isocyanate groups of component K1 and the amount of the reactive groups (hydroxyl groups, primary amino groups and aldimine groups) component K2 always 0.6/1.

Table 9
Composition of two-component elastic adhesives of examples 22, 23 and comparative example 24
Example222324 (Cf.)
Component K118,218,718,4
Component K2:
Polyola47,047,047,0
ValdimirA-1
the 4.7
A-2
the 4.7
A-9
the 4.7
Diamineb1,01,01,0
Thickener10,010,010,0
Amine catalystc0,10,10,1
The acid catalystd0,20,20,2
Water0,1390,1530,145
Molecular sievee2,02,02,0
Chalk35,035,035,0
aPolyoxypropylenediamine low monol (Preminol ®S-X5006, Asahi Glass; OH-number of 28.0 mg KOH/g).
b1,3-xylylenediamine.
cDABCO®33-LV, Air Products.
dSalicylic acid (5% weight. in dioctyladipate).
eMolecular sieves 8 angstroms (Purmol®13, Zeochem Europe).

Thus obtained two-component elastic adhesives were applied directly after mixing both components and has been tested on waiting time before bonding, curing rate and mechanical properties after curing.

As a measure of time before pasting considered the time until necklacesthe glue. This test was similar to the timing of crust formation, as in example 1.

As a measure of the speed of curing considered the curing time. To determine the time of curing the cured adhesive was measured in relative phases a-shore hardness (measured according to DIN 53505) and assessed the glue as a fully cured when the value of the A-shore hardness remained almost constant.

To determine the mechanical properties after curing was measured And the shore hardness, tensile strength, elongation and E-module. A-shore Hardness was determined according to DIN 53505 samples cured for 4 days in normal conditions. For testing other mechanical is their adhesive properties directly after receipt by the press extruded to a film thickness of about 2 mm, the film was utverjdali for 4 days in normal conditions and tested according to DIN EN 53504 tensile strength, elongation and E-module (exhaust velocity: 200 mm/min).

All adhesives were overidealize completely without bubbles.

The results are given in table 10.

Table 10
Properties of two-component elastic adhesives of examples 22, 23 and comparative example 24
Example222324 (Comparative)
The time until necklacesthe (min)12010545
Curing time (hour)12119
A-shore Hardness474649
Tensile strength (MPa)2,42,02,3
Elongation (%) 600600610
E-modulus at 0.5-5% elongation (MPa)2,42,12,3

From the examples show that compositions according to the invention is comparable to the speed of curing is characterized by clearly longer waiting time before bonding than the compositions of comparative examples. In the respective other specific properties such as storage stability, consumer properties, mechanical properties after curing or adhesion no significant differences between the compositions according to the invention and compositions of the comparative examples.

1. Curable composition consisting of two components K1 and K2, containing
a) at least one aromatic polyisocyanate P containing isocyanate groups, and
b) at least one Valdimir And formulas (I)

where X represents a residue of the diamine DA with two primary amino groups after the separation of these two amino groups; and
Y1and Y2independently from each other represent a monovalent hydrocarbon residue with 1 to 12 atoms; and
Y3represents a monovalent hydrocarbon residue, which enabled the but has at least one heteroatom, especially oxygen in the form of a simple ether, carbonyl or ester groups;
(C) compounds reactive towards isocyanate groups, in particular water and/or polyols, and/or polyamine;
provided that at least one of the two primary amino groups of the diamine DA is an aliphatic amino group and two primary amino groups of the diamine DA differ from each other, or
the number of hydrogen atoms of carbon atoms (Cα), located in the α-position to the corresponding amino group by at least one, or
the number of hydrogen atoms of carbon atoms (Cβ), located in the β-position to the corresponding amino group by at least two.

