Aldimines having hydroxy groups and aldimine-containing compositions

FIELD: chemistry.

SUBSTANCE: invention relates to aldimines of formula (I)

where A does not contain active hydrogen and a primary amine group, or together with R7 denotes a (n+2)-valent hydrocarbon radical containing 3-20 carbon atoms and, if necessary, at least one heteroatom in form of oxygen of an ether group or nitrogen or a tertiary amine group; n equals 1, 2, 3 or 4; m equals 0,1, 2, 3 or 4; R1 and R2 each denotes a univalent hydrocarbon residue with 1-12 carbon atoms or together denote a divalent hydrocarbon radical which is part of a carbocyclic ring with 5-8 carbon atoms; R3 denotes H or alkyl; R4 and R5 independently denote CH3 or a univalent aliphatic radical containing 2-12 carbon atoms and optionally hydroxy groups; X denotes O, S, N-R6, or N-R7, where R6 denotes a univalent hydrocarbon radical containing 1-20 carbon atoms and having at least one hydroxy group; as well as curable compositions containing such aldimines and use of said compositions.

EFFECT: obtaining novel aldimines which can be used as curing agents in curable compositions.

22 cl, 18 ex, 6 tbl

 

The technical field

The invention relates to the field of aldimines.

The level of technology

Aldimine are condensation products of primary amines and aldehydes and belong to well-known class of compounds. Upon contact with water aldimine can be either hydrolyzed with formation of the corresponding amines and aldehydes. Due to these peculiarities, they can be used as a protected form amines or aldehydes. For example, aldimine used in polyurethane chemistry, where they serve as activated by the moisture cross-linking agents, the so-called "blocked amines as hardeners for one or both supplied in two packages of compositions containing isocyanate groups.

The use of aldimines as curing agents in the compositions containing isocyanate groups, has some advantages. First, aldimine have moderate, well-controlled reactivity in relation to isocyanate groups, while the corresponding free amines react significantly faster and as hardeners in the General case cannot be applied. Secondly, the presence of aldimines complicates the direct reaction of isocyanate groups with moisture, which produces carbon dioxide (CO2), and thereby significantly suppresses unwanted image is of gas bubbles in the composition.

However, the use of aldimines as curing agents in the compositions containing isocyanate groups, may also cause problems, in particular, due to the fact that during curing of such compositions are released aldehydes, which are not embedded in the formed polymer. Depending on the aldehyde composition can have a very strong smell, which for many applications is invalid. In addition, aldehydes due to migration effects can vyparivat of the composition or to reduce their mechanical strength or durability.

In WO 2004/013088 A1 describes odorless polyamidimide derived from primary polyamines and odorless aldehydes. In WO 2007/036571 A1 describes odorless aldimine containing at least one hydroxy-, mercapto - or secondary amino group and received on the basis of odorless aldehydes. The aldehydes released from such aldimines due to their low volatility largely remain in utverzhdenii compositions and can have a plasticizing and/or reduce the strength of the action. In addition, relatively high molecular weight data of aldehydes leads to aldimine must be used in relatively large quantities, which makes them expensive.

Op is a description of the invention

The objective of the invention is to develop a new aldimines that can be used as curing agents in curable compositions, in particular with preferred properties of the compositions containing isocyanate groups, and released during curing of the composition aldehydes are embedded in the formed polymer.

Unexpectedly it has been found that this problem can be solved at the expense of aldimines under item 1 of the claims. These are the compounds that are thermally stable, in most cases at room temperature are in the liquid state, have little odor and can be a simple method derived from readily available starting materials. They contain tertiary amino groups with relatively low basicity and can have a catalytic effect in chemical reaction systems. They also contain hydroxy-group, which is available for further reactions, for example, with isocyanate groups.

Such aldimine are, for example, acceptable as curing agents for curable compositions containing groups which are reactive in relation amines, such as epoxypropyl, anhydrite group and, in particular, isocyanate group. In compositions containing isocyanate groups is, the aldehydes released from aldimines during curing, due to their hydroxyl groups covalently embedded in the resulting polyurethane polymer and, thus, remain fully in composition.

Another object of the present invention are aldimine under item 15 of the claims, the interaction products which are aldimine under item 1 of the claims.

Another object of the present invention are curable compositions containing the described aldimine under item 17 of the claims.

The following objects of this invention are the method of obtaining aldimines under item 12, the application under item 16 and article on p. 29 of the claims.

Other aspects of the present invention are objects of the other independent claims. Preferred embodiments of the present invention are objects of the dependent claims.

Embodiments of the invention

The object of the present invention are aldimine formula (I):

,

where:

A denotes a radical amine after removal of n primary aliphatic amino groups and m HX-groups

or together with R7means (n+2)-valent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least the Dean heteroatom, in particular, in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group;

n is 1 or 2, or 3, or 4;

m is 0 or 1, or 2, or 3, or 4;

R1and R2independently from each other respectively denote monovalent hydrocarbon radicals containing from 1 to 12 C atoms,

or together denote divalent hydrocarbon radical that contains from 4 to 12 C atoms, part of which is an optionally substituted carbocyclic ring containing from 5 to 8 and preferably 6 C atoms;

R3means a hydrogen atom or alkyl, or arylalkyl, or alkoxycarbonyl, in particular containing from 1 to 12 C atoms;

R4and R5independently from each other, respectively, mean

methyl or a monovalent aliphatic, cycloaliphatic or arylaliphatic radical containing from 2 to 12 C atoms and optionally hydroxy-group and heteroatoms in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino groups,

provided that R4contains at least one hydroxy-group,

or

together means having at least one hydroxyl group, divalent aliphatic radical containing from 4 to 12 C atoms, part of which is an optionally substituted heterocyclic ring containing from to 8 and preferably 6 atoms in the ring, moreover, this ring optionally containing other heteroatoms in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group;

X stands for O or S or N-R6or N-R7,

where

R6means monovalent hydrocarbon radical containing from 1 to 20 C atoms and optionally at least one group of the ether carboxylic acid, a nitrile group, a nitro-group, group, ester phosphonic acid, sulfonic group or a group of ether sulfonic acid, or means the Deputy of the formula (II):

,

where:

p is 0 or an integer from 1 to 10,000; and

B means (p+1)-valent hydrocarbon radical, optionally containing oxygen, a simple ester group, a tertiary nitrogen of an amino group, a hydroxy-group, secondary amino group or mercaptopropyl; and

R7together with A means (n+2)-valent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least one heteroatom, in particular in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group.

The dotted line in formulas listed in this description represent respectively the relationship between the Deputy and relate to it the rest of the molecule.

The term "primary amino group" in this description means an amino group in the form of GRU the dust NH 2associated with organic radical. The term "secondary amino group" means an amino group in which the nitrogen atom is linked to two organic radicals, which can also be a common part of the ring. The term "tertiary amino group" means an amino group in which the nitrogen atom is linked to three organic radicals, and two of these radicals can also be a common part of the ring (= nitrogen of the tertiary amino group).

"Aliphatic" is called amine or amino group in which the nitrogen atom is linked exclusively with aliphatic, cycloaliphatic or arylaliphatic radicals.

The term "active hydrogen" in this description means a hydrogen atom, hydroxy-, mercapto - or secondary amino group.

R1and R2accordingly, means are preferably methyl.

R3preferably means hydrogen atom.

R4and R5accordingly, means are preferably 2-hydroxyethylene group or 2-hydroxyproline group.

The preferred aldimine formula (I) are aldimine, in which R4and R5together contain at least two hydroxy-group, and the radical A is at least bifunctional. Such preferred aldimine formula (I) are aldimine formula (I'):

,

g is e:

A' denotes the radical amine after removal of v primary aliphatic amino groups and u HX'-groups

or together with R7'means (v+2)-valent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least one heteroatom, in particular in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group;

u is 1 or 2, or 3, or 4; and

v is 0 or 1, or 2, or 3, or 4;

provided that u+v is 2 or 3, or 4, or 5;

R4'and R5'independently from each other, respectively, mean

methyl or a monovalent aliphatic, cycloaliphatic or arylaliphatic radical containing from 2 to 12 C atoms and optionally hydroxy-group and heteroatoms in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino groups,

provided that R4'contains at least one hydroxy-group, and R4'and R5'together contain at least two hydroxy-group,

or

together means having at least two hydroxy-group of the divalent aliphatic radical containing from 4 to 12 C atoms, part of which is an optionally substituted heterocyclic ring containing from 5 to 8 and preferably 6 atoms in the ring, and this ring optionally containing other heteroatoms in the form of a simple oxygen EF the nuclear biological chemical (NBC group or the nitrogen of the tertiary amino group;

X' represents O or S or N-R6'or N-R7',

where R6'means monovalent hydrocarbon radical containing from 1 to 20 C atoms and optionally at least one group of the ether carboxylic acid, a nitrile group, a nitro-group, group, ester phosphonic acid, sulfonic group or a group of ether sulfonic acid,

or does the Deputy of the formula (II'):

and

R7'together with A' mean (v+2)-valent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least one heteroatom, in particular in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group; and

B, p, R1, R2and R3have the previously mentioned values.

The sum (u+v) in the formula (I') is preferably equal to 2 or 3.

R4'and R5'in the formula (I') together preferably contain two hydroxy-group. In one embodiment, the implementation of such preferred aldimine formula (I') contains the radical R4'with two hydroxy groups and the radical R5'without the hydroxy-group or in another embodiment, R4'and R5'have one hydroxy-group each.

In one embodiment, implementation of the preferred aldimine formula (I') are aldimine formula (I a):

,

where:

A1does not contain active hydrogen and a primary amino group and

means a divalent hydrocarbon radical containing from 2 to 20 C atoms and optionally at least one heteroatom, in particular in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino groups,

or

together with R9means trivalent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least one heteroatom, in particular in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group;

X1means O or S or N-R8or N-R9,

where R8

means monovalent hydrocarbon radical containing from 1 to 20 C atoms and optionally at least one group of the ether carboxylic acid, a nitrile group, a nitro-group, group, ester phosphonic acid, sulfonic group or a group of ether sulfonic acid,

or does the Deputy of the formula (II a):

,

where B1means a divalent hydrocarbon radical, optionally containing oxygen, a simple ester group or the nitrogen of the tertiary amino groups and 2 to 12 C atoms; and

R9together with A1means trivalent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least one gets what roath, in particular, in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group;

and R1, R2, R3, R4'and R5'have the previously mentioned values.

In another embodiment, more preferred aldimine formula (I') are aldimine formula (I b):

,

where:

t is 2 or 3;

A2means radical polyamine with t primary amino groups after removal of the t primary amino groups and contains no active hydrogen;

and R1, R2, R3, R4'and R5'have the previously mentioned values.

Aldimine formula (I) is produced by interaction of at least one amineBformula (III) at least one sterically impeded, aliphatic, having at least one hydroxy-group of the aldehydeALDformula (IV):

,

where:

Xameans O or S or N-R6aor N-R7,

where R6ameans monovalent hydrocarbon radical containing from 1 to 20 C atoms and optionally at least one group of the ether carboxylic acid, a nitrile group, a nitro-group, group, ester phosphonic acid, sulfonic group or a group of ether sulfonic acid,

or does the Deputy of the formula (III'):

and m, n, p, A, B, R1, Rsup> 2, R3, R4and R5have the previously mentioned values.

Interaction AminBformula (III) and aldehydeALDformula (IV) carry out the condensation reaction with elimination of water. Such condensation reaction is very well known and is described, for example, in Houben-Weyl, "Methods der organischen Chemie", Vol. XI/2, page 73ff. This aldehydeALDrelative to the primary amino groups AminBuse equal or excess amount relative to stoichiometric. As a rule, the condensation reaction is carried out in the presence of a solvent, by means of which formed during the reaction water is removed in the form of an azeotropic mixture. However, for aldimines formula (I) is the preferred way to obtain without the use of solvents, and formed by condensation of the water removed from the reaction mixture by vacuum. By getting without the use of solvents, distillation of the solvent after completion of receipt is not required, which simplifies the manufacturing process. In addition, so aldimine does not contain a residue of the solvent, which could lead to nuisance odor.

In one of the embodiments as AminBacceptable are primary amines, such as, for example, the isomers of butyl, pentyl-, hexyl-, heptyl-, octyl, nonyl-, decyl-, undecyl to ecil and tridecylamine, alkoxyalkyl, such as 2-methoxyethylamine, 2-amoxicillin, 3-methoxypropylamine, 3-ethoxypropylamine, 3-(2-ethylhexyloxy)Propylamine, and higher homologues, such as, for example, 3-(2-methoxyethoxy)Propylamine, cyclohexylamine, benzylamine and 2-phenylethylamine.

As AminBacceptable are also compounds that along with one or more primary amino groups have at least one reactive group containing active hydrogen, in the form of a hydroxy-, mercapto - or secondary amino group. Examples of aminesBhaving more than one reactive group containing active hydrogen, are:

- aliphatic amines containing more than one secondary amino group and one or more primary amino groups, such as N,N'-bis-(3-aminopropyl)Ethylenediamine, Triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), pentamethylenebis and higher homologues linear polyethylenimine, N,N'-bis-(3-aminopropyl)Ethylenediamine, products multiple cinetelerevue or zhanbotayevna with the final hydrogenation primary di - and polyamines with several primary amino groups, such as N,N'-bis-(3-aminopropyl)Ethylenediamine, N,N'-bis-(3-aminopropyl)-1,4-diaminobutane, N,N'-bis-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N,N'-bis-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine and polietilene the ins with different degrees of polymerization (range of molecular weights from 500 to 1 000 000 g/mol), such as, for example, sold by the company BASF under the trade name Lupasol®in its pure form or in the form of aqueous solutions, and such polyethylenimine along with primary and secondary amino groups also contain tertiary amino groups;

- hydroxyamine containing more than one hydroxy-group and one or more primary amino groups, in particular derivatives polyalkoxysiloxanes three - or polybasic alcohols or polyalkoxysiloxanes polyamines, and amino sugar, such as glucosamine or galactosamine;

- hydroxyproline containing at least one hydroxy-group and at least one secondary amino group and received by cinetelerevue or zhanbotayevna with subsequent hydrogenation hydroxyamino, such as N-hydroxyethyl-1,2-amandemen, N-hydroxypropyl-1,2-amandemen, N-hydroxyethyl-1,3-propandiamine, N-3-hydroxyethyl-1,3-pentanediamine.

As AminBacceptable are also polyamine containing two or more primary aliphatic amino groups. Examples of aminesBwith more than three primary aliphatic amino groups are polyvinylene or copolymers containing primary amino groups, for example copolymers of allylamine and (meth)acrylates.

As AminBpreferably acceptable are, first, aminesB1formula is (III a),

,

where:

X1ameans O or S or N-R8aor N-R9,

and R8ameans monovalent hydrocarbon radical containing from 1 to 20 C atoms and optionally at least one group of the ether carboxylic acid, a nitrile group, a nitro-group, group, ester phosphonic acid, sulfonic group or a group of ether sulfonic acid,

or does the Deputy of the formula (III'):

and A1B1and R9have the previously mentioned values.

AminesB1are preferably acceptable for receipt of aldimines formula (I a).