2. The composition according to claim 1, characterized in that the diamine DA selected from the group consisting of 1,2-propandiamine, 2-methyl-1,2-propandiamine, 1,3-butanediamine, 1,3-diaminopentane (DAMP), 4-aminoacetanilide, 4-aminomethylpyridine, 4-[(4-aminocyclohexane)methyl]aniline, 2-aminoethylamino, 2-aminotetralin, 2-[(4-aminocyclohexane)methyl]aniline, 4-[(2-aminocyclohexanol)methyl]aniline; 2,2,4-trimethylhexamethylenediamine (TMD), 1,5-diamino-2-butyl-2-ethylpentane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (=ISOPHORONEDIAMINE=ACCESSORIES>) and 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA).

3. The composition according to claim 1 or 2, characterized in that aromatic on isocyanat P, containing isocyanate groups is an aromatic polyurethane polymer PUP, containing isocyanate groups, in particular, obtained by reacting at least one polyol with at least one aromatic polyisocyanate.

4. The composition according to claim 3, characterized in that the polyisocyanate used for the preparation of aromatic polyurethane polymer PUP, containing isocyanate groups, is an aromatic polyisocyanate selected from the group consisting of 2,4 - and 2,6-toluylenediisocyanate and any mixtures of these isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any mixtures of these isomers (MDI), mixtures of MDI and MDI homologues (polymeric MDI or PMDI), 1,3 - and 1,4-phenylendiamine, 2,3,5,6-tetramethyl-1,4-diisocyanatobutane, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatobutane (TODI), densityindependent (DADI), oligomers and polymers of the aforementioned isocyanates, and also any mixtures of the aforementioned isocyanates.

5. The composition according to claim 1 or 2, characterized in that the aromatic polyisocyanate P containing isocyanate groups is aromatic polyisocyanate PI, selected from the group consisting of 2,4 - and 2,6-toluylenediisocyanate and any mixtures of these isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any mixtures of these isomers (MDI), mixtures of MDI and MDI homologues (on kernie MDI or PMDI), 1,3 - and 1,4-phenylendiamine, 2,3,5,6-tetramethyl-1,4-diisocyanatobutane, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatobutane (TODI), densityindependent (DADI), oligomers and polymers of the aforementioned isocyanates, and also any mixtures of the aforementioned isocyanates.

6. The composition according to claim 1 or 2, characterized in that the diamine DA selected from the group consisting of 1,3-diaminopentane (DAMP), 1,5-diamino-2-butyl-2-ethylpentane, 2,2,4-trimethylhexamethylenediamine (TMD) and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (=ISOPHORONEDIAMINE=ACCESSORIES>).

7. The composition according to claim 1 or 2, characterized in that Y3means the residue of formula (II) or (III), preferably a residue of the formula (III)

where R3represents a hydrogen atom or alkyl group, in particular from 1 to 12 atoms, preferably a hydrogen atom;
R4represents a hydrocarbon residue with 1-30, in particular 11-30, atoms, which may contain heteroatom; and
R5or represents a hydrogen atom or a linear or branched alkyl residue with 1-30, in particular 11-30, atoms, possibly with a cyclic part and possibly with at least one heteroatom, or is a mono - or polyunsaturated, linear or branched hydrocarbon residue with 5 to 30 atoms, or represents a possibly substituted Aro eticheski or heteroaromatic 5 - or 6-membered cycle.

8. The composition according to claim 1 or 2, characterized in that each of the Y1and Y2represent a methyl group.

9. The composition according to claim 1 or 2, characterized in that the polyisocyanate P is present in amounts of 5-95 wt.%, preferably in the amount of 10-90 wt.% calculated on the whole composition.

10. The composition according to claim 1 or 2, characterized in that Valdimir And formula (I) in the composition is present in such quantities that the ratio of the number aldimine groups to the number of isocyanate groups is 0.1 to 1.1, preferably of 0.15 to 1.0, particularly preferably from 0.2 to 0.9.

11. The composition according to claim 1 or 2, characterized in that it contains at least one catalyst, particularly a catalyst accelerating the hydrolysis of aldimines, preferably the acid.

12. The composition according to claim 1 or 2, characterized in that the aromatic polyisocyanate P containing isocyanate groups, and Valdimir And formula (I) are part of component K1 and a component K2 contains compounds reactive towards isocyanate groups, in particular water and/or polyols, and/or polyamine.

13. The composition according to claim 1 or 2, characterized in that the aromatic polyisocyanate P containing isocyanate groups, is part of component K1 and K2 contains Valdimir And formulas (I)and compounds reactive towards isocyanate groups is m, in particular water and/or polyols, and/or polyamine.

14. The cured composition obtained by mixing the two components K1 and K2 of the composition according to any one of claims 1, 12 or 13 after its interaction with water.

15. The use of a composition according to any one of claims 1 to 14 as an adhesive, sealant, potting mass or coating.

16. The use of a composition according to any one of claims 1 to 14 for sealing joints, particularly joints facilities above-ground and underground buildings.

17. Method of bonding a substrate S1 to a substrate S2, comprising the steps:
i) applying a composition according to any one of claims 1 to 14 on the substrate S1;
ii) contacting the applied composition with a substrate S2 within the exposure time before the bonding composition;
or
i') applying a composition according to any one of claims 1 to 14 on a substrate S1 and a substrate S2;
ii') contacting the applied compositions with each other during the exposure time before the bonding composition;
moreover, the substrate S2 consists of the same or different material as compared with the substrate S1.

18. Packing method, including the state
I') applying a composition according to any one of claims 1 to 13 between the substrate S1 and a substrate S2, so that the composition is in contact with the substrate S1 and the substrate S2;
moreover, the substrate S2 consists of the same or different material as compared with the substrate S1.

19. Method of coating a substrate S1 including the state
I') applying a composition according to any one of claims 1 to 13 on a substrate S1 within the exposure time of the composition.

20. The method according to any of PP-19, characterized in that the substrate S1 and/or a substrate S2 before gluing or sealing, or by coating the pre-treated, in particular, a primer layer or the composition of the adhesion promoter.

21. The method according to 17, wherein the substrate S1 and/or the substrate S2 is an inorganic substrate, such as glass, glass ceramic, concrete, construction, cement, brick, tile, gypsum or natural stone such as granite or marble; metals or alloys such as aluminum, steel, non-ferrous metal, galvanized metals; organic substrates, such as wood, polymer, such as PVC, polycarbonate, emission spectra obtained for pure, polyethylene, polypropylene, complex, polyester, epoxy resin, polyurethane (PUR); a substrate with a coating, such as metal or alloy with powder coating or paint or varnish, in particular automotive top coat varnish.

22. The product, which is glued, sealed or coated by the method according to any of PP-21.

23. The product according to item 22, wherein a is a structure, in particular ground or underground construction, or industrial product, or a consumer product, such as, in particular, window, machine for household or vehicle, in particular a water or land vehicle, preferably, car, bus, truck, train or ship, or structural element of the vehicle.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to elastic repairable thixotropic cold setting compounds with high adhesion strength, which retain improved electrical insulation properties when exposed to high moisture, which are meant for sealing components of electric radio products. The compound contains the following, pts.wt: oligodiene urethane epoxide PDI-ZAK 40-45, trifunctional oligoether epoxide 8-12, monoglycidyl ether of alkyl phenol 8-12, low-molecular weight polyamide resin 7-22, amine 2-5. The compound can be successfully used for moisture protection of components since after exposure to 98% moisture for 30 days, its volume resistivity drops from 1.5-1012-9.1·1013 ohm·cm to 6.0·108 ohm·cm, but remains sufficient to ensure electrical insulation of components of electric radio products.

EFFECT: obtaining a cold setting compound for moisture protection of components of electric radio products with sufficient working life, which is elastic, thixotropic and repairable.

1 tbl

FIELD: process engineering.

SUBSTANCE: extrudes rod is heated to temperature exceeding that of vitrification temperature to bend it into ring structure at temperature higher than that of vitrification. Then, first and second ends are jointed together to anneal half-finished ring.

EFFECT: large-diameter seal rings from extruded rods of selected materials.