Examples of aminesB1are:

connection with one or two primary aliphatic amino groups and one secondary amino group, such as, for example, N-methyl-1,2-amandemen, N-ethyl-1,2-amandemen, N-butyl-1,2-amandemen, N-hexyl-1,2-amandemen, N-(2-ethylhexyl)-1,2-amandemen, N-cyclohexyl-1,2-amandemen, 4-aminomethylpyridine, 3-(4-aminobutyl)piperidine, N-(2-amino-ethyl)piperazine, Diethylenetriamine (DETA), bis-hexamethylendiamine (BHMT), 3-(2-amino-ethyl)aminopropylation; di - and triamine received by cinetelerevue or zhanbotayevna with subsequent hydrogenation of primary mono - and diamines, such as N-methyl-1,3-propandiamine, N-ethyl-1,3-propandiamine, N-butyl-1,3-propandiamine, N-hexyl-1,3-about Indiamen, N-(2 - ethylhexyl)-1,3-propandiamine, N-dodecyl-1,3-propandiamine, N-cyclohexyl-1,3-propandiamine, 3-methylamino-1-pentylamine, 3-ethylamino-1-pentylamine, 3-butylamino-1-pentylamine, 3-hexylamino-1-pentylamine, 3-(2-ethylhexyl)amino-1-pentylamine, 3-dodecylamino-1-pentylamine, 3-cyclohexylamino-1-pentylamine, dipropylenetriamine (DPTA), N-3-(3-aminopentyl)-1,3-pentanediamine, N-5-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N-5-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, and aliphatic diamines, such as N-alkyl-1,3-prapadyamanasya coconut oil, N-alkyl-1,3-prapadyamanasya sunflower oil, N-alkyl-1,3-prapadyamanasya soybean oil, N-alkyl-1,3-prapadyamanasya grease fats or N-(C16-22-alkyl)-1,3-propandiamine, such as, for example, sold by the company Akzo Nobel under the trade name Duomeen®; products obtained analogously to the reaction of the Michael reaction accession aliphatic primary di - or triamino with Acrylonitrile, diesters of maleic or fumaric acid diesters tarakanovas acid, esters of acrylic and methacrylic acid, acrylic - and methacrylamide and diesters basis of itaconic acid with a molar ratio of 1:1;

- aliphatic hydroxyamine, such as, for example, 2-aminoethanol, 2-methylaminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-amino-2-butanol, 2-and the Ino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 4-(2-amino-ethyl)-2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol; containing primary amino derivatives of glycols, such as diethylene glycol, dipropyleneglycol, dibutylamino, and higher oligomers and polymers of these glycols, for example, 2-(2-aminoethoxy)ethanol, triethylenemelamine, α-(2-hydroxymethylene)-ω-(2-aminomethylated)poly(oxy(methyl-1,2-ethandiyl)); containing the hydroxy-group and a primary amino group derived polyalkoxysiloxanes three - or polybasic alcohols; products obtained with a single cinetelerevue with subsequent hydrogenation of glycols, for example, 3-(2-hydroxyethoxy)Propylamine, 3-(2-(2-hydroxyethoxy)ethoxy)Propylamine and 3-(6-hydroxyhexyloxy)Propylamine;

- aliphatic mercaptamine, such as, for example, 2-aminoethanethiol (group probably facilitates), 3-aminopropanol, 4-amino-1-butanethiol, 6-amino-1-hexanethiol, 8-amino-1-octanethiol, 10-amino-1-decanter, 12-amino-1-dodecanthiol, and amenitieshere, for example, 2-amino-2-deoxy-6-thioglucose.

As AminB1preferred are N-methyl-1,2-amandemen, N-ethyl-1,2-amandemen, N-cyclohexyl-1,2-amandemen, N-methyl-1,3-propandiamine, N-ethyl-1,3-propandiamine, N-butyl-1,3-propandiamine, N-cyclohexyl-1,3-propandiamine, 4-aminomethy is piperidine, 3-(4-aminobutyl)piperidine, DETA, DPTA, BHMT, and aliphatic diamines, such as N-alkyl-1,3-prapadyamanasya coconut oil, N-alkyl-1,3-prapadyamanasya sunflower oil, N-alkyl-1,3-prapadyamanasya soybean oil, N-alkyl-1,3-prapadyamanasya grease fats; products obtained analogously to the reaction of the Michael reaction accession of aliphatic primary diamines with diesters of maleic and fumaric acid, esters of acrylic and methacrylic acid, acrylic - and methacrylamide, preferably the diesters of maleic acid, in particular with dimethyl, diethyl, dipropionyl and debutalbum esters of maleic acid, and esters of acrylic acid, in particular with methyl ester of acrylic acid, with a molar ratio of 1:1; and aliphatic hydroxy - or mercaptoamines, in which the primary amino group separated from the hydroxy - or mercaptopropyl chain of at least 5 atoms, or ring, in particular, 5-amino-1-pentanol, 6-amino-1-hexanol and their higher homologues, 4-(2-amino-ethyl)-2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2-(2-aminoethoxy)ethanol, triethylenemelamine and higher oligomers and polymers, 3-(2-hydroxyethoxy)Propylamine, 3-(2-(2-hydroxyethoxy)ethoxy)Propylamine and 3-(6-hydroxyhexyloxy)Propylamine.

As AminB1more predpochtite lname are amines, selected from the group comprising N-methyl-1,2-amandemen, N-ethyl-1,2-amandemen, N-cyclohexyl-1,2-amandemen, N-methyl-1,3-propandiamine, N-ethyl-1,3-propandiamine, N-butyl-1,3-propandiamine, N-cyclohexyl-1,3-propandiamine, 4-aminomethylpyridine, 3-(4-aminobutyl)piperidine, DETA, DPTA, BHMT, aliphatic diamines, such as N-alkyl-1,3-prapadyamanasya coconut oil, N-alkyl-1,3-prapadyamanasya sunflower oil, N-alkyl-1,3-prapadyamanasya soybean oil, N-alkyl-1,3-prapadyamanasya grease fats, 5-amino-1 - pentanol, 6-amino-1-hexanol, 4-(2-amino-ethyl)-2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2-(2-aminoethoxy)ethanol, triethylenemelamine, 3-(2-hydroxyethoxy)Propylamine, 3-(2-(2-hydroxyethoxy)ethoxy)Propylamine and 3-(6 hydroxyhexyloxy)Propylamine.

As AminBpreferably acceptable are, first, aminesB2formula (III-b):

,

where A2and t have the previously mentioned values.

AminesB2are preferably acceptable for receipt of aldimines formula (I b).

Examples of aminesB2are:

- aliphatic, cycloaliphatic or arylaliphatic diamines, such as Ethylenediamine, 1,2-propandiamine, 1,3-propandiamine, 2-methyl-1,2-propandiamine, 2,2-dimethyl-1,3-propandiamine, 1,3-butanediamine, 1,4-butandiol is h, 1,3-pentanediamine (DAMP), 1,5-pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2,4 - and 2,4,4-trimethylhexamethylenediamine (TMD), 1,7-heptadien, 1,8-octanediamine, 1,9-enantiomer, 1,10-decontamin, 1,11-undecanedioic, 1,12-dodecandioic and methyl-bis-(3-aminopropyl)amine, 1,2-, 1,3 - and 1,4-diaminocyclohexane, bis-(4-aminocyclohexane)methane, bis-(4-amino-3-methylcyclohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5-dimethylcyclohexyl)methane, bis-(4-amino-3-ethyl-5-methylcyclohexyl)methane (M-MECA), 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= ISOPHORONEDIAMINE or ACCESSORIES>), 2 - and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3 - and 1,4-bis-(aminomethyl)cyclohexane, 2,5(2,6)-bis-(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-bis-(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and 1,3 - and 1,4-xylylenediamine;

- aliphatic diamines containing ether groups, for example, bis-(2-amino-ethyl)new ether, 3,6-dioxaoctyl-1,8-diamine, 4,7-dioctadecyl-1,10-diamine, 4,7-dioctadecyl-2,9-diamine, 4,9-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine and higher oligomers of these diamines, bis-(3-aminopropyl)polytetrahydrofuran and other polytetrahydrofurans with molecular masses of, for example, in the range from 350 to 5200, and polyoxyalkylene. Last PR what the products are, as a rule, the products obtained by aminating polyoxyalkylene, and are sold, for example under the name Jeffamine®(Huntsman Chemicals), under the name Polyetheramin (BASF) or under the name PC Amine®(Nitroil). Preferably acceptable polyoxyalkylene are Jeffamine®D-230, Jeffamine®D-400, Jeffamine®D-2000, Jeffamine®D-4000, Jeffamine®XTJ-511, Jeffamine®ED-600, Jeffamine®ED-900, Jeffamine®ED-2003, Jeffamine®XTJ-568, Jeffamine®XTJ-569, Jeffamine®XTJ-523, Jeffamine®XTJ-536, Jeffamine®XTJ-542, Jeffamine®XTJ-559; Polyetheramin D 230, Polyetheramin D 400 and Polyetheramin D 2000, PC Amine®DA 250, PC Amine®DA 400, PC Amine®DA 650 and PC Amine®DA 2000;

- aliphatic triamine, such as 4-aminomethyl-1,8-octanediamine, 1,3,5-Tris-(aminomethyl)benzene, 1,3,5-Tris-(aminomethyl)cyclohexane;

- polyoxyalkylene, which are, as a rule, the products obtained by aminating polyoxyalkylene and sold, for example, under the trade name Jeffamine®(Huntsman Chemicals), under the name Polyetheramin (BASF) or under the name PC Amine®(Nitroil), such as, for example, Jeffamine®T-403, Jeffamine®T-5000; Polyetheramin T403, Polyetheramin T5000 and PC Amine®TA 403, PC Amine®TA 5000.

As AminB2preferred are polyamine selected from the group comprising 1,6-hexamethylenediamine were, MPMD, DAMP, ACCESSORIES>, TMD, 1,3-xylylenediamine, 1,3-bis-(aminol who yl)cyclohexane, bis-(4-aminocyclohexane)methane, bis-(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis-(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,2-, 1,3 - and 1,4-diaminocyclohexane, 1,4-diamino-2,2,6-trimethylcyclohexane, 3,6-dioxaoctyl-1,8-diamine, 4,7-dioctadecyl-1,10-diamine, 4-aminomethyl-1,8-octanediamine and polyoxyalkylene with two or three amino groups, in particular the products sold by the company Huntsman under the trade name Jeffamine®type D-230, D-400, D-2000, T-403 and T-5000, and also similar products of BASF or Nitroil.

The aldehydeALDformula (IV') R1and R2accordingly, means are preferably methyl. R3preferably means hydrogen atom.

Preferred aldehydesALDare having at least two hydroxy-group aldehydesALD1formula (IV'):

,

where R1, R2, R3, R4'and R5'have the previously mentioned values.

R4'and R5'in the formula (IV') together preferably contain two hydroxy-group.

AldehydesALDformula (IV) are obtained, in particular, as the reaction product of manniche or α-aminoalkylsilane similar reaction manniche what is known from the literature; therefore, they can be characterized as Mannich bases. This aldehydeY1formula (V), aldehydeY2formula (VI) and Audi at least one hydroxy-group secondary aliphatic amine Cformula (VII) with the cleavage of water into the aldehydeALDformula (IV):

,

where R1, R2, R3, R4and R5have the previously mentioned values.

This interaction can be done with free reagentsY1,Y2andCaccordingly, formulas (V), (VI) and (VII) or reagents can be used to partially or completely in the form of derivative compounds. So, for example, aldehydeY1can be used in the form of enolate, in the form of an enol ether, in particular in the form of a simple ester of silylene, or enamine. AldehydeY2can be used, for example, in the form of oligomer in the case of formaldehyde, in particular, in the form of 1,3,5-trioxane or in the form of paraformaldehyde or in the form of a hydrate, polyacetale, acetal, N,O-acetal, aminal or polyamines. Having at least one hydroxy-group secondary aliphatic amineCcan also be used, for example, in the form of a salt, in particular in the form of amine hydrochloride or hydrosulfate Amin. It is possible to use a portion of the reactants in the free form and part in the form of derivatives or only come from derivatives. When using reagents in the form of derivatives aldehydeALDunder certain circumstances is formed also in the derived form, for example, in the form of a salt; in such cases is by appropriate processing, it can be converted into a free form, accordingly, the formula (IV). Accordingly, the rational can be of additional use in such reactions the transformation of auxiliary substances, such as Lewis acid or catalysts.

The interaction can be carried out also in the form of combined reactions, in which all three reagent can react with each other at the same time; or may be selected phased actions, in which two of the first reagent interact with each other, and the thus obtained intermediate product is then interacts with the third reagent, and the intermediate product can not be selected. As such intermediate products are acceptable, in particular, iminium salts, which are produced by interaction of the aldehydeY2in free or derived form salt having at least one hydroxy-group secondary aliphatic amineCwho aldehydeY1in free or derived form allows you to obtain the corresponding salt of the aldehydeALDformula (IV). This option is phased actions may have an advantage in that it is possible to provide a more mild reaction conditions, and thus to obtain a higher yield of product.

The interaction may be carried out using solvents, particularly polar solvents, such as water or alcohols, or the interaction may be carried out without using solvents.

In a preferred embodiment, the interaction of all reagents in the free form is in the form of combined reaction and aldehydeALDafter the implementation of the interaction between purified by distillation. However, preferably do not use organic solvents.

As aldehydeY1formula (V) are acceptable, for example, the following connections: Isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, 2-ethylcapronaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde and diphenylacetaldehyde. It is preferable to Isobutyraldehyde.

As aldehydeY2formula (VI) are acceptable, for example, the following compounds: formaldehyde, acetaldehyde, propanal, Butyraldehyde, Isobutyraldehyde, phenylacetaldehyde, benzaldehyde and substituted benzaldehyde, as well as the ester of Glyoxylic acid, in particular the ethyl ester of Glyoxylic acid. Preferred is formaldehyde.

As AminCformula (IV) are acceptable secondary aliphatic amines containing a hydroxy-group, such as, for example, amines selected from the group comprising Ala xiety primary amines, such as 2-(N-methylamino)ethanol, 2-(N-ethylamino)ethanol, 2-(N-propylamino)ethanol, 2-(N-isopropylamino)ethanol, 2-(N-butylamino)ethanol, 2-(N-cyclohexylamino)ethanol, 3-(N-methylamino)-2-propanol, 3-(N-ethylamino)-2-propanol, 3-(N-propylamino)-2-propanol, 3-(N-isopropylamino)-2-propanol, 3-(N-butylamino)-2-propanol, 3-(N-cyclohexylamino)-2-propanol, 2-(N-ethyleneoxy)ethanol; cycloaliphatic hydroxyamine, such as 2-pyrrolidineethanol, 3-hydroxypyrrolidine, 2-piperidinemethanol, 3 - or 4-hydroxypiperidine and 1-(2-hydroxyethyl)piperazine.

As AminCformula (IV) preferably are acceptable secondary aliphatic aminesC1containing at least two hydroxy-group. AminesC1are preferably acceptable for obtaining the preferred aldehydesALD1formula (IV').

Acceptable aminesC1with two hydroxy groups are, in particular, amines selected from the group consisting of diethanolamine, dipropylamine, diisopropanolamine, 3-(2-hydroxyethylamino)-1-propanol and 3-(2-hydroxypropylamino)-1-propanol, N-methyl-2,3-dihydroxypropyl, 3,4 - dihydroxypyrrolidine 2,5-bis-(hydroxymethyl)pyrrolidine, 2,6-bis-(hydroxymethyl)piperidine, 3,4 - or 3,5-dihydroxypyridine, 2-(2,3-dihydroxypropyl)pyrrolidine and 2-(2,3-dihydroxypropyl)piperidine, and the products of interaction of ammonia with two molecules of the mi connections, each of which contains apachegroup, in particular the group pilgramage ether.

Acceptable aminesC1having more than two hydroxy groups are, for example, the following compounds: 2-(2,3-dihydroxypropyl)ethanol, 3,4,5-trihydroxypyrimidine, N,N-bis-(2,3-dihydroxypropyl)amine, 2,5-bis-(2,3-dihydroxypropyl)pyrrolidin and 2,6-bis-(2,3-dihydroxypropyl)piperidine.

As AminC1preferred are diethanolamine and diisopropanolamine.

Preferred aldehydesALD1formula (IV') are 3-(N-bis-(2-hydroxyethyl)amino)-2,2-dimethylpropyl and 3-(N-bis-(2-hydroxy-2-methylethyl)amino)-2,2-dimethylpropyl.

AldehydesALDformula (IV) have a number of special properties. For example, they possess good thermal stability, because the C atom in α-position to the aldehyde group is not associated with the hydrogen atom and it is therefore not possible dissociation of the secondary amino groups with the formation of the alkene. In addition, they have unexpectedly good stability against oxidation by air oxygen. Their basicity unexpectedly turned out to be significantly lower than expected basicity of aliphatic amines such structures; the value of the pKameasured for the conjugate acid aldehydeALDabout 2 units lower values for the conjugate acids of the secondary amineC, use sovannara to obtain this aldehyde ALD. Such unexpected properties possibly associated with intramolecular 1,4-interaction between the amino group and aldehyde group (the overlap between the orbitals of the free electron pair of nitrogen and π - or π*orbitals of the carbonyl group), which was expressed P.Y. Johnson et al. (J. Org. Chem., Vol. 40, Nr. 19, 1975; Seiten 2710-2720) on the basis of NMR and UV spectroscopic studies of β-aminoaldehyde.

Finally, aldehydesALDeven at relatively low molecular weight, do not smell or have only a very faint odor. This unexpectedly low for aldehyde odor intensity, on the one hand, due to the fact that aldehydesALDdue to the presence of OH-groups are relatively low volatile. In addition, a slight smell, probably favors mentioned intramolecular 1,4-interaction and steric obstruction aldehyde groups associated with tertiary atom C.

Hydroxy-group of aldehydesALDallow subsequent reaction with the formation of other functionalized reaction products. Preferred aldehydesALD1formula (IV')containing at least two hydroxy-group, can be used, in particular, as a hardener compositions containing components that are reactive towards hydroxyl groups, for example, the components with isoci the more groups.