19 cl, 6 dwg, 10 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to silicone compositions for use in insulating double glazing. The curable sealing composition contains a) polydiorganosiloxane with terminal silanol groups; b) a cross-linking agent selected from a group consisting of a cross-linking agent of general formula: (R7O)(R8O)(R9O)(R10O)Si, where R7, R8, R9 and R10 are independently selected univalent hydrocarbon C1-C60-radicals, and methyltrimethoxysilane; c) a cross-linking reaction catalyst; d) an amount of zinc oxide for rapid deep curing in a volume with average particle size smaller than one micron.

EFFECT: invention provides rapid deep curing of a sealing composition in a volume.

26 cl, 3 dwg, 7 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: composition has the following component ratio, wt %: non-specified synthetic rubber SKD - structured production wastes - 17.0-20.0; non-specified synthetic rubber SKS - production wastes - 23.0-25.0; bitumen BNK-90/30 - 18.0-20.5; alkylphenol resin-octophore-N - 2.0-1.5; chalk -20.0-12.0; kaolin - 5.0-3.0; industrial oil wastes -15.0-18.0.

EFFECT: high quality of the water-proofing and adhesive sealing composition owing to improved physical and mechanical properties thereof and low water absorption thereof.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to particles, such as microparticles, and compositions, such as coating compositions and sealing compositions, which contain such particles. Disclosed is a particle whose outer surface is coated with a thin coating having film thickness of less than 25 mcm, wherein the (I) the thin coating contains a reaction product of (a) an aminoplastic resin and (b) a compound containing functional groups which are reactive with respect to the aminoplastic resin; or (II) the thin coating contains a sulphur-containing polymer. The compound (b) or sulphur-containing polymer contains thiol groups (polythiol, dithiol). The particle is a lightweight particle having specific weight of not more than 0.7 g/cm3 before applying the thin coating. The sulphur-containing polymer is a reaction product of the aminoplastic resin and a polyol, which preferably contains dithiol. The invention also relates to a method of using the particles, which involves adding the particles to a composition containing a binder in which the particles are dispersed. The invention also relates to a composition containing (a) a sulphur-containing polymeric binder; and (b) lightweight particles having specific weight of not more than 0.7 g/cm3 before applying the thin coating which are dispersed in the binder. The composition has specific weight of less than 1.0 or less than 0.9 or less than 0.85 g/cm3 and after deposition onto a substrate and curing turns into a curable composition which is characterised by: (i) swelling value of not more than 40 vol. % after immersion for one week at 140°F and ambient pressure in jet reference fluid (JRF) type 1; (ii) an elongation of at least 80% when measured according to AMS 3269a; and (iii) tensile strength of at least 2000 MPa when measured according to AS 5127/1a 7.7. The invention also relates to an aerospace vehicle having at least one slit sealed by a sealant made from said composition.

EFFECT: obtaining a composition which is capable of forming a film having resistance to weather elements such as moisture and temperature, and at least partially blocks such materials as water, fuel and other liquids and gases, and the curable sealant compositions have low temperature of elasticity and high tensile strength.

16 cl, 2 dwg, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a curable sealing resin composition. The curable composition contains at least one anhydride-functionalised polymer in amount of 30-60 wt %, a polyol in amount of 10-25 wt %, an epoxide-functionalised polymer, oligomer or monomer in amount of 15-40 wt %, a urethane polyol-functionalised compound selected from a group consisting of urethane diol, polyurethane diol and combination thereof in amount of 5-15 wt % and a catalyst with respect to total weight of the resin. The resin composition can be cured at room temperature. Components used to prepare and cure the resin composition can be provided in form of two or more parts.

EFFECT: hydrolytic stability, high hardness, flexibility and low cost of production of the sealing resin which can be used to restore insulation and/or for environmental protection of cable joints, sealed articles etc.

13 cl, 4 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: sealant contains a liquid phase consisting of glycerol, water and CMC adhesive and a solid phase consisting of a fine fraction of aerosil and a coarse fraction of chemically inert filler. The inert filler used is ground husks of grain crops, particularly rice husks. The weight ratio of glycerol in the liquid phase ranges from 56 to 67 wt %, which provides frost-resistance of the sealant from minus 30°C to minus 46°C.

EFFECT: sealant has low demixing during storage and is not harmful for humans, the rubber of the tyre and the environment.

3 cl, 2 ex, 2 dwg

FIELD: construction.

SUBSTANCE: compound contains oligodieneurethane epoxide, isomethyl tetrahydrophthalic anhydride. The compound additionally contains a monoglycidyl ether of butyl cellosolve and a hexagonal boron nitride. To produce the compound, the pre-heated oligodieneurethane epoxide, monoglycidyl ether of butyl cellosolve and hexagonal boron nitride are mixed. Then the isomethyl hydrophthalic anhydride is added into the produced mixture and hardened.

EFFECT: compound has lower temperature of hardening and has lower specific volume resistance after durable impact of high moisture and resistance to a compression stroke.

2 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: disclosed is a sealing composition which contains the following (pts.wt): a compound based on low-molecular weight siloxane rubber (100), oligodimethyl siloxane with kinematic viscosity of 10-350 mm2/s (10-50) and finely dispersed silicon dioxide with specific surface area of 50-300 m2/s (10-40). Also disclosed is a method of producing said composition, wherein a pre-dried and vacuum-treated mixture of silicon dioxide and oligodimethyl siloxane is added to a dried and deaerated compound based on low-molecular weight siloxane rubber.

EFFECT: method of producing sealing composition having the disclosed composition improves physical and mechanical properties of coating electronic devices in order to protect them from mechanical and electric factors and prolong stable operation of electronic devices in conditions of high humidity and high supply voltages.

2 cl, 2 dwg, 1 tbl, 7 ex

Epoxide compound // 2472820

FIELD: chemistry.

SUBSTANCE: invention is meant for gluing, sealing and repairing materials and articles for medical and household purposes, and materials used in closed and sealed premises. The epoxide compound contains the following (pts.wt): epoxy diane resin - 100, plasticiser - 1.5-20, curing agent - 10-100 and nanostructured bentonite powder which is intercalated with cerium ions (Ce3+) - 0.5-5.

EFFECT: reduced emission of volatile organic compounds from the epoxide compound in operating conditions with ageing and decomposition.

8 cl, 2 dwg, 2 ex

FIELD: process engineering.

SUBSTANCE: invention relates to food packing materials, particularly, to production of packing flexible laminate. At least, one plastic film and, at least, other plastic film, metal foil or paper are coated with adhesive to make laminate layers and bonded together to make said laminate. Then, laminate is continuously irradiated at the line with microwave radiation station for hardening the adhesive.

EFFECT: faster hardening.

9 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an adhesive composition for mutual attachment of two objects and a method of attaching an article to a substrate and can be used to attach articles to building walls and similar bases. The adhesive composition is double-packed in form of mounting set. The adhesive composition consists of a mixture of an aerobic adhesive substance and a hydrophilic material. The set has two containers for separate storage of the aerobic adhesive substance and the hydrophilic material. The adhesive aerobic substance is silane MS polymers. The method of attaching an object to a base using the adhesive composition involves mixing the aerobic adhesive substance with the hydrophilic substance, attaching the object by pressing a layer of the adhesive composition to the base and hardening the adhesive composition.

EFFECT: invention provides fast hardening of the adhesive layer and easier attachment of objects to each other.

8 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to moisture-cured hot-melt adhesives. Disclosed is a moisture-cured hot-melt adhesive composition containing at least one silane group-containing polyurethane prepolymer of formula (I), where R1 is an n-valent organic radical of prepolymer P, which is obtained from at least one polyol and at least one polyisocyanate and has at least n isocyanate groups, followed by removal of the n isocyanate groups; R2 is a C1-C10 alkyl group; R3 is a linear or branched C1-C10 alkylene group; X is a hydrolysable radical OR4, wherein R4 is a C1-C10 alkyl group which can contain 1 or 2 oxygen atoms of an ether; a equals 0, 1 or 2; n equals 2 or more; where the prepolymer of formula (I) is obtained from reaction of the polyurethane prepolymer P with a mercaptosilane of formula (II), wherein the prepolymer P is solid at room temperature and does not have an additional silane group, and the composition has longer storage life (viscosity stability) in uncured form. Disclosed also is a method for adhesive binding of substrates using the disclosed adhesive composition and an article obtained using the adhesive.