Aldimine formula (I) can be obtained, as described earlier, directly from aminesBand aldehydesALD.

Aldimine formula (I)having as substituents X N substituents-R6if necessary, you can easily get through that differ from those described previously. This variant of the synthesis is that the aldehydeALDformula (IV) interaction with two - or trivalent and preferably divalent aliphatic primary amine, as described previously AminB2in the first stage is transformed into an intermediate product, which, along with one or two eliminarpremio contains one or two and preferably one primary amino group. Then this intermediate product in the second stage is transformed into aldimine formula (I) via a single alkylation of the primary amino group. For alkylation is preferably used compounds with only one reactive double bond, which may be involved in the reactions of addition of the primary amine, similar to Michael's reaction; such compounds in the further description as "Michael acceptors".

The conversion of aldehydeALDinteraction with the amineB2in the intermediate product having a primary amino group, carry out the condensation reaction with elimination of water according to the reaction described is Oh earlier in relation to the interaction of the aldehyde ALDwith AminBformula (III). Thus, the stoichiometric ratio between the aldehydeALDand AminB2choose a so that 1 mol of aldehydeALDon 1 mole of the amineB2having two primary amino groups, or so that two moles of aldehydeALDfall on one mole of the amineB2having three primary amino groups. When applied AminB2preferably is asymmetric relative to the amino groups. Preferred is a method of obtaining without the use of solvent, and formed by condensation water is removed from the reaction mixture by vacuum.

The interaction of the intermediate product, having a primary amino group, with a Michael acceptor is carried out, for example, mixing the intermediate product with a Michael acceptor, taken in an amount equal to or slightly greater than the stoichiometric amount, and heating the mixture at a temperature in the range from 20 to 110°C until complete conversion of the intermediate product in algemin formula (I). The interaction is preferably carried out without using solvents.

As AminB2for this option receive preferred are the diamines in which the primary amino groups separated by a chain of at least 5 atoms, or ring, in particular 1,5-diamino-2-methylpentane, 1,6-hexamethylene is in, 2,2,4 - and 2,4,4-trimethylhexamethylenediamine and mixtures thereof, 1,10-decontamin, 1,12-dodecandioic, 1,3 - and 1,4-diaminocyclohexane, bis-(4-aminocyclohexane)methane, bis-(4-amino-3-methylcyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3 - and 1,4-bis-(aminomethyl)cyclohexane, 2,5(2,6)-bis-(aminomethyl)bicyclo[2.2.1]heptane, 3(4),8(9)-bis-(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3 - and 1,4-xylylenediamine, as well as the aforementioned aliphatic diamines containing ether groups, and polyoxyalkylene.

Examples of acceptable Michael acceptors are the diesters of maleic or fumaric acid, such as dimethylmaleic, diethylmalonate, dibutylamine, diethylfumarate; diesters tarakanovas acid, such as dimethylcarbonate; esters of acrylic or methacrylic acid such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, tetrahydrofuryl(meth)acrylate, isobornyl(meth)acrylate; diesters basis of itaconic acid such as dimethylethanol; esters of cinnamic acid, such as methylcinnamic; diesters vinylphosphonic acid, such as dimethyl ether vinylphosphonic acid; esters vinylsulfonic acid, in particular arrowy ether vinylsulfonic acid; vinylsulfonic; wininit the crystals, such as Acrylonitrile, 2-Nitrilite or fumaronitrile; 1-nitroethylenes, such as β-nitrosothiol; and condensation products of knoevenagel, such as, for example, products derived from diesters of malonic acid and aldehydes, such as formaldehyde, acetaldehyde or benzaldehyde. Preferred are diesters of maleic acid, esters of acrylic acid, diesters of phosphonic acid and wininit.ini.

Aldimine formula (I) in the variants of implementation, in that they contain at least one group HX, if necessary, can be in equilibrium with cyclic forms, as shown, for example, for the formula (VIII) in the case m=1. Data cyclic form are, in the case of aminoalkenes, cyclic aminal, such as imidazolidine or tetrahydropyrimidine, in the case of hydroxyarginine - cyclic aminoacetate, such as oxazolidine or tetrahydroazepine, and in the case of mercaptoethylamine - circular thiaminase, such as thiazolidine or tetrahydrothiophene.

In the formula (VIII) n, A, X, R1, R2, R3, R4and R5have the previously mentioned values.

Unexpectedly, the majority of aldimines formula (I)containing HX-group, do not show any tendency to cyclization. In particular, for aminoalkenes by IR - and NMR-spectroscopy can b the th shows these compounds are mainly in the form of an open circuit, i.e. in the form of aldimines, while a circular shape, i.e. the shape of Amidala, absent or present only in trace quantities. Hydroxy - and mercaptoamines, in which the primary amino group separated from the hydroxy - or mercaptopropyl chain of at least 5 atoms, or ring, also show a weak degree of cyclization.

In the case of aldimines formula (I) refers to new, hitherto not described compounds with unexpected properties. They contain sterically complicated working antiminority, in which the C atom located at the α-position, is not associated with the hydrogen atom, and therefore cannot become through tautomerizations in inlinegroup. Consequently, such antiminority are especially well protected (locked) primary amino groups, which in the presence of water are moderate, well-controlled reactivity in relation to groups which are reactive in relation amines, such as epoxypropyl, anhydrite group and, in particular, isocyanate group, which is a strong contrast compared to the high reactivity of the corresponding free amino groups, derivatives of which are antiminority. Aldimine formula (I) will also gain a tertiary amino group, which under certain conditions can exhibit catalytic activity in chemical reaction systems; however, the basicity of aldimines formula (I), due to the tertiary amino group is, as mentioned earlier in relation to aldehydesALDformula (IV), lower. Aldimine formula (I) even at relatively low molecular weight aldehydesALDthat make up their base, do not smell or have only a weak odor characteristic of amines.

Aldimine formula (I) possess good thermal stability, because the C atom in the α-position relative to antiminority, as mentioned, is not associated with the hydrogen atom and it is therefore not possible dissociation of the secondary amino groups with the formation of the alkene.

Aldimine formula (I) are stable when stored under appropriate conditions. When the access of moisture their antiminority, passing through intermediate stages, formally can be either hydrolyzed to amino groups, and frees the corresponding aldehydesALDformula (IV), which were used to obtain aldimines and which, as mentioned earlier, have low odor or odorless. Since this hydrolysis reaction is reversible and the chemical equilibrium is markedly shifted towards aldimine, it should be assumed that in the absence of a link is, which is reactive against amines, partially hydrolyzed or fully only part of alvinegro. In an unexpected way hydrolysis of alvinegro, despite the presence of tertiary amino groups, can be catalysed by acids.

Aldimine formula (I) contain aldehyde in part by at least one hydroxy-group. This causes the subsequent reactions of these hydroxyl groups with compounds which are reactive towards hydroxyl groups, in particular, even after the recent release of the aldehydeALDduring the hydrolysis of alvinegro.

Aldimine formula (I) can be obtained in a relatively straightforward manner from readily available starting materials. If when you receive them use low-viscosity aminesBformula (III), the corresponding aldimine formula (I) partially are also low-viscosity compounds.

Aldimine formula (I) allow a very wide range of uses. For example, they can be used where they can serve as a source of aldehydesALDformula (IV) or aminesBformula (III). In particular, they can be used as a protected amine or protected aldehydes in systems that are reactive towards aldehydes and/or amines, and optionally purposefully can be release is found from protection. In particular, they find application in systems in which there are compounds that react with primary amines and/or hydroxy groups. Removing protection from a primary amino groups carried out by hydrolysis, for example, by contact with water or moisture, in particular, with air moisture. In an unexpected way hydrolysis of alvinegro, despite the presence of tertiary amino groups, can similarly be catalysed by acids, as in the case of aldimines, not containing tertiary amino groups in the molecule.

On the other hand, aldimine formula (I) with index m greater than zero, are used in obtaining other functionalized reaction products data aldimines. For example, aldimine formula (I) with index m greater than zero, can be brought into interaction with compounds that can react with a group HX, in particular, if the HX groups are secondary amino groups. Compounds suitable for interaction with a group HX, possess reactive groups, such as, for example, isocyanate group, epoxypropyl, anhydrite group or groups with double or triple bonds, activated to a greater or lesser extent, such as (meth)acrylate, acrylamide, 1-tinykernel, 1-propionylcarnitine, maleinimide, citrullinemia, vinyl, from propylene or allyl group. The interaction products containing antiminority and received by such reactions proceed, if necessary, to hydrolyze with obtaining aldehydesALDformula (IV) and compounds with a primary amino group and use them in other reactions, such as reactions stitching, and the hydrolysis reaction can be catalysed by acids.

In addition, aldimine formula (I) can act as catalysts in chemical reaction systems, for example, curable compositions containing isocyanate groups, in particular, to reduce the time of curing.

Finally, aldimine formula (I) can be used as a source cationogenic compounds due to the fact' that the tertiary amino groups are partially or completely protonium to ammonium groups or alkylate to Quaternary ammonium groups. The protonation or alkylation of aldimines formula (I) can be obtained aldimine formula (IX):

,

where:

R10means a hydrogen atom or alkyl, cycloalkyl or arylalkyl containing from 1 to 20 C atoms;

X2means O or S or N-R11or N-R7,

where R11

means monovalent hydrocarbon radical containing from 1 to 20 C atoms and optionally at least one group of the ether carboxylic acids, n is trilogy group, the nitro-group, group, ester phosphonic acid, sulfonic group or a group of ether sulfonic acid,

or does the Deputy of the formula (IX'):

m, n, p, A, B, R1, R2, R3, R4, R5and R7have the previously mentioned values.

Aldimine formula (IX) are also based on the previously mentioned aminesBformula (III) and aldehydeALDformula (IV), and tertiary amino aldehydeALDbefore interaction with the amineBpartially or fully protonium or alkylate.

For protonation of aldimines formula (I) or aldehydesALDcan be used any acid Branstad, for example, hydrochloric, sulfuric, phosphoric acid, carboxylic acids such as acetic or benzoic acid, and sulfonic acids such as methanesulfonate or p-toluensulfonate acid. For alkylation of aldimines formula (I) or aldehydesALDcan be used known alkylating agents, in particular meteorous agents, for example, methyliodide, dimethylsulfate, dimethylphosphate, diazomethane, methyl ester persulfonic acid or trimethyloctadecylammonium.

Specialists in the art it is clear that to nationalincome aldimine formula (IX) is the anion that balances the positive charge aldim is on.

Aldimine formula (I) or formula (IX), particularly preferred aldimine formula (I')having at least two hydroxy-group, are preferably acceptable for use as ingredients of the compositions derived from isocyanates or epoxy resins, in particular for use as adhesives, sealants, casting masses, coatings, floor coverings, coatings, varnishes, coatings and foams. Such compositions preferably contain acid is at least one species, in particular carboxylic or sulfonic acid, or a compound hydrolyzable to such acids, and acid in an unexpected way catalyse the hydrolysis of alvinegro, despite the presence of tertiary amino groups.

Aldimine formula (I) or aldimine formula (IX), in particular aldimine formula (I')having at least two hydroxy-group, are preferably acceptable as hardeners or as precursors of hardeners for one or both supplied in two packages of compositions containing isocyanate groups, such as adhesives, sealants, casting masses, coatings, floor coverings, coatings, varnishes, primers and foam. Thus aldehydesALDformula (IV), released during the hydrolysis of alvinegro, react through their hydroxyl groups with isocyanate groups is thus covalently incorporated in the polymer, formed during curing. In the case of the use of aldimines formula (I') are released aldehydesALD1having at least two hydroxy-group; in addition, these aldehydes with his hand can also serve as hardeners due to the fact' that they contribute to the lengthening of the chains and/or crosslinking of the resulting polymer and do not lead to breakage of the chains.

As mentioned earlier, aldimine formula (I) contain sterically complicated working antiminority that cannot turn through tautomerizations in inlinegroup and are especially well protected (locked) primary amino groups. Such amino groups react in the presence of water with the present isocyanate groups, and their reactivity compared to the free primary amino groups is substantially less, so that such systems possess good technologically acceptable speed curing.

Hydroxy-group released aldehydesALDreact also with the present isocyanate groups and thus, as mentioned, covalently incorporated in the polymer formed during curing, which is a big advantage. By embedding the aldehydes do not cause the composition of harmful effects, such as, for example, increased shrinkage, zag is Yasnaya emissions into the ambient air, in particular, unpleasant odor, or migration effects, such as wypadanie; they also do not render harmful influence on the mechanical properties of the composition, for example, due to the provision of plasticizing action or decrease the resistance of the composition to influences from the environment, such as heat or UV radiation. As mentioned earlier, aldimine formula (I') are preferred, as emitted aldehydesALD1contain at least two hydroxy-group and thus during curing of compositions containing isocyanate groups, as at least bifunctional curing agent by chain-extending or crosslinking covalently incorporated in the resulting polymer.

In compositions containing isocyanate groups and containing as a hardener aldimine formula (I) or formula (IX), hydroxy-group, and optionally available secondary amino groups react directly with isocyanate groups, while antiminority react with isocyanate groups during the hydrolysis in the presence of water. This isocyanate groups react with primary amino groups released formally free in the hydrolysis of alvinegro, and the corresponding aldehydeALDreleased in free form or in the form of an adduct. Isocyanate GRU is dust, which is excessive in relation to eliminarprem, secondary amino groups and hydroxy groups react directly with water with formation of urea groups. At the proper stoichiometric ratio of isocyanate groups and aldimine formula (I) by the result of these reactions is the curing of the composition; this is also referred to as stitching. The reaction of the isocyanate groups with gidrolizuemye eliminarpremio does not have to occur only at the expense of free amino groups. Of course, it is also possible reactions at intermediate stages of hydrolysis. For example, the possible reaction gidrolizuacy antiminority as polyamines directly with the isocyanate group. For curing such a composition is also irrelevant whether they respond hydroxy-group of the aldehyde part of aldimines with isocyanate groups before the hydrolyzed antiminority, or only afterwards. Once in the composition will be sufficient moisture, for example, from the air in the form of moisture in the air, immediately hydrolysis alvinegro and interaction formally released the primary amino groups with isocyanate groups, even if the available hydroxy-group has entered into cooperation with isocyanate groups. Unexpectedly, the presence of t is etycznych of amino groups does not interfere with the acid-catalyzed hydrolysis of alvinegro.

The tertiary amino group of aldimines formula (I) can have a catalytic effect on the reaction of isocyanate groups and can therefore speed up the stitching. This accelerating effect is additionally due to the fact that the tertiary amino groups are localized in the aldehyde part of aldimines. The advantage is that the basicity of the tertiary amine groups is relatively low, as strongly alkaline tertiary amines can extremely speed up the direct reaction of the isocyanate groups, in particular with water, which when cured can have a disturbing effect. During the hydrolysis of alvinegro released aldehydesALDformula (IV)containing a tertiary amino group and at least one hydroxy-group. AldehydesALDdue to the reaction of hydroxyl groups with isocyanate groups covalently incorporated in the resulting polymer. After embedding in polymer catalytic activity of the tertiary amine groups due to their limited mobility is greatly reduced, which may provide advantages in terms of durability of the material. Aldehyde groups formed during the hydrolysis of alvinegro, during curing are saved and can be used for subsequent reactions.

It is also possible to store aldimine formula (I) together with water. The hydrolysis takes place is full of the stew only when a mixture of water aldimine" comes in contact with isocyanate groups. The reaction between aldimine formula (I) and the isocyanate groups is very slow compared to the reaction of the corresponding free amines exactly when aldimine are mixed with water or when water is in excess.

You can also use aldimines formula (I) or formula (IX) in the compositions, which otverzhdajutsja under the action of heat, for example, through the use of compounds with thermally labile blocked isocyanate groups. You can also use aldimines formula (I) or formula (IX) in the compositions, which are thermosetting low-melting or refractory hot melt adhesives. Such adhesives include hot melt compounds having, in particular, isocyanate group; at room temperature they are in the solid state and put them in a hot or warm.

Another object of the present invention are curable compositions containing at least one polyisocyanate and at least one aldimine formula (I) or formula (IX).

The term "polyisocyanate" in this description refers to compounds with two or more isocyanate groups, regardless of whether it about a Monomeric diisocyanates, oligomeric-or polyisocyanates having isocyanate g is uppy polymers with relatively high molecular weight.

As aldimine formula (I) acceptable are described in detail earlier aldimine formula (I), respectively, and their preferred options, in particular aldimine formula (I'). Acceptable aldimine formula (IX) have also been described previously.

Preferred are curable composition containing at least one polyisocyanate and at least one aldimine formula (I'), in particular at least one aldimine formula (I a) or formula I (b).

In one embodiment, the implementation of the curable composition is odnoupakovochnye.

Under odnoupakovochnye composition in this description to understand curable composition, in which case all the ingredients of the composition are mixed in the same package and which at room temperature is stable during storage for a long time, so it consumer or operational properties due to storage do not change or change in insignificant extent, and which after application cures under the influence of moisture and/or heat.

Tropicabana curable composition preferably contains at least one polyisocyanate, isocyanate groups which preferably represent a blocked isocyanate group.

Under "blocked isocyanate group in this description and in imaut isocyanate group, which due to the previous interaction of the free isocyanate groups with a blocking agent known in the prior art, such as, for example, phenol, ketoxime, pyrazole, lactam or fluids malonic acid, reduced reactivity against nucleophiles so strongly that it is at room temperature stable when stored together with appropriate hardeners and begins to respond to these hardeners only under the action of heat and/or moisture, and a blocking agent, depending on the type released is optional.

Acceptable polyisocyanates with blocked isocyanate groups are supplied on sale, for example, under the commercial names Desmocap®11, 12 and 2540 XP (all supplied by Bayer), Trixene®BI 7641, BI 7642, BI 7770, BI 7771, BI 7772, BI 7774 and BI 7779 (all supplied by Baxenden), Vestanat®B 1358A, B 1358/100 or B 1370 (all supplied by Degussa), and Tolonate®D2 (supplied by the company Rhodia) or, if necessary, may be obtained by interaction of polyisocyanates with acceptable blocking agents.

Tropicabana curable composition may be moisture curing and/or thermoset.

Under "thermosetting composition" in this description to understand the composition with blocked isocyanate groups is mi, in the case of which when heated to the appropriate temperature, typically in the range from 120 to 200°C, in special cases even at a temperature of from 80°C, blocked isocyanate groups are activated so that starts stitching acceptable hardeners and accordingly curing. This process is also called thermal drying is carried out, as a rule, after application of the composition.

As a rule, the complete curing described odnoupakovochnye composition occurs by the combined action of moisture and heat.

In a preferred embodiment, the curable composition is the two packages.

Under the two packages" composition in this description to understand curable composition, in which case the ingredients of the composition are in the form of two different components, which are stored in separated from other packages and each of which is stable during storage. Components identified as a component ofK1and theK2. Both components are mixed with each other only for a short time prior to application or during application of the composition, after which the mixed composition is cured, and curing under certain circumstances occurs or is completed only under the influence of moisture and/or heat.

More preferred are Documation the e-curable composition, consisting of componentK1and theK2moreover , such compositions contain at least one polyisocyanatePand at least one aldimine formula (I'). When curing is released with at least two hydroxy-group aldehydesALD1formula (IV), which on its part to act as a hardener in the ratio of MDIPand by chain-extending or crosslinking covalently incorporated in the resulting polymer.

ComponentK1preferred curing the two packages of the composition contains at least one polyisocyanateP.

As MDIPin one embodiment, the implementation is acceptable polyisocyanatePIin the form of a Monomeric di - or triisocyanate or oligomer of Monomeric diisocyanate or a derivative of a Monomeric diisocyanate.

As a Monomeric di - or triisocyanate are acceptable, for example, the following compounds: 1,4-tetramethyldisilane, 2-methylpentanediol-1,5-diisocyanate, 1,6-hexamethylenediisocyanate (HDI), 2,2,4 - and 2,4,4-trimethyl-1,6-hexamethylenediisocyanate (TMDI), 1,10-decamethylenediamine, 1,12-dodecyltrimethoxysilane, liaindizecign, disorientatingly ether, cyclohexane-1,3 - and cyclohexane-1,4-diisocyanate, 1-methyl-2,4 - and 1-methyl-2,6-diisocyanatohexane and any mixtures of these isomers (HTDI and the and H 6TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (= isophorondiisocyanate or IPDI), perhydro-2,4'- and perhydro-4,4'-diphenylmethanediisocyanate (HMDI or H12MDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3 - and 1,4-bis-(isocyanatomethyl)cyclohexane, m - and p-xylylenediisocyanate (m - and p-XDI), m - and p-tetramethyl-1,3 - and m - and p-tetramethyl-1,4-xylylenediisocyanate (m - and p-TMXDI), bis-(1-isocyanato-1-methylethyl)naphthalene, isocyanates dimeric and trimeric fatty acids such as 3,6-bis-(9-isocyanatophenyl)-4,5-di-(1-heptenyl)cyclohexene (dimerisation), α,α,α',α',α",α"-HEXAMETHYL-1,3,5-mesitylenesulfonic, 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 homologs (polymer MDI or PMDI), 1,3 - and 1,4-delete the entry, 2,3,5,6-tetramethyl-1,4-diisocyanates, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatobutane (TODI), densityindependent (DADI), 1,3,5-Tris-(isocyanatomethyl)benzene, Tris-(4-isocyanatophenyl)methane and Tris(4-isocyanatophenyl)thiophosphate.

As MDIPIpreferably acceptable are oligomers or derivatives of Monomeric diisocyanates, in particular HDI, IPDI, TDI and MDI. Commercially available types are, in particular, HDI-biuret, for example, Desmodur®N 100 and N 3200 (Bayer), Tolonate®HDB and HDB-LV (Rhodia) and Duranate® 24A-100 (Asahi Kasei), HDI-isocyanurate, for example, Desmodur®N 3300, N 3600 and N 3790 BA (all supplied by Bayer), Tolonate®HDT, HDT-LV and HDT-LV2 (Rhodia), Duranate®TPA-100 and THA-100 (Asahi Kasei) and Coronate®HX (Nippon Polyurethane), HDI-uretdione, for example, Desmodur®N 3400 (Bayer), HDI-iminoimidazolidine, for example, Desmodur®XP 2410 (Bayer), HDI-allophanate, for example, Desmodur®VP LS 2102 (Bayer), IPDI-isocyanurate, for example, Desmodur®Z 4470 (Bayer) in the form of a solution or Vestanat®T1890/100 (Degussa) in the form of solids, TDI-oligomers, for example, Desmodur®IL (Bayer), and mixed isocyanurate based on TDI/HDI, for example, Desmodur®HL (Bayer). Also preferred are acceptable forms of MDI at room temperature in a liquid state (the so-called "modified MDI"), which in the form of mixtures of MDI and MDI derivatives, such as, for example, MDI carbodiimide or MDI-uretonimine, or MDI urethanes, known, for example, under the commercial names Desmodur®CD, Desmodur®PF, Desmodur®PC (all supplied by Bayer), as well as mixtures of MDI and MDI homologs (polymer MDI or PMDI) are sold under the commercial names Desmodur®VL, Desmodur®VL50, Desmodur®VL R10, Desmodur®VL R20 and Desmodur®VKS 20F (all supplied by Bayer), Isonate®M 309, Voranate®M 229 and Voranate®M 580 (all supplied by Dow) or Lupranat®M 10 R (BASF).

In practice upon is by oligomeric polyisocyanates PIrepresent, as a rule, mixtures of substances with different degrees of oligomerization and/or chemical structure. Preferably they have an average NCO functionality in the range from 2.1 to 4.0 and contain, in particular, which is, iminoimidazolidine, uretdione, urethane, biuret, allophanate, carbodiimide, uretonimine or oxidization group. These oligomers preferably have a low content of Monomeric diisocyanates.

As MDIPIpreferred are the MDI form at room temperature in the liquid state, as well as oligomers HDI, IPDI and TDI, in particular isocyanurate.

In another embodiment, as MDIPacceptable is a polyurethane polymerPUP,having isocyanate groups.

The term "polymer" in this description refers, on the one hand, to a collection of chemically homogeneous, but about the degree of polymerization, molecular weight and chain length of different macromolecules obtained by polyreactive (polymerization, polyprionidae, polycondensation). On the other hand, the term also refers to a derivative of such a set of macromolecules obtained by polyreactive, i.e. compounds that are produced by interactions, such as, for example, joining or samadani is, with the functional groups of pre-defined macromolecules and which may be chemically uniform or chemically non-uniform. In further description, the term refers also to the so-called prepolymers, i.e. reactive oligomeric previous adducts, functional groups which participate in the formation of macromolecules.

The term "polyurethane polymer" refers to polymers obtained by the method so-called diisocyanate polyaddition. The term also refers to polymers which contain urethane groups in small quantities or not at all contain them. Examples of polyurethane polymers are politicomilitary on the basis of simple esters, politicomilitary based esters, politicalisation on the basis of simple esters, polyureas, politicalisation based esters, polyisocyanurate and polycarbamide.

Acceptable polyurethane polymerPUP,having isocyanate groups can be obtained by the interaction of at least one polyol with at least one polyisocyanate.

As polyols to obtain a polyurethane polymerPUPcan be used, for example, the following polyols or mixtures thereof.

- Simple polyether polyols, also called polyoxyalkylene or simply is and oligohidrosis and representing the polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2 - or 2,3-butilenica, tetrahydrofuran or mixtures thereof, optionally polymerized using ioniziruyuscyego compounds, such as, for example, water, ammonia, 1,2-ethanediol, 1,2 - and 1,3-propandiol, neopentylglycol, diethylene glycol, triethylene glycol, the isomeric dipropyleneglycol and dipropyleneglycol, isomeric butandiol, pentandiol, hexandiol, heptanediol, octanediol, nonanediol, decanediol, undemandingly, 1,3 - and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, glycerol, aniline, and mixtures of the abovementioned compounds. Can be used as polyoxyalkylene having a low degree of unsaturation (measured according to ASTM D-2849-69 and specified in milliequivalent unsaturated bonds per gram of polyol (mEq/g)) and we get, for example, by using so-called double metallocyanide complex catalysts (DMC catalysts), and polyoxyalkylene with a higher degree of unsaturation obtained, for example, anionic catalysts such as NaOH, KOH, CsOH or alkali metal alcoholate.

As a simple polyether polyols preferably are acceptable polyoxyalkylene and polyoxyalkylene, in particular polyoxyalkylene. Especially acceptable polyoxyalkylene and polyoxyalkylene what trioligy are polyoxyethylenic and polyoxyethylene, and polyoxypropylene and polyoxypropylene.

Preferably acceptable are polyoxypropylene and polyoxypropylene with a degree of unsaturation less than 0.02 mEq/g and a molecular weight in the range from 1 000 to 30 000 g/mol, and polyoxypropylene and polyoxypropylene with a molecular weight in the range of from 400 to 8000 g/mol. Under the molecular or molar mass in this description always understand srednekamennogo molecular mass Mn. Preferably acceptable are Polyoxypropylenediamine with a degree of unsaturation less than 0.02 mEq/g and a molecular weight in the range from 1 000 to 12 000, in particular in the range from 1 000 to 8 000 g/mol. Such simple polyether polyols implements, for example, the company Bayer under the trade name Acclaim®.

Preferably acceptable are also so-called "EO-terminal" (ethylene oxide-terminal) polyoxypropylene and polyoxypropylene. The latter compounds are a special Polyoxypropylenediamine obtained, for example, due to the fact that the individual polyoxypropyleneamine after polipropilenovaya alkoxylated with ethylene oxide, leaving behind a primary hydroxy-group.

Grafted styrolacrylonitrile or acrylonitrilebutadiene atnie the polyether polyols based on ethers.

The polyether polyols based on esters, also called complex oligohidrosis and obtained by known methods, in particular by polycondensation hydroxycarbonic acids or the polycondensation of aliphatic and/or aromatic polycarboxylic acids with two - or polyhydric alcohols.

Preferably acceptable are the polyether polyols based on esters derived from two - or trivalent and preferably from diatomic alcohols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, neopentylglycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,12-hydroxystearates alcohol, 1,4-cyclohexanedimethanol, dimeric fatty dihydroxyindole (dimetyl), neopentylglycol ether hydroxypivalic acid, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols, and organic di - or tricarboxylic acids, preferably dicarboxylic acids or their anhydrides or esters, such as, for example, succinic, glutaric, adipic, trimethyladipic, cork, azelaic, sabotinova, dodecadienol, maleic and fumaric acid, dimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethylmaleic the lat, hexahydrophthalic acid, trimellitate acid and anhydride trimellitic acid, or mixtures of the aforementioned acids, and also the polyether polyols based on esters derived from lactones, such as ε-caprolactone, and initiators, such as the two - or trivalent alcohols.

More acceptable polyether polyols are polyetherdiol based esters.

- Polycarbonatediol obtained by the interaction, for example, mentioned earlier, is used for production of polyether polyols based on esters of alcohols with diallylmalonate, such as dimethylcarbonate, dellcorporate, such as diphenylcarbonate, or phosgene.

Preferably acceptable are polycarbonatediol.

As polyols are also acceptable having at least two hydroxy-group block copolymers containing at least two different block structure of polyethers, polyesters and/or polycarbonates described earlier type.

- Polyacrylate and polymethacrylamide.

- Polyhydroxybutyrate fats and oils, for example natural fats and oils, in particular castor oil, or obtained by chemical modification of natural fats and oils, the so - called oleochemical - polyols, for example, epoxypolyester based on complex or simple the air is s, derived from carboxylic acids or alcohols by epoxydecane unsaturated oils and subsequent disclosure of the cycle, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils, or polyols obtained from the products of cleavage or their derivatives, derived from natural fats and oils, cleavage, such as alcoholysis or ozonolysis and subsequent chemical binding, for example, by transesterification or dimerization. Acceptable products of the cleavage of natural fats and oils are, in particular, fatty acids and fatty alcohols, and fatty acid esters, in particular methyl esters (FAME), of which, for example, hydroformylation and hydrogenation can be obtained derivatives of esters of fatty hydroxyacids.

- Polyesterpolyol, also called oligoclonality, such as, for example, polyhydroxybutyrate polyolefins, polyisobutylene, polyisoprene; polyhydroxybutyrate ethylene-propylene-, ethylene-butylene or ethylene-propylene-diene copolymers, such as, for example, produced by the company Kraton Polymers; polyhydroxybutyrate polymers of dienes, in particular 1,3-butadiene, which can be obtained, in particular, also anionic polymerization; polyhydroxybutyrate the copolymers of dienes such as 1,3-butadiene or a mixture of dienes, and VI is silt monomers, such as styrene, Acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example, polyhydroxybutyrate Acrylonitrile/butadiene copolymers, which can be obtained, for example, Acrylonitrile/butadiene copolymers with integral carboxyglutamic (sold by the company a Noveon under the name Hycar®CTBN) and epoxides or aminoalcohols; and hydrogenated polyhydroxybutyrate polymers or copolymers of dienes.

The above-mentioned polyols preferably have an average molecular weight of 250-30, 000 g/mol, in particular 400-20 000 g/mol, and preferably have an average OH functionality in the range from 1.6 to 3.

Upon receipt of the polyurethane polymerPUPin addition to the aforementioned polyols can be shared in small quantities of low molecular weight two - or polyhydric alcohols, such as, for example, 1,2-ethanediol, 1,2 - and 1,3 - propandiol, neopentylglycol, diethylene glycol, triethylene glycol, the isomeric dipropyleneglycol and dipropyleneglycol, isomeric butandiol, pentandiol, hexandiol, heptanediol, octanediol, nonanediol, decanediol, undemandingly, 1,3 - and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, such as, for example, dimeric fatty dihydroxyindole, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, glycerin, pentaerythritol, low) - Rev. molecular products alkoxysilane mentioned two - or polyhydric alcohols, and also mixtures of the aforementioned alcohols.

As polyisocyanates to obtain a polyurethane polymerPUPcan be used aliphatic, cycloaliphatic or aromatic polyisocyanates, in particular diisocyanates, for example Monomeric diisocyanates mentioned earlier as a suitable polyisocyanatesPIand also oligomers and polymers such Monomeric diisocyanate and any mixtures of such isocyanates. Preferred are Monomeric diisocyanates, in particular MDI, TDI, HDI and IPDI.

Obtaining polyurethane polymerPUPcarried out in a known manner directly from polyisocyanates and polyols or phased method of the formation of adducts, also known as the reactions of chain elongation.

In a preferred embodiment, the polyurethane polymerPUPobtained by reaction of at least one MDI and at least one polyol and isocyanate groups relative to the hydroxy groups are in excess compared with the stoichiometric quantity. The ratio between isocyanate groups and hydroxyl groups is preferably in the range from 1.3 to 10, in particular in the range from 1.5 to 5.

The interaction is preferably carried out at a temperature at which the applied polyols, polyisocyanates and the resulting p is lauretanae polymers are in the liquid state.

Polyurethane polymerPUPhas a molecular weight of preferably more than 500 g/mol, in particular between 1 000 and 30 000 g/mol.

When this polyurethane polymerPUPpreferably have an average NCO functionality in the range from 1.8 to 3.

As MDIPacceptable are also mixtures containing polyurethane polymerPUPand the polyisocyanatePIin particular, on the one hand, a mixture containing polyurethane polymerPUPbased on MDI and Monomeric and/or polymeric MDI, and, on the other hand, mixtures containing polyurethane polymerPUPbased on IPDI and Monomeric and/or oligomeric IPDI.

ComponentK2preferred curing the two packages of the composition contains at least one aldimine formula (I'). In this case, reasonable are previously described aldimine formula (I') and accordingly preferred for this purpose, options, described previously, in particular aldimine formula (I a) and aldimine formula (I b).

More preferred are aldimine formula (I')in which R4'and R5'jointly contain two hydroxy-group.

If necessary, theK2contains other compounds, which are reactive in relation to isocyanate groups, such as polyamine, polyols, aminoalcohols, politely or the other is their blocked amines.

As the polyamine componentK2acceptable are the primary aliphatic polyamine, such as those described previously as aminesB2formula (III b); secondary aliphatic polyamine, such as, for example, N,N'-dibutylethanolamine; N,N'-di-tert-butylethylenediamine, N,N'-diethyl-1,6-hexanediamine, 1-(1-methylethylamine)-3-(1-methylaminomethyl)-3,5,5-trimethylcyclohexane (Jefflink®754 Huntsman), N-4-cyclohexyl-2-methyl-N-2-(2-methylpropyl)-2,4-pentanediamine, N,N'-dialkyl-1,3-xylylenediamine, bis-(4-(N-alkylamino)cyclohexyl)methane, N-alkylated the polyetheramines, for example, Jeffamine type®SD-231, SD-401 SD-404 SD-2001 (all supplied by Huntsman), products are obtained analogously to the reaction of the Michael reaction of joining mentioned as examples of the primary aliphatic polyamines with Michael acceptors such as fluids maleic acid fluids fumaric acid fluids tarakanovas acid, ester of acrylic acid, methacrylic acid, ester of cinnamic acid fluids basis of itaconic acid fluids vinylphosphonic acid, arrowy ether vinylsulfonic acid, vinylsulfonic, wininit.ini, 1-nitroethylene, or condensation products of knoevenagel, such as, for example, products, retrieved from diesters of malonic acid and aldehydes, such as formaldehyde, acetaldehyde or benzaldehyde; aliphatic who Alumini with primary and secondary amino groups, such as, for example, N-butyl-1,6-hexanediamine; primary and/or secondary aromatic polyamine, such as, for example, m - and p-phenylenediamine, 4,4'-diaminodiphenylmethane (MDA), 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), mixtures of 3,5-dimethyldi-2,4 - and 3,5-dimethyldi-2,6-toluylenediamine (implemented as Ethacure®300 company Albemarle), mixtures of 3,5-diethyl-2,4 - and 3,5-diethyl-2,6-toluenediamine (DETDA), 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA), 3,3',5,5'-tetraethyl-2,2'-dichloro-4,4'-diaminodiphenylmethane (M-CDEA), 3,3'-aminobutiramida 5,5'-dimethyl-4,4'-diaminodiphenylmethane (M-MIPA.), 3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane (M-DIPA), 4,4'-diaminodiphenylsulfone (DDS), 4-amino-N-(4-AMINOPHENYL)benzosulfimide, 5,5'-etilendiaminova acid, dimethyl-(5,5'-methylenedinitramine), 1,3-propylene-bis-(4-aminobenzoate), 1,4-butylene-bis-(4-aminobenzoate), polytetramethylene-bis-(4-aminobenzoate) (implemented as Versalink®company Air Products), 1,2-bis-(2-aminophenylthio)ethane, N,N'-dialkyl-p-phenylenediamine, N,N'-dialkyl-4,4'-diaminodiphenylmethane, 2-methylpropyl-(4-chloro-3,5-diaminobenzoate) and tert-butyl(4-chloro-3,5-diaminobenzoate); and polyamine having more than three amino groups.

As polyols in componentK2acceptable are the polyols mentioned earlier as acceptable to obtain a polyurethane polymerPUPand low molecular weight two - or polyhydric alcohols mentioned is anee as acceptable for joint use in preparation of a polyurethane polymer PUP.

As aminoalcohols in the componentK2acceptable are also compounds having at least one primary or secondary amino group and at least one hydroxy-group, such as, for example, aliphatic hydroxyamine mentioned earlier as an acceptable aminesB1to obtain aldimines formula (I), and, for example, diethanolamine, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 2-(butylamino)ethanol and 2-(cyclohexylamino)ethanol.

As policylaw componentK2acceptable are, for example, known under the trade name Thiokol®liquid mercaptoacetate polymers, such as LP-3, LP-33 LP-980, LP-23 LP-55 LP-56 LP-12, LP-31, LP-32 LP-2 (Morton Thiokol; comes, for example, SPI Supplies, USA, or by the company Toray Fine Chemicals, Japan), and polyesters thiocarbonic acids, for example, pentaerythritoltetranitrate, trimethylpentanediol, glycolipoprotein, pentaerythrityl-(3-mercaptopropionate), trimethylolpropane(3-mercaptopropionate), glycolide(3-mercaptopropionate).

Along with aldimine formula (I') as an ingredient componentK2can be used other blocked amines, in particular catimini, oxazolidines, enamines, and other aldimine. Other aldimine get from aldehydes, which differs from the previously KJV is anutech aldehydes ALD1formula (IV'), such as, for example, aldehydesALDformula (IV), with only one hydroxy-group, for example, Isobutyraldehyde, as well as of the products of esterification of carboxylic acids, such as described in WO 2004/013088 A1, in particular, products from the esterification of lauric acid with 3-hydroxybenzaldehyde. Ketimine can be obtained, for example, by the interaction of the previously described aminesBformula (III) with ketones. Acceptable oxazolidine are, in particular, polyoxazolines, such as, for example, the hardener OZ (Bayer). Acceptable enamines can be obtained, for example, the interaction of amines with multiple secondary amino groups with aliphatic or cycloaliphatic aldehydes or ketones containing the C atom in α-position to the carbonyl group at least one hydrogen atom.

In one embodiment, the implementation of theK2contains water. ComponentK2includes water in an amount necessary for the hydrolysis of alvinegro and other blocked amino groups, or part of such amount.

Preferred curing the two packages, the composition optionally contains other ingredients, in particular, traditionally used in polyurethane compositions, excipients and additives, for example, such compounds as:

- plasti who ictory, for example, esters of carboxylic acids, such as phthalates, for example, dioctylphthalate, diisononylphthalate or diisodecylphthalate, adipinate, for example, dioctyladipate, atalanti and Sabatini, organic esters of phosphoric and sulfonic acid or polybutene;

- directionspanel thermoplastic polymers, such as, for example, Homo - or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl(meth)acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylenevinylacetate copolymers (EVA) and atactic poly-α-olefins (APAO);

- solvents;

inorganic and organic fillers, for example, ground or precipitated calcium carbonate, covered if necessary fatty acids, in particular stearates, barite (BaSO4, also called heavy spar), quartz powder, calcined kaolin, aluminum oxide, aluminum hydroxide, silicic acid, in particular highly dispersed silicic acid obtained by pyrolysis, soot, in particular soot produced in an industrial scale (hereafter referred to as "soot"), powder or hollow balls made of PVC;

fiber, for example, polyethylene;

- pigments, for example titanium dioxide or iron oxide;

- catalysts, which accelerate the hydrolysis of aldimines,in particular acid, for example, carboxylic acids such as benzoic acid, salicylic acid or 2-nitrobenzoic acid, anhydrides of carboxylic acids, such as phthalic anhydride, the anhydride hexahydrophthalic acid and anhydride hexahydromethylphthalic acid, Silovye esters of carboxylic acids, sulfonic acids, such as methanesulfonate, p-toluensulfonate or 4-dodecylbenzenesulfonic acid, esters of sulfonic acids, other organic or inorganic acids or mixtures of the aforementioned acids and esters;

- catalysts that accelerate the reaction of isocyanate groups, for example, ORGANOTIN compounds such as dibutylaminoethanol, dibutyltindilaurate, dibutyltindilaurate, dibutyltindilaurate and dioctyladipate, bismuth compounds, such as tristant bismuth Tris(neodecanoate) bismuth, and compounds containing tertiary amino groups, such as 2,2'-disorganizational ether and 1,4-diazabicyclo[2.2.2]octane;

- rheology modifiers such as, for example, the thickener or thixotropic agent, for example, compounds of urea, polyamide waxes, bentonites or pyrogenic silicic acids;

- active diluents and crosslinking agents, for example, Monomeric diisocyanates, and also oligomers and derivatives of these polyisocyanates, adducts of Monomeric, polyisocyanates polyols with a short circuit, and dehydrated adipic acid and other dihydrazide, as well as the aforementioned polyisocyanates with blocked isocyanate groups;

- blocked amines, for example, in the form of ketimines, oxazolidines, enamines or other aldimines;

drier, such as, for example, molecular sieve, calcium oxide, highly reactive isocyanates such as p-totalitarian, ether orthomorphisms acid, alkoxysilane, such as tetraethoxysilane;

- organoalkoxysilanes, hereafter referred to as "silanes", such as, for example, epoxysilane, (meth)acrylicana, isocyanatobenzene, vinylsilane, carbonatation, alkylsilanes, S-(alkylsulphonyl)mercaptoethane and eliminazione, and also oligomeric forms of these silanes;

- stabilizers against heat, light and UV radiation;

- flame-retardant substances;

- surfactants, such as, for example, a wetting agent, a means of facilitating the spreading tool to remove air or non;

- biocides, such as, for example, algaecides, fungicides or growth inhibition of fungi.

When the use of such other ingredients should pay attention to the fact that they would not exert a strong negative influence on the storage stability of each of the components ofK1orK2of the composition. In the presence of such additives in quality is TBE ingredients component K1you need to pay attention to during storage did not cause crosslinking of isocyanate groups to a great extent. In particular, this means that the additives used, therefore, should not contain water or contain only trace quantities. It seems rational to dry some chemical additives or by physical means before the introduction of theK1.

In the case of the componentK2along with the mentioned additives may be used optionally other auxiliary substances and additives, in the presence of free isocyanate groups are not saved or stored only for a short time. In particular, they are catalysts, such as:

compounds of zinc, manganese, iron, chromium, cobalt, copper, Nickel, molybdenum, lead, cadmium, mercury, antimony, vanadium, titanium, zirconium, or potassium, such as zinc acetate (II)2-ethylhexanoate zinc (II)laurate zinc (II), oleate of zinc (II)naphthenate, zinc (II)acetylacetonate, zinc (II), salicylate zinc (II)2-ethylhexanoate manganese (II)2-ethylhexanoate iron (III)acetylacetonate iron (III), 2-ethylhexanoate chromium (III)naphthenate, cobalt (II)2-ethylhexanoate, cobalt (II)2-ethylhexanoate, copper (II)naphthenate, Nickel (II), neodecanoate finalstate, acetate of lead (II)2-ethylhexanoate, lead (II), neodecanoate lead II), acetylacetonate lead (II), aluminum lactate, aluminum oleate, aluminum acetylacetonate (III), bis(ethylacetoacetate) diisopropoxide, bis-(ethylacetoacetate) dilutability, bis-(acetylacetonate) dilutability, potassium acetate, octanoate 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'-dimethylaminomethylphenol, bis-(dimethylaminoethyl)piperazine, 1,3,5-Tris-(dimethylaminopropyl)hexahydrotriazine, bis-(2-dimethylaminoethyl)new simple ether; nitrogen-containing aromatic compounds such as 4-dimethylaminopyridine, N-Mei, N-vinylimidazole or 1.2-dimethylimidazole; amidine and guanidine, such as 1,1,3,3-tetramethylguanidine; tertiary amines containing activiety hydrogen, such as triethanolamine, triisopropanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, 3-(dimethylamino)propertiesproperty, bis-(3-(dimethylamino)propyl)isopropanolamine, bis-(3-dimethylaminopropyl)amine, 3-(dimethylamino)proprotein, phenolic Mannich bases, such as 2,4,6-Tris-(dimethylaminomethyl)phenol or 2,4,6-Tris-(3-(dimethylamino)propylaminoethyl)phenol, imidazoles, such as, for example, N-hydroxypropylamino or N-(3-aminopropyl)imidazole, as alkoxysilane and polyalkoxysiloxanes such compounds, for example, dimethylaminoethoxide; organic ammonium compounds such as the hydroxide designed or alkoxysilane tertiary amines; the so-called catalysts "slow motion", which is a modification of the known metal or aminecontaining catalysts, such as the interaction products of tertiary amines and carboxylic acids or phenols, for example, 1,4-diazabicyclo[2.2.2]octane or DBU and formic or acetic acid; and combinations of the above-mentioned compounds, in particular metal compounds and tertiary amines.

The composition preferably contains at least one catalyst in the form of ORGANOMETALLIC compounds and/or tertiary amine and/or acids, in particular carboxylic or sulfonic acid.

Getting both the comp is required K1andK2carried out separately from each other, while for componentK1excludes the presence of moisture. BothK1andK2separately from each other are stable during storage, i.e. before use they can be stored in appropriate packaging or device, such as, for example, barrels, bags, buckets, cartridges or bottles, within a few months to a year or more without changing their respective properties to the extent essential for their application.

When applying the two packages compositions bothK1andK2mix with each other. It is necessary to draw attention to the fact that the ratio of the components are chosen so that the ingredients, which are reactive in relation to isocyanate groups, were in the appropriate ratio with the isocyanate groups of the componentK1. In particular, the ratio is in the range from 0.1 to 1.1, preferably from 0.5 to 0.95, and more preferably from 0.6 to 0.9 total equivalent contained hydroxyl groups, amino groups, mercaptopropyl and protected amino groups per equivalent of isocyanate groups, protected amino groups in the form oxazolidinone groups are taken into account in double quantity. During curing of excess isocyanate groups react with moisture, in particular with air moisture.

Mixing both to the of mponents K1andK2implement appropriate way, for example, in a static mixer. Mixing can be carried out in continuous or batch mode. Then the mixed composition is applied to the substrate, if necessary by reasonable means for applying. This should draw attention to the fact that between the mixing components and the application was not too much time, because excessively high degree of primary response of the ingredients of the mixed composition before application may be degraded function utverzhdenii composition, for example, due to the fact' that the adhesion to the substrate is achieved unsatisfactory or slow. The maximum period of time during which the mixed composition should be applied, called the "viability".

After mixingK1andK2starts curing. Antiminority begin to react with isocyanate groups previously described way, as soon as they come into contact with water. The water in the mixed composition or already have - due to the fact' that she was the ingredient componentK2or due to the fact' that it was added to the composition before mixing or during mixing of both componentsK1andK2or diffuses into the mixed composition in the form in which AGI air. In the latter case, the reaction alvinegro with isocyanate groups takes place in the inward parallel with the penetration of moisture from the air into the composition. As described previously, the reaction of the isocyanate groups with gidrolizuemye eliminarpremio does not have to occur only at the expense of free amino groups, but can also occur through intermediate stages of hydrolysis. Similarly released reactive group other blocked amines contained if necessary in the composition. After mixingK1andK2with isocyanate groups react well hydroxy-, mercapto - and amino groups present in the composition. Hydroxy-group of the radicals R4'and R5'can react with isocyanate groups before, during or after the formal release of the aldehydeALD1. As a result of these reactions mixed composition crosslinks and eventually cures to a solid state material.

Curing described curable composition is in the General case, without the formation of gas bubbles even at high speed curing. On the curing rate can be influenced by the type and quantity of one or more available if necessary catalysts, the temperature at which curing occurs, as well as humidity or to the number of added water.

Described curable compositions have a number of advantages.

Aldimine formula (I') contain sterically complicated working antiminority that cannot turn through tautomerizations in inlinegroup. Such aldimine react in the presence of water with isocyanate groups formally as primary amino groups, and their reactivity compared to the free primary amino groups is substantially less, so that such systems possess good technologically acceptable speed curing.

The presence of aldimines makes a straight line, causing the formation of carbon dioxide (CO2) the reaction of isocyanate groups with moisture that is already in the composition or enters into the composition after its application, and thus largely suppresses the undesirable formation of gas bubbles during curing of the composition.

Thus aldehydesALD1formula (IV'), released from aldimines formula (I') during curing, with his hand acting as a hardener, since the radicals R4'and R5'together contain at least two hydroxy-group and therefore react with isocyanate groups with a chain elongation or crosslinking of the resulting polyurethane polymer and do not lead to breakage of the chains. As a consequence covalent the second embedding aldehydes ALD1the polymer is a particular advantage, as it prevents problems that can lead to utverzhdenii non linkable composition aldehydes, such as, in particular, shrinkage, unpleasant odors, wypadanie or decrease in mechanical strength and durability.

In addition, aldimine formula (I') due to their content of tertiary amino groups can have a catalytic effect on the reaction of isocyanate groups and thus to accelerate the curing. This accelerating effect is additionally due to the fact that the tertiary amino groups are localized in the aldehyde part of aldimines, i.e. released after hydrolysis of the aldehydesALD1. The advantage is that the basicity of the data of the tertiary amino groups is relatively low, as strongly alkaline tertiary amines interfere with the acid-catalyzed hydrolysis of alvinegro and/or can extremely speed up the direct reaction of the isocyanate groups, in particular with water, the result may be incomplete curing. Tertiary amino groups are localized in the aldehyde part of aldimines formula (I') and during curing by the reaction of hydroxyl groups with isocyanate groups covalently incorporated in the resulting polymer. After embedding in polymer catalytic activity of the tertiary amine groups as a result of what their their limited mobility is greatly reduced, that may provide an advantage in relation to the durability of the material.

Aldehyde groups formed during the hydrolysis of alvinegro, during curing and remain due to the reactions that covalently incorporated in the resulting polymer. If necessary, they can be used for subsequent reactions.

Another advantage of the described compositions is relatively low odor described by aldimines formula (I') and aldehydesALD1. Because of this composition before, during, and after curing, do not smell or have only a faint odor.

The preferred application of the described curable compositions are used as adhesives, sealants, casting masses, coatings, floor coverings, coatings, varnishes, coatings and foams. The following briefly describes the individual applications, which, however, does not restrict other use of these compositions.

In the preferred embodiment described curable composition used as an adhesive or sealant. In the case of this application of the curable composition preferably contains at least one filler, and the filler effect on the rheological properties of the uncured composition and the mechanical and surface properties utverzhdenii to the notizie. Acceptable excipients are previously mentioned inorganic and organic fillers. The preferred fillers are carbon black, calcium carbonate, calcined kaolin, highly dispersed silicic acid, powder PVC and flame-retardant fillers such as hydrates or hydroxides, in particular aluminum hydroxide. The content of the filler is, in particular, in the range from 10 to 70 wt.%. and preferably from 20 to 60% wt. in terms of the whole composition. Preferred may be the use of mixtures of different fillers.

When applied as an adhesive or sealant curable composition preferably contains at least one of the previously mentioned catalysts, accelerating the hydrolysis of alvinegro or the reaction of the isocyanate groups. Preferably acceptable is a mixture of organic acids and ORGANOMETALLIC compound or complex of a metal, organic acids and compounds containing tertiary amino groups, or a mixture of organic acids, ORGANOMETALLIC compound or complex of the metal and compounds containing tertiary amino groups. Typical content of the catalysts is 0.005 to 2 wt.%. in terms of the whole composition, and specialists in the art known to the applied quantity of the corresponding catalysts, is the mark of a rational.

The adhesive or sealant and get put in the way described earlier.

Acceptable use of the adhesive is, for example, gluing in a high-rise building or construction of underground facilities and for finishing or repair of the goods of industrial or domestic purposes, in particular Windows, appliances or vehicles, such as water or land vehicles, preferably automobiles, buses, trucks, trains, or ships, as well as bonding in the manufacture of furniture, textile or packaging; or sealing of joints, seams or cavities in finishing or repair industrial or high-rise building or construction of underground structures.

Acceptable sealant application is, for example, sealing of buildings, in particular sealing joints in building construction or construction of underground facilities, or sealing of the building, for example, Windows or floor, or the industrial sealing products, such as, for example, household machine or vehicle, in particular a water or land vehicle, or parts thereof.

The adhesive or sealant in dry condition has a generally elastic properties.

In another preferred embodiment, described curable composition used is as a coating. In the case of this application of the curable composition preferably contains at least one filler, and the filler effect on the rheological properties of the uncured composition and the mechanical and surface properties utverzhdenii composition. Acceptable excipients are previously mentioned inorganic and organic fillers. Preferred fillers are calcium carbonate, barite and quartz flour, and flame-retardant fillers such as hydrates or hydroxides, in particular aluminum hydroxide. The content of the filler is, in particular, in the range from 10 to 70 wt.%. and preferably from 20 to 60% wt. in terms of the whole composition. Preferred may be the use of mixtures of different fillers.

When applied as a coating curable composition preferably also contains at least one catalyst. If this is acceptable are the same catalysts and their number, respectively, mentioned earlier in relation to acceptable ingredients of adhesives and sealants.

When applied as a coating curable composition preferably also contains at least one of the previously mentioned auxiliary substances and additives, in particular selected from the group comprising pigments, solvents,tools, contributing to the spreading, antispyware and stabilizers.

Acceptable solvents are, for example, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyrate and mesityloxide, as well as cyclic ketones such as cyclohexanone and methylcyclohexanone; esters such as methyl acetate, ethyl acetate, propyl, butyl acetate, tert-butyl acetate, formate, propionate or malonate; ethers, such as ketoesters, mixed ethers and dialkylamide ethers, such as diisopropyl ether, diethyl ether, disutility ether, methyl tert-butyl ether, dietilenglikoluretan ether, and etilenglikolevye ether; aliphatic and aromatic hydrocarbons, such as toluene, xylene, heptane, octane, and petroleum fractions such as naphtha, white spirit, petroleum ether or benzene; halogenated hydrocarbons such as methylene chloride; and N-alkylated lactams, such as N-organic N-cyclohexylpiperidine or N-dodecylmercaptan. The solvent content is, in particular, in the interval from 0 to 30 wt.%, preferably from 0 to 20 wt.%. in terms of the whole composition.

Floor and get put in the way described earlier. The coating preferably has a liquid consistency with good flow characteristics. This makes it n what to wear just as a self-leveling coating on a mostly flat surface, for example, as a floor covering. Before applying bothK1andK2acceptable way mixed together and the mixed composition is applied within the pot life.

Applying the curable composition in the form of a coating is carried out, as a rule, the loading on the coated substrate and liquid evenly distribute through, for example, squeegee or notched trowel. Additional material can be aligned with needle roller and remove it from the air. However, it is also possible mechanized application, such as application of the spray.

Acceptable substrate, which, as a rule, put the composition is, for example, concrete, cement, asphalt, steel, wood, ceramic or plastic, and the substrate can be pre-treated, krasivuyu or sandblasted and/or primed. As a primer can be used, for example, solutions of the adhesion promoter or primer.

By "primer" in this description to understand acceptable as a primary coating composition, which, along with the inert volatile substances and optional solid filler contains at least one polymer and/or at least one substance with reactive groups and capable when applied to the substrate summer evati in the form of a solid, well adherent film with a thickness of typically less than 5 μm, and curing is effected by evaporation of the inert volatile substances, such as, for example, a solvent or water, or by chemical reaction, or by a combination of these factors, and has good adhesion to subsequently applied layer, for example, adhesive or sealant.

In the case of the clean flooring it often refers to a structure composed of several distinct layers. A typical structure may begin, for example, with the so-called primers, the purpose of which is to prepare the substrate for applying a polyurethane coating. Then applied, for example, describes a composition which in the cured state, as a rule, has elastic properties, and application depending on the properties of the substrate and layer thickness can be carried out in one or several stages. At one time applied, as a rule, the layer thickness of from 0.5 to 3 mm and preferably from 0.5 to 2 mm In the last turn can be applied to so-called external finishing layer which is a thin layer, for example, with a thickness from several micrometers up to several tenths of a millimeter and finally determines the surface properties of the floor covering. It can be transparent or p is generowania external finishing layer.

Described coating may preferably be used in interior or exterior areas of a building or structure, for example, as a floor covering for indoor application, such as office and industrial areas, sports halls or the refrigerating chamber, or in the outside areas for balconies, terraces, bridges, Parking areas or sports and playgrounds.

In one of the other aspects, the invention relates to a method for bonding substratesS1backingS2that includes the following stages:

i) applying the previously described curable composition on a substrateS1;

ii) contacting the applied composition with a substrateS2during the time before the bonding composition;

or

i') applying the previously described curable composition on a substrateS1and substrateS2;

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

moreover, the substrate isS2consists of material similar to or different from the substrate materialS1.

In one of the other aspects, the invention relates to a method of sealing. In this method includes a stage:

i) applying the previously described curable composition between the substrateS1and substrateS2so that the composition is odiles in contact with the substrate S1and substrateS2;

moreover, the substrate isS2consists of material similar to or different from the substrate materialS1.

Typically, the sealant is pressed into the so-called junction.

In one of the other aspects, the invention relates to a method for coating a substrateS1. In this method includes a stage:

i') applying the previously described curable composition on a substrateS1during the time before the bonding composition.

In these three methods are acceptable substratesS1and/orS2are, for example, inorganic substrates such as glass, glass ceramic, concrete, mortar, brick, tile, plaster, and natural stones such as granite or marble; metals or alloys such as aluminum, steel, nonferrous metals, galvanized metals; organic substrates such as leather, cloth, paper, wood, wood materials associated with resin composite material of resin and fabrics, plastics, such as polyvinyl chloride (hard and soft PVC)resin plant copolymers (ABS), SMC (sheet molded composite materials), polycarbonates (PC), polyamide (PA), polyesters, PMMA, polyesters, epoxy resins, polyurethanes (PUR), Polyoxymethylene (POM), polyolefins (PO), in particular, processed on the surface of the plasma cor is authorized discharge or flame polyethylene (PE) or polypropylene (PP), ethylene/propylene copolymers (EPM) and ethylene/propylenediene terpolymer (EPDM); coated substrates such as substrates, powder coated metals or alloys; and also paints and varnishes, in particular automotive lacquers.

If necessary, the substrate before application of the composition can be pre-processed. This type of pre-processing includes, in particular, treatment of physical and/or chemical methods, for example, by sanding, sandblasting, brazevanje or the like, or treatment with cleaners or solvents, or the application of the adhesion promoter, the solution of the adhesion promoter or primer.

In the case of the two packages compositions bothK1andK2mixed together shortly before application.

In the case of the composition of hot-curing the applied composition for bonding, sealing or formation of the coating is subjected to a hot drying by heating to the appropriate temperature.

The curable coating compositions can be carried out in a wide temperature range. For example, the composition may be applied at room temperature, which is typical for the adhesive or sealant. The composition may also be applied at lower or higher temperatures. The latter is especially preferred when the composition with the holding of a high-viscosity or fusible components, such as contained, as a rule, hot melts, for example, low-melting hot melt adhesives (HMAS (Warm-Melt) or refractory adhesives-melt (Hot-Melt). Temperature during application in the case of fusible adhesives can be, for example, in the range from 40 to 80°C, in the case of refractory adhesives is in the range of from 85 to 200°C.

Methods of bonding, sealing or coating or the application of the described compositions as an adhesive, sealant, casting masses, coatings, floor coverings, paint, varnish, primer or foam - enable to produce the product.

This product represents, in particular, the construction, in particular high-rise or underground structure, or the product of an industrial or domestic purposes, in particular the window, household machine, or vehicle, in particular a water or land vehicle, preferably a car, bus, truck, train or ship, or hinged portion of the vehicle, or furniture, textile or packaging the product.

Examples

1. Description of measurement methods

Viscositymeasured temperature-controlled plate-cone viscometer Physica UM (cone diameter 20 mm, cone angle: 1°, the gap between the cone and plate: 0.05 mm, shear rate: from 10 to 1000-1).

With the holding of the amino groups i.e. the total content of free amino groups and blocked amino groups (alvinegro) in the obtained compounds was determined by titrimetric (0.1 N. the solution of HClO4in glacial acetic acid with crystal violet) and in all cases indicated in mmol N/g

The value pKafor the conjugate acid Mannich bases were determined approximately on the potential of the half-neutralization in potentiometric titration of a solution of approximately 1 mmol Mannich bases in 50 ml of water a solution of 0.1 G. of HCl.

Infrared spectrarecorded on the instrument FT-IR 1600 Perkin-Elmer for undiluted films on a horizontal measuring node ATR crystal of ZnSe; the absorption bands are indicated in wave numbers (cm-1) (measurement bandwidth:4000-650 cm-1); note the "square" indicates a strip in the form of a plateau, note "ush." refers to the broadening of the band.

Analysis ofLC/MScarried out under the following conditions: column Optima-5-MS, 30 m × 0.25 mm, film thickness: 0.5 µm; heating rate: 15°C/min from 60 to 320°C, then the extract for 15 min at 320°C; carrier gas: He, 14-foot per square inch; feed rate: 15 ml/min; ionization method: EI+. For chromatograms indicated the retention time of the compound (tR). In the mass spectra indicated only the largest peaks (m/z); the relative intensity (in %) and, when it was prob the tenderly, the proposed structure of the molecular fragment are shown in parentheses.

2. Obtaining aldehydes

3-(N-bis-(2-hydroxyethyl)amino)-2,2-dimethylpropyl

In a round bottom flask under nitrogen atmosphere were placed by 83.4 g (1.00 mol) of 36%aqueous solution of formaldehyde and to 75.7 g (1.05 mol) of Isobutyraldehyde. Under vigorous stirring and cooling with ice from the dropping funnel was slowly added dropwise 105,1 g (1.00 mol) of diethanolamine, and followed so that the temperature of the reaction mixture did not exceed 20°C. Upon completion of addition, the reaction mixture was stirred for one hour at room temperature. The resulting clear, colorless reaction mixture was stirred on an oil bath at 80°C for 2 hours under reflux, then cooled to room temperature and the volatile components are kept at 80 °C in vacuum, created a water vacuum pump. Received 181,2 g (96% of theoretical) of crude compound as a transparent butter-like substance yellowish containing amino groups 5.40 mmol N/g and a viscosity of 23.7 PA·s at 20°C. the Crude substance contained along with 3-(N-bis-(2-hydroxyethyl)amino)-2,2-DIMETHYLPROPANE a small amount of 3-hydroxy-2,2-DIMETHYLPROPANE, N-(2-hydroxyethyl)oxazolidine and N-(2-hydroxyethyl)-2-isopropylacetanilide (according to the analysis of LC/MS).

pKa≈ 7,1.

IR: 3358 ush. (OH), 2950, 2929 square, 2913, 2870, 2830, 2719 square ush. (CHO), 1721 (C=O), 1464, 1391, 1359, 1302 ush., 1206, 1147, 1078 square, 1037, 966, 940, 920, 883, 786.

LC/MS: tR=10,3 min; mass spectrum: 189 (2, [M]+), 172 (3, [M - OH]+), 158 (11, [M-CH2OH]+), 128 (4), 118 (100, [M-C(CH3)2CHO]+), 116 (15), 102 (6), 98 (5), 88 (2, [118-CHOH]+), 88 (72), 86 (21), 74 (50), 56 (51).

3-(N-bis-(2-hydroxy-2-methylethyl)amino)-2,2-dimethylpropyl

In conditions similar to the conditions described previously for the preparation of 3-(N-bis-(2-hydroxyethyl)amino)-2,2-DIMETHYLPROPANE, of 83.4 g (1.00 mol) of 36%aqueous solution of formaldehyde was brought into interaction with 75,7 g (1.05 mol) of Isobutyraldehyde and 133,2 g (1.00 mol) of diisopropanolamine and processed. Received 199,4 g (92% of theoretical) of crude compound as a transparent butter-like substance yellowish color with a content of amino groups to 4.87 mmol N/g and a viscosity of 8.2 PA·s at 20°C. the Crude substance contained along with 3-(N-bis-(2-hydroxy-2-methylethyl)amino)-2,2-DIMETHYLPROPANE a small amount of 3-hydroxy-2,2-DIMETHYLPROPANE, N-(2-hydroxy-2-methylethyl)oxazolidine and N-(2-hydroxy-2-methylethyl)-2-isopropylacetanilide (according to the analysis of LC/MS).

pKa≈ 7,1.

IR: 3392 ush. (OH), 2966, 2933, 2872, 2818, 2719 square ush. (CHO), 1722 (C=O), 1461, 1409, 1375, 1328, 1274, 1209, 1158, 1130, 1090 square, 1055, 1028 square, 978, 945, 914, 891, 864, 839, 818, 786.

LC/MS: tR=10,3 min; mass spectrum: 217 (3, [M]+), 172 (30 [M-CH(CH 3)OH]+), 146 (44, [M-C(CH3)2CHO]+), 144 (21), 130 (6), 126 (6), 116 (7), 114 (10), 102 (100, [146-C(CH3)OH]+), 100 (18), 88 (16), 70 (38).

3. Getting aldimines

Example 1.AldimineA-1

In a round bottom flask under nitrogen atmosphere were placed with subsequent weighing of 68.2 g of polyetherdiamine (Polyoxypropylenediamine with an average molecular weight of about 240 g/mol; Jeffamine®D-230, Huntsman; the content of amino groups: 8,29 mmol N/g) and of 117.6 g of 3-(N-bis-(2-hydroxyethyl)amino)-2,2-dimethylpropyl and the mixture was stirred for one hour at room temperature. Then in vacuo (10 mbar, 80°C) to remove volatile components. Output: 177,1 g butter-like transparent yellow substance containing amine groups of 6.78 mmol N/g and a viscosity of 9.8 PA·s at 20°C.

IR: 3391 ush. (OH), 2964, 2926, 2868, 1662 (C=N), 1469, 1456 square, 1392 square, 1373, 1294, 1106 square, 1049, 1004 square, 926, 903, 877.

Example 2.AldimineA-2

In conditions similar to the conditions described in example 1 to 27.2 g of ISOPHORONEDIAMINE (Vestamin®IPD, Degussa; the content of amino groups: 11,67 mmol N/g) was brought into interaction from 71.8 g of 3-(N-bis-(2-hydroxy-2-methylethyl)amino)-2,2-DIMETHYLPROPANE. Output: 93,2 g transparent methodologi yellow substance containing amine groups 7,66 mmol N/g and a viscosity of 150 PA·s at 20°C.

IR: 3393 ush. (OH), 2962, 2926, 2898, 2868, 2837, 2818, 1662 (C=N), 1459, 1408, 1373, 1364, 1333, 1273, 1159, 1133, 1116 square, 1058, 1003, 976 square, 945, 909, 891 864 square, 838.

Example 3.AldimineA-3

In conditions similar to the conditions described in example 1 of 37.7 g of polyetherdiamine (Polyoxypropylenediamine with an average molecular weight of about 240 g/mol; Jeffamine®D-230, Huntsman; the content of amino groups: 8,29 mmol N/g) was brought into interaction from 70.6 g of 3-(N-bis-(2-hydroxy-2-methylethyl)amino)-2,2-DIMETHYLPROPANE. Output: 103,4 g butter-like transparent substance yellow-brownish color with a content of amino groups 6.26 mmol N/g and a viscosity of 4.0 PA·s at 20°C.

IR: 3419 ush. (OH), 2965, 2925, 2918, 2868, 2822 square, 1662 (C=N), 1457, 1408 square, 1373, 1331, 1274, 1196 square, 1106, 1089, 1059, 1019, 1002, 977, 944, 910, 865, 838.

Example 4.AldimineA-4

In conditions similar to the conditions described in example 1, 6,55 g 2-(2-aminoethoxy)ethanol (DGA; Diglycolamine®Agent, Huntsman; the content of amino groups: 9,39 mmol N/g) was brought into interaction from 13.36 g of 3-(N-bis-(2-hydroxyethyl)amino)-2,2-DIMETHYLPROPANE. Output: 16,25 g butter-like transparent substance is yellow with a content of amino groups to 7.18 mmol N/g and a viscosity of 3.4 PA·s at 20°C.

IR: 3358 ush. (OH), 2928, 2865, 2716 square, 1943 ush., 1663 (C=N), 1467, 1459, 1391, 1358, 1285, 1238, 1123, 1044, 1003 square, 940 square, 924 square, 890, 815, 785, 770.

Comparative example 5.AldimineA-5

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 heated droplets is Oh funnel was slowly added 30.0 g (0.25 mol N) polyetherdiamine (Polyoxypropylenediamine with an average molecular weight of about 240 g/mol; Jeffamine®D-230, Huntsman; the content of amino groups: 8,29 mmol N/g)and the reaction mixture was heated and gradually mutela. Then in vacuo (10 mbar, 80°C) to remove volatile components. Output: 99,5 g butter-like transparent substance slightly yellow in color with a content of amino groups of 2.50 mmol N/g

4. Getting curable compositions

Examples 6-9 and comparative examples 10 and 11. Both supplied in two packages casting masses

In each example in polypropylene cups with screw-on lid weighed the relevant ingredients of the componentK2in mass fractions shown in table 1, without pre-drying and stirred by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.; for 2 min at 3000 rpm) until a homogeneous krivodanova state. Then as a component ofK1added PMDI in mass fractions shown in table 1, and mixed for 30 s at 3000 rpm). The ratio between the isocyanate groups of the componentK1and the amount of the reactive groups of (hydroxy - and alvinegro) componentK2in all cases was 1.1.

Table 1
The compositions of both supplied in two packages filling mass
Example6 78910 (EUR.)11 (EUR.)
ComponentK1:
PMDIa35,035,434,438,028,929,7
ComponentK2:
Castor oilb22,522,522,522,522,522,5
Dimeric fatty dihydroxyindolewithof 17.5of 17.5of 17.5of 17.5of 17.522,5
Triold4,754,754,754,754,754,75
AldimineA-1, 5,0A-2, 5,0A-3,5,0A-4, 5,0A-5, 5,0-
The acid catalyste0,250,250,250,250,250,25
Chalkf50,050,050,050,050,050,0
aDesmodur®VKS 20 F, Bayer; the content of NCO groups=30,0% wtbcarboxyl number=165 mg KOH/gcSovermol®908, Cognis; carboxyl number=200 mg KOH/gdDesmophen®4011 T, Bayer; carboxyl number=550 mg KOH/geSalicylic acid (5% wt. in dioctyladipate).fOmyacarb®5-GU, Omya.

P is obtained thus casting masses were tested in terms of speed curing, mechanical properties and formation of bubbles.

For characterizing the speed of curing, first, defined thethe curing time to tack-free(tack-free time). To this end a small part of the composition immediately after mixing was applied with a layer thickness of approximately 2 mm to cardboard and in normal conditions (23±1°C, relative humidity 50±5%) was determined by time, held up to the moment in which, after a slight touch of the surface composition of the pipette of LDPE on the pipette was no sticky residue. Secondly, monitored the progress of the curing by periodic measurement ofshore hardness Daccording to DIN 53505.

To determine the mechanical properties of the casting mass was poured in the form of a film with a thickness of approximately 2 mm in a flat shape PTFE, gave the film to cure for 7 days in normal conditions according to DIN EN 53504 definedthe limit tensile stress,elongation at breakandthe modulus of elasticity(0,5-3,0%relative elongation and rate of elongation of 10 mm/min).

Bubblesassessed qualitatively by the number of bubbles that occurred during the curing of the film with a layer thickness of 2 mm under normal conditions.

The results of these tests are shown in table 2.

table 2
Properties of both supplied in two packages filling mass
Example678910 (EUR.)11 (EUR.)
Time to tack-free (min)a211918425848
Hardness shore D after 1 day817883786060
The shore hardness D in 3 days939389877375
Hardness shore D after 7 days939493938482
Hardness shore D after heat treatmentb 939693948685
Ultimate tensile strength (MPa)23,426,725,513,711,08,1
Elongation at break (%)635237560
The modulus of elasticity (MPa)58078061529085100
Bubblesnononononoa lot
aThe curing time to tack-free (tack-free time).bFor 4 h at 105°C for the test sample, cured for 7 days in normal the conditions.

Examples 12-14. Semi-structured both supplied in two packages adhesives

In each example in polypropylene cups with screw-on lid weighed the relevant ingredients of the componentK2in mass fractions shown in table 3, without pre-drying and stirred by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.; for 2 min at 3000 rpm) until a homogeneous krivodanova state. Then as a component ofK1added PMDI in mass fractions shown in table 3, and were mixed for 30 s at 3000 rpm). The ratio between the isocyanate groups of the componentK1and the amount of the reactive groups of (hydroxy - and alvinegro) componentK2in all cases was 1.1.

Table 3
The semi-structured compositions of both supplied in two packages adhesives
Example121314
ComponentK1:
PMDIa24,528,019,0
ComponentK2:
Castor oilb22,422,422,4
PPG 1000c22,422,422,4
Triold2,252,252,25
AldimineA-1, 5,0A-2, 5,0A-3, 5,0
The acid catalyste0,250,250,25
Chalkf505050
aDesmodur®VKS 20 F, Bayer; the content of NCO groups=30,0% wtbCarboxyl number=165 mg KOH/gcDesmophen®1112 BD, Bayer; carboxyl number=112 mg KOH/gdDesmophen®4011 T, Bayer; carboxyl number=550 mg KOH/geSalicylic acid (5% wt. in dioctyladipate). Omyacarb®5-GU, Omya.

The resulting adhesives were tested in terms of speed curing, mechanical properties and formation of bubbles, respectively, described in example 6. The results are given in table 4.

Table 4
Properties of semi-structured both supplied in two packages adhesives
Example121314
Time to tack-free (min)a283842
Hardness shore D after 1 day657362
The shore hardness D in 3 days778174
Hardness shore D after 7 days828682
Hardness shore D after heat treatmentb848786
Ultimate tensile strength (MPa)10,913,110,2
Elongation at break (%)422543
The modulus of elasticity (MPa)109186100
Bubblesnonono
aThe curing time to tack-free (tack-free time) in minutes.bFor 4 h at 105°C for the test sample, cured for 7 days under normal conditions.

Examples 15 and 16. Elastic both supplied in two packages cover(for example, floor covering)

In each example in polypropylene beaker weighed the relevant ingredients of the componentK1in mass fractions shown in table 5, without pre-drying and stirred by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.; after 30 seconds at 2500 rpm). Then as a component ofK2added aldimine in mass fractions shown in table 4, and stirred for 30 s at 2500 rpm). With the ratio between the isocyanate groups of the component K1and the amount of the reactive groups of (hydroxy - and alvinegro) componentK2in all cases was 1.1.

Polyurethane polymer 1 was obtained in the following way.

1060 g polyoxypropylene (Desmophen®1111 BD, Bayer; carboxyl number=byr111.4 mg KOH/g), 650 g of polyoxypropylene (Desmophen®2061 BD, Bayer; carboxyl number=56,1 mg KOH/g), 770 g of isophoronediisocyanate (Vestanat®IPDI, Degussa) and 0.25 g of dibutyltindilaurate brought into interaction at 80°C with NCO-end polyurethane polymer with a content of free isocyanate groups of 6.8 wt.%.

Table 5
The composition of both supplied in two packages coatings
Example1516
ComponentK1:
Polyurethane polymer164,064,0
The IPDI trimera32,032,0
The acid catalystb1,01,5
Amine rolled the ATOR c0,50,5
Tin catalystd1,01,0
The none1,51,5
ComponentK2:
AldimineA-2, 13,6A-3, 15,3
a45% wt. the IPDI trimer (Vestanat®T 1890/100, Degussa; the content of NCO groups=17,3% wt.) in xylene.b5% wt. salicylic acid dioctyladipate.c2,2'-Disorganizational ether (DABCO®DMDEE Catalyst, Air Products).d10% wt. dibutyltindilaurate in diisodecylphthalate.eBYK-088 (BYK-Chemie/ALTANA).

Thus obtained coatings were tested in relation to the curing time to tack-free, mechanical properties after curing and formation of bubbles, respectively, described in example 6. Additionally out of line gave a qualitative assessmenteducation smellat a distance of 10 cm from utverzhdenii film.

The results of these tests are shown in table 6.

Table 6
Properties of both supplied in two packages coatings
Example1516
Time to tack-free (min)a110185
Hardness shore D after 28 days6550
Ultimate tensile strength (MPa)9,38,3
Elongation at break (%)190310
The modulus of elasticity (MPa)b11546
Bubblesnono
Education smellnono
aThe curing time to tack-free (tack-free time) in minutes.
bAt 0.5 to 5.0%relative elongation.

1. Aldimine formula (I):

where not contain active hydrogen and primary s is nogroup or together with R 7means (n+2)-valent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least one heteroatom in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino groups, n = 1 or 2, or 3, or 4;
m = 0 or 1, or 2, or 3, or 4;
R1and R2each means a monovalent hydrocarbon residue with 1 to 12 atoms
or together denote divalent hydrocarbon radical, which is part of a carbocyclic ring with 5 to 8 and preferably 6 atoms;
R3means a hydrogen atom or alkyl group;
R4and R5independently from each other, respectively, mean
methyl or a monovalent aliphatic radical containing from 2 to 12 C atoms and optionally hydroxy-group;
X is O or S or N-R6or N-R7,
where R6means monovalent hydrocarbon radical containing from 1 to 20 atoms, and
R7together with a means (n+2)-valent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least one heteroatom, in particular in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group.

2. Aldimine according to claim 1, wherein R1and R2each individually denotes methyl.

3. Aldimine according to claim 1 or 2, wherein R4and R5each individual p the STI represents 2-hydroxyethyl or 2-hydroxypropyl.

4. The method of obtaining aldimine according to any one of claims 1 to 3, characterized in that at least one amine of formula (III) is subjected to interaction with at least one sterically impeded, aliphatic, having at least one hydroxy-group of the aldehyde ALD of formula (IV):

where not contain active hydrogen and a primary amino group or, together with R2means (n+2)-valent hydrocarbon radical containing from 3 to 20 C atoms and optionally at least one heteroatom in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino groups,
n = 1 or 2, or 3, or 4;
m = 0 or 1, or 2, or 3, or 4; and
R1and R2each means a monovalent hydrocarbon residue with 1 to 12 atoms or together denote divalent hydrocarbon radical, which is part of a carbocyclic ring with 5 to 8 and preferably 6 atoms;
R3means a hydrogen atom or alkyl group;
R4and R5independently from each other, respectively, denote methyl or a monovalent aliphatic radical containing from 2 to 12 C atoms and optionally hydroxy-group;
Xameans O or S or N-R6aor N-R7,
where R6ameans monovalent hydrocarbon radical containing from 1 to 20 atoms, and
R7together with And Osnach is o (n+2)-valent hydrocarbon radical, containing from 3 to 20 C atoms and optionally at least one heteroatom, in particular in the form of a simple oxygen of the ether group or the nitrogen of the tertiary amino group.

5. The method according to claim 4, characterized in that the aldehyde Y1 of the formula (V), aldehyde Y2 of the formula (VI) and secondary aliphatic having at least one hydroxy-group amine With formula (VII) when the removal of water is transformed into the aldehyde ALD of formula (IV)

where R1-R5have the meanings as in paragraph 4.

6. The method according to claim 5, characterized in that having at least one hydroxy-group amine With formula (VII) represents a secondary aliphatic amine which contains at least two hydroxy-group and is preferably selected from the group consisting of diethanolamine, dipropylamine, diisopropanolamine, 3-(2-hydroxyethylamino)-1-propanol and 3-(2-hydroxypropylamino)-1-propanol, N-methyl-2,3-dihydroxypropyl, 3,4-dihydroxypyrrolidine 2,5-bis-(hydroxymethyl)pyrrolidine, 2,6-bis-(hydroxymethyl)piperidine, 3,4 - or 3,5-dihydroxypyridine, 2-(2,3-dihydroxypropyl)pyrrolidine and 2-(2,3-dihydroxypropyl)of piperidine, and the products of interaction of ammonia with two molecules of compounds, each of which contains apachegroup, in particular the group pilgramage ether.

7. Application aldimine formula (I) according to any one of claims 1 to 3 in Kacha is TBE ingredient compositions derived from isocyanates or epoxy resin, in particular, for adhesives.

8. Curable composition containing at least one polyisocyanate and at least one aldimine formula (I) according to any one of claims 1 to 3.

9. Curable composition according to claim 8, characterized in that it is tropicoco composition and contains at least one polyisocyanate, isocyanate groups of which are blocked isocyanate group.

10. Curable composition according to claim 8, characterized in that it is supplied in two packages composition consisting of component component K1 and K2, and the component K1 contains at least one polyisocyanate P.

11. Curable composition of claim 10, wherein the polyisocyanate P is a polyisocyanate P1 in the form of a Monomeric di - or triisocyanate or oligomer of Monomeric diisocyanate or a derivative of a Monomeric diisocyanate, in particular 1,6-hexamethylenediisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (=isophorondiisocyanate or IPDI), 2,4 - and 2,6-toluylene diisocyanate and any mixtures of these isomers (TDI)or 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any mixtures of these isomers (MDI).

12. Curable composition of claim 10, wherein the polyisocyanate P is a polyurethane polymer clay the PUP, having isocyanate groups and obtained, in particular, the interaction of at least one polyol, at least one polyisocyanate, in particular Monomeric diisocyanate.

13. Curable composition according to any one of p-12, characterized in that the component K2 contains water.

14. The cured composition obtained by the reaction-curable composition according to any one of PP-13 water, in particular in the form of moisture in the air.

15. Method of bonding a substrate S1 to a substrate S2, comprising the following stages:
i) applying a curable composition according to any one of PP-13 on the substrate S1;
ii) contacting the applied composition with a substrate S2 within the exposure time before bonding composition
or
i') applying a curable composition according to any one of PP-13 on a substrate S1 and a substrate S2;
ii') contacting the applied composition with each other during the exposure time before the bonding composition;
moreover, the substrate S2 consists of material similar to or different from the substrate material S1.

16. The method according to item 15, wherein the substrate S1 and/or the substrate S2 are inorganic substrate such as glass, glass ceramic, concrete, mortar, brick, tile, gypsum or natural stone such as granite or marble; metals or alloys such as aluminum, steel, non-ferrous metal is ll, galvanized metals; organic substrates such as wood, plastics such as PVC, polycarbonate, emission spectra obtained for pure, polyethylene, polypropylene, complex, polyester, epoxy resins; coated substrates such as a substrate, coated with a powder of metal or alloy; or paint, or varnish, in particular automotive top coat varnish.

17. Method of sealing comprising the following stage:
i) applying a curable composition according to any one of PP-13 between the substrate S 1 and a substrate S2, so that the composition was kept in contact with the substrate S1 and the substrate S2;
moreover, the substrate S2 consists of material similar to or different from the substrate material S1.

18. The method according to 17, wherein the substrate S1 and/or the substrate S2 are inorganic substrate such as glass, glass ceramic, concrete, mortar, 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, plastics such as PVC, polycarbonate, emission spectra obtained for pure, polyethylene, polypropylene, complex, polyester, epoxy resins; coated substrates such as the substrate coated with the powder of metal or alloy; or paint, or varnish, in particular automotive top coat varnish.

19. Method of coating a substrate S1, the switch is in store next stage:
i') applying a curable composition according to any one of PP-13 on a substrate S1 within the exposure time before the bonding composition.

20. The method according to claim 19, characterized in that the substrate S1 and/or the substrate S2 are inorganic substrate such as glass, glass ceramic, concrete, mortar, 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, plastics such as PVC, polycarbonate, emission spectra obtained for pure, polyethylene, polypropylene, complex, polyester, epoxy resins; coated substrates such as the substrate coated with the powder of metal or alloy; or paint, or varnish, in particular automotive top coat varnish.

21. The product, containing curable composition and a substrate, characterized in that the quality of the songs it contains a composition according to any one of PP-13.

22. The product according to item 21, wherein the product is a structure, preferably a high-rise or underground structure, or the product of an industrial or domestic purposes, in particular the window, household machine, or vehicle, in particular a water or land vehicle, preferably a car, bus, truck, train or ship, or hinged part of the transport is the main means, or the furniture, textile or packaging the product.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: composition contains a polysulphide oligomer, manganese dioxide, filler, a plasticiser, a solvent, diphenyl guanidine and a modifier. The filler is modified montmorillonite obtained by reacting montmorillonite with polyfluoroalkyloligo-ε-caproamides. The modifier is di(1,1,5-trihydroperfluoropentyl) phthalic ester.

EFFECT: invention improves physical and mechanical, adhesion and waterproofing properties of the coating and widens the field of use of the composition.

2 tbl, 4 ex

Urethane putty // 2451703

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry, particularly quick-setting polyurethane compositions and can be used in construction to seal joints between enclosing structures of buildings and control joints of concrete floors, slits and cracks. The urethane putty contains a component A as the basic paste, which contains a hydroxyl-containing polyether with molecular weight 3600, silicon dioxide, diethylene glycol, a cationic catalyst, a plasticiser containing dibutylphthalate and chloroparaffin, filler, and a component B as the putty hardener, which is obtained by reacting the hydroxyl-containing polyether - laprol 3603-2-12 with toluylene diisocyanate and further contains a stabiliser, wherein before application, components A and B are mixed with each other in ratio 9:1 pts.wt, respectively.

EFFECT: broader processing capability of urethane putty in construction of buildings.

4 cl

FIELD: chemistry.

SUBSTANCE: invention relates to acrylic rubber compositions which are used to make industrial rubber products, e.g., rubber hose, sealing articles, rubber vibration insulators etc. The composition contains carboxyl group-containing acrylic rubber, a diazabicycloalkene compound, a polyamine compound and a tertiary amine compound of formula (1), where each of R1, R2 and R3 independently denotes a substitute containing at least one saturated aliphatic hydrocarbon or an unsaturated aliphatic hydrocarbon with a linear structure, a branched structure or a cyclic structure, or a benzyl group. The polyamine compound is an aromatic polyamine of formula (2): H2N-Ph-M-Ph-NH2 (2) where M denotes O, S, SO2, CONH or O-R-O; R in O-R-O is Ph, Ph-Ph, Ph-SO2Ph, (CH2)m, m ranges from 3 to 5, Ph-CH2-C(CX3)2CH2-Pn, where X is H or F, or (CH2)C(CH3)2(CH2); Ph denotes a benzene ring.

EFFECT: good curing parameters and excellent combination of processability, mechanical properties of rubber and compression set of acrylic rubber compositions and curing products thereof.

9 cl, 5 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: composition contains the following in pts.wt: polysulphide oligomer 100, manganese dioxide 9-15, filler - modified montmorillonite 1-5, plasticiser 30-60, diphenyl guanidine 0.2-0.6 and a modifier 5-7. The modifier is an oligodiene diol ester prepolymer of an oligomer of ε-aminocaproic acid.

EFFECT: invention improves physical and mechanical, adhesion and waterproofing properties of the coating.

2 tbl, 2 ex

Coating composition // 2448141

FIELD: chemistry.

SUBSTANCE: composition contains the following in pts.wt: polysulphide oligomer - liquid thiocols with number-average molecular weight 1700-5500 and viscosity at 25°C 7.5-50 Pa·s 100, manganese dioxide 9-15, glycerine 15-25, 2,4,6-tris- (dimethylaminomethyl)-phenol 0.2-0.6, oligobutadiene diol 10-20, polyisocyanate 3-5, urethane-formation catalyst 0.01-1.00, diatomite 60-80, modifier 0.1-1.

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2 tbl

FIELD: chemistry.

SUBSTANCE: insulating double-glased window has at least two glass sheets spaced apart, a low thermal conductivity gas in between and a gas sealing element containing a curable sealing compound. The sealing compound consists of a) polydiorganosiloxane, which is permeable to said gas and the polydiorganosiloxane has a silanol end, having the following formula: MaDbD'c, in which a=2, b≥1, c equals zero or a positive whole number, M=(HO)3-x-yR1xR2ySiO1/2, in which x=0, 1 or 2, and y=0 or 1, provided that (x+y)≤2, R1 and R2 denote univalent C1-C60 hydrocarbon radicals; D=R3R4SiO1/2, in which R3 and R4 denote univalent C1-C60 hydrocarbon radicals; D'=R5R6SiO2/2, in which R5 and R6 are independently selected from univalent C1-C60 hydrocarbon radicals; b) at least one polymer which is at least less permeable to said gas than the polydiorganosiloxane polymer; c) a cross-linking agent; and d) a cross-linking catalyst.

EFFECT: obtaining insulating double-glased window with improved heat insulation stability and longer service life.

36 cl, 4 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: disclosed sealing composition contains the following (wt %): (A) a moisture-curable silane-functional elastomeric organic polymer (10-65); (B) a condensation catalyst (0.12-3); (C) a physical drying agent (15-25); (D) an agent for releasing water in the application temperature interval (5-30); (E) filler (0-30) (D); (F) a non-reactive elastomeric organic polymer (0-30); (G) a crosslinker (0-5); (H) a chemical drying agent other than (G) (0-5); (I) an adhesion promoter other than (G) and (H) (0-5); (J) microcrystalline wax, which is solid at 25°C (0-20); (K) an anti-ageing agent (0-3); and (L) a tackifying agent (0-20). Disclosed also is a method of preparing said composition, an insulating unit made from said composition and versions of the method of preparing said composition, as well as versions of the method of curing said composition.

EFFECT: when used as edge sealer in an insulating unit, the hardened product of the compositions simultaneously performs functions such as sealing, joining, spacing and drying.

16 cl, 2 dwg, 16 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry, particularly sealing compounds, and can be used to seal double-glased windows. The polysulphide oligomer based sealing compound contains a component A made from sealing paste and a component B made from hardening paste, which, before application, are mixed with each other in ratio of 10:1 pts.wt, respectively. Component A is made by mixing a liquid polysulphide oligomer, butylbenzylphthalate and/or chloroparaffin with successive batched addition of an adhesive, chemically precipitated chalk and hydrophobic chalk. Component B is made by mixing manganese dioxide and butylbenzylphthalate with successive addition of technical carbon, thiuram and diphenyl guanidine.

EFFECT: invention improves basic operational properties of the sealing compound.

2 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to precipitated silicic acid and a method of obtaining said acid. Precipitated silicic acid has coefficient of extinction SiOHizolir equal to or greater than 1. The silicic acid is obtained through reaction of a silicate with an acidic substance. The obtained silicic acid is then filtered, washed, dried and annealed.

EFFECT: silicic acid in silicone rubber compositions provides high stability during storage, high strength and optimum fluidity characteristics.

21 cl, 9 dwg, 6 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: epoxy composition for polymerisation contains (A2) a fluorene epoxy compound of formula

,

(A3) an epoxy compound with softening point of 30°C or lower, and (B) a thiol compound containing two or more thiol groups per molecule. As one version, the composition contains a curing accelerator or a curing accelerator and a silane modifier. The group of inventions also includes a transparent resin for optical materials (versions), a sealing compound (versions), a hardened article (versions), a method of producing the epoxy composition for polymerisation, an optical device and an organic EL display.

EFFECT: article made from the composition has high refraction index and high heat-resistance; by sealing an optical device with the epoxy composition for polymerisation, light-harvesting efficiency can be improved and moisture penetration into the device can be prevented.

25 cl, 3 dwg, 17 ex

FIELD: chemistry.

SUBSTANCE: composition contains one or more urethane prepolymers, having isocyanate residues, one or more compounds which catalyse the reaction of isocyanate residues with water or a compound which contains active hydrogen and one or more alpha-hydrocarbyl silane compounds. The urethane propolymer additionally contains a silane functional group. The composition additionally contains a compound or a polymer, containing silane residues. The composition additionally contains one or more compounds which catalyse silanol condensation. The composition is deposited onto the surface of glass or plastic with a coating or onto the surface of a substrate to obtain a sealant, then brought into contact and the composition is then hardened. The composition is placed between the glass or plastic with coating and the substrate. The sealing composition is used for binding an unprimed surface with a coating, such as a window lintel with glass with a transparent plastic, coated with an abrasive-resistant coating or with glass or plastic with a coating, additionally coated with glass cement, such as ceramic or organic glass cement.

EFFECT: improved composition properties.

10 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of gluing involves processing the surfaces to be glued, applying the glue, pressing the components together and solidification of the glue. The glued surfaces are processed through external heating of the glued components until formation of a 0.5-2.0 mm deep coked layer. The glue joint works at temperature conditions at which material of one or both of the components undergoes thermal decomposition.

EFFECT: method improves adhesion characteristics of gluing carbon fibre reinforced plastic, as well as other composites with heat-resistant filler, increases reliability of operation, particularly glued heat shielding of sockets and reduces their weight.

1 tbl, 2 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to woodworking. Proposed method comprises pressing the stack of two or more boards wherein every board has surface layer and base layer. Surface layer side stays in contact with base layer side. Aforesaid sides in contact have fast-curing glue arranged there between that comprises(a) emulsion polymer selected from the group consisting of latex of butadiene-styrene rubber, latex of modified butadiene-styrene rubber, polyvinyl acetate, ethylene vinyl acetate and combination thereof, and (b) cross-linking compound. Pressing consist in application of uniform pressure to the stack, perpendicular to its surface, at ambient temperature for time equal to, at least 0.1 min, without hot pressing.

EFFECT: pressing of wood lamina materials at ambient temperature using glues not containing formaldehydes.

19 cl, 12 ex, 3 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention can be used in rubber industry to make rubber-metal articles, particularly water-resistant articles used at high temperatures (up to 90°C). The invention relates to a method of gluing rubber to metal through a cold curing method, which involves applying a layer of glue onto a processed metal surface. Rubber is glued to the metal using a ternary adhesive composition: a first layer of Chemosil 211 glue is applied onto a processed metal surface and dried, a second layer of Chemosil 221 or Chemosil 222 glue is applied on the first layer and dried, and two layers of 88 KR glue are applied on each processed metal and rubber surfaces, drying each of the layers and then gluing the surfaces.

EFFECT: higher bonding strength of polar raw rubber-based rubber with a metal alloy while maintaining high adhesiveness and adhesion strength when the article is used in water at high temperatures.

2 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of gluing vulcanised rubber to each other and can be used in rubber industry. The method of gluing different types of vulcanised rubber to each other involves application of polychloroprene rubber based glue onto vulcanised rubber surfaces to be glued and then bringing the surfaces into contact. The base of the polychloroprene glue used is nairit NT or nairit DP combined with butyl phenolformaldehyde resin in 88NT or 88SA adhesive. Before application onto the surface, the adhesive is mixed with a trichloroethylphosphate or trichloropropylphosphate modifier in amount of 0.05-2.0 pts. wt per 100 pts. wt of the adhesive, and after application, the adhesive film is dried at room temperature for 1-2 minutes and the surfaces to be glued are brought into contact under a load for 24 hours.

EFFECT: increased strength of the glue joint when gluing vulcanised rubber and simplification of the gluing process.

2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of gluing vulcanised rubber of the same type to each other involves depositing glue based on polychloroprene rubber on the surfaces to be glued and subsequently bringing the surfaces into contact. 88NT or 88SA glue based on polychloroprene rubber nairite NT or nairite DP combined with butylphenol formaldehyde resin is used. Before depositing the glue onto the surface, a modifier which is ortho-phenylenediamine is added to the glue in amount of 0.5-3.0 pts. wt per 100 pts. wt of glue, and after deposition, the glue film is dried at room temperature for 1-2 minutes. The glued surfaces are brought into contact under a load for 24 hours. Rubber based on SKI-3, SKEPT-40, SKN-18 and neoprene is glued.

EFFECT: increased strength of the glue joint when gluing vulcanised rubber and simplification of the gluing process.

2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of bonding vulcanised rubber of the same type to each other involves depositing glue based on polychloroprene rubber on the surfaces to be glued together, as well as 88NT or 88SA glue based on polychloroprene rubber nairite NT or nairite DP combined with butylphenol formaldehyde resin. Before depositing onto the surface, a modifier which is paraoxydiphenylamine is added to the glue in amount of 0.3-4.0 pts. wt per 100 pts. wt of glue, and after depositing, the glue film is dried at room temperature for 1-2 minutes, and the surfaces are brought into contact under a load for 24 hours. Rubber based on SKI-3, SKEPT-40, SKN-18M and neoprene AS is glued together.

EFFECT: increased strength of the glued joint when gluing vulcanised rubber of the same type, simplification of the gluing process.

2 tbl, 2 ex

FIELD: technological processes.

SUBSTANCE: synthetic glue is applied on the surface of parts from wood materials, glued surfaces are joined until glue hardens completely, at that glued parts are located between plates of electrostatic field capacitor so that power lines of electrostatic field are directed perpendicular to glue line and treated in electrostatic field with intensity of 2.16-9.5·102 V/cm, and glue applied on glued surfaces is polyvinyl acetate PVAC or epoxy K-153.

EFFECT: higher strength of glued connections of wood materials and higher speed of glue line hardening.

2 tbl

FIELD: technological processes.

SUBSTANCE: invention pertains to method and device to apply glue and curative components of multicomponent glue system to wooden part surfaces. The problem is solved due to the fact, that the method consists in capability to apply glue mixture components to the parts either separately, or as a ready-to-use mixture with application device, which is produced to support the mentioned alternative modes. At that, the device contains at least two glue application units. At least one of them, designed to apply curative components, can be switched off. Besides, the device contains at least one unit, which is used to apply either glue components, or mixed curative and glue components. The multicomponent glue system must contain at least one of the following glue components: urea-formaldehyde resin (UF), melamine urea-formaldehyde resin (MUF), melamine urea-phenol-formaldehyde resin (MUPF), phenol-resorcinol-formaldehyde resin (PRF), resorcinol-formaldehyde resin (RF), phenol-formaldehyde resin (PF