EFFECT: disclosed adhesive compositions do not form bubbles neither when heated nor during curing and have stable viscosity at high temperatures.

20 cl, 7 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to an aqueous polyurethane-polyurethane-urea dispersion which is used as a starting adhesive material in dispersion adhesives, as well as a method of producing such a dispersion, use thereof, adhesive compositions containing said dispersion and adhesive composite materials. The aqueous polyurethane-polyurethane-urea dispersion is composed of: A) one or more di- or higher functional polyols, having average molecular weight of 400-5000 Da, B) optionally one or more di- or higher functional polyol components, having molecular weight of 62-399 Da, C) one or more di- or higher polyisocyanate components, and D) a mixture (D) of primary and/or secondary monoamine compounds D1) and primary and/or secondary diamine compounds D2), wherein at least one of the components (D1) and/or (D2) contains sulphonate groups, wherein the average amine functionality of the mixture (D) is 1.65-1.95, and the equivalent ratio of NCO groups in the NCO prepolymer and total number of amine and hydroxyl groups of the mixture (D) which react with the isocyanate is equal to 1.04-1.9.

EFFECT: obtaining stable aqueous dispersions of adhesives without the need to use an emulsifying agent, films from which have improved initial thermal stability and high final thermal stability.

14 cl, 10 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to an aqueous polyurethane-polyurethane-urea dispersion which is used as a starting adhesive material in dispersion adhesives, as well as a method of producing such a dispersion, use thereof, adhesive compositions containing said dispersion and adhesive composite materials. The aqueous polyurethane-polyurethane-urea dispersion is composed of: A) one or more di- or higher functional polyols, having average molecular weight of 400-5000 Da, B) optionally one or more di- or higher functional polyol components, having molecular weight of 62-399 Da, C) one or more compounds which are monofunctional when reacting with a polyisocyanate and which have ethylene oxide content of at least 50 wt % and molecular weight of at least 400 Da, D) one or more di- or higher polyisocyanate components, and E) a mixture (E) of primary and/or secondary monoamine compounds E1) and primary and/or secondary diamine compounds E2), wherein at least one of the components (E1) and/or (E2) contains sulphonate groups, wherein the average amine functionality of the mixture (E) is 1.65-1.98, and the equivalent ratio of NCO groups in the NCO prepolymer and the total number of amine and hydroxyl groups of the mixture (E) which react with the isocyanate is equal to 1.04-1.9.

EFFECT: obtaining stable aqueous dispersions of adhesives without the need to use an emulsifying agent, films from which have improved initial thermal stability and high final heat stability.

14 cl, 4 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: adhesive composition contains a polyfunctional isocyanate, polyether polyol and a catalyst. The catalyst consists of at least one organic compound of iron and at least one chelating ligand. The multicomponent adhesive composition is prepared in form of at least two inter-reacting chemical components. One of the at least two inter-reacting chemical components contains a polyfunctional isocyanate and a catalyst, and the other contains polyether polyol. The multicomponent adhesive composition is used to produce articles from bound lignocellulose composite based on a lignocellulose substrate, especially for making oriented fibre panels.

EFFECT: invention enables to obtain articles using filler with high moisture content, which are structured at low pressing temperatures without reducing efficiency of the press.

4 tbl, 1 ex, 17 cl

FIELD: chemistry.

SUBSTANCE: moisture-curable and biodegradable adhesive which contains a reaction product of: (a) an isocyanate component having an average functionality of at least 2, the isocyanate component being selected from a group consisting of lysine diisocyanate and derivatives thereof, lysine triisocyanate and derivatives thereof, and combinations thereof; (b) an active hydrogen component having an average functionality greater than 2.1, the active hydrogen component containing a component with a hydroxyl functional group; and (c) an ionic salt component having an average hydroxyl or amino functionality, or combination thereof, of at least 1, selected from a group consisting of ammonium salts, halides, sulphonates, phosphonates, carboxylates and combinations thereof.

EFFECT: obtaining a moisture-curable and biodegradable adhesive.

18 cl, 1 dwg, 17 ex

FIELD: chemistry.

SUBSTANCE: adhesive polyurethane composition consists of a prime coat and polyurethane adhesive, comprising urethane rubber and ethyl acetate, applied on its surface. The prime coat consists of a solution of polyurethane thermoplastic elastomer with ethyl acetate in ratio: polyurethane thermoplastic elastomer 10-18 wt % and ethyl acetate - the balance. The polyurethane adhesive contains a solution of polyurethane thermoplastic elastomer and a mixture of polar organic solvents consisting of ethyl acetate and methylene chloride, with the following ratio of components: polyurethane thermoplastic elastomer 17-27 wt %; methylene chloride 7-10 wt % and ethyl acetate - the balance. The polyurethane adhesive can contain perchlorovinyl resin as a target additive in amount of 0-10% to the total weight of the adhesive.

EFFECT: low cost and improved adhesion properties of the adhesive composition and cohesion strength characteristics of the adhesive joints.

2 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: composition contains the following in pts.wt: 100 bifunctional prepolymer with terminal isocyanate groups, 10.6-12.8 - 3,3'-dichloro-4,4'-diaminodiphenylmethane, 15.9-19.2 dioctylsebacate, 1.2-1.4 - 1,4-butanediol, 0.31-0.35 - para-phenylenediamine and 0.015-0.030 - Agidol 51,52,53 (mixture of 2-dimethylaminomethylphenol, 4-dimethylaminophenol, 2,6-bis (dimethylaminomethyl)phenol, 2,4-bis-(dimethylaminomethyl)phenol,2,4,6-tris-dimethylaminomethyl)phenol.

EFFECT: obtaining a fixing composition which, after prolonged storage, retains strength and adhesion parameters vital for operation of charges of antitank grenades at both high and low temperatures, and also prevents accidental exposure to substances which are harmful to health of personnel, in cases of technical faults and emergencies.

3 tbl

FIELD: transport.

SUBSTANCE: invention relates to method for covering light airplanes with polyester sheathing fabric, as well as to dispersive hot-gluing glue and its application for covering. For covering, polyester sheathing fabric with longitudinal shrinkage of 7% and transversal shrinkage of 5% at 160-180°C is used. In the process of covering light airplanes and/or their parts consisting of frame system, sheathing fabric in the area of its overhangs and frame parts is covered by dispersive hot-gluing glue and wrapped around longeron part of frame so that when connection between sheathing fabric and frame produced by glue is destructed the fabric could be held on frame carcass. Dispersive hot-gluing glue contains 80-88% of adhesive, 12-15% of hardener and 0.15-0.3% thickener, and the glue is polymerised at temperatures >40°C. The hardener contains 54-60% of solvent, 0.35-0.5% of naphthalensulfonic acid sodium salt-based stabiliser, 0.25-0.35% of propoxylated spirit-based emulsifier, 1.7-1.9% of polyetheramines-based hardener, 37-41% of polyisocyanate.

EFFECT: reliability and durability of light airplanes and/or their parts covering.

15 cl, 3 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to multilayer combined materials. Proposed material comprises: top layer of textile web with porous polymer layer applied on its wrong side, adhesion layer and bottom layer. Porous polymer layer is formed on said working side and consists of the following components in wt %: polyesterurethane - 92.08-94.84; dimethyl formamide - 0.759-1.106; surfactant - 0.759-1.106; di-(2-ethylhexyl)phthalate - 0.759-1.106; microcrystalline cellulose - 2.884-4.604. Said composition is diluted by dimethyl formamide to viscosity of 170-180 poises.

EFFECT: optimised thermophysical and hygienic properties.

6 cl, 5 tbl, 2 ex

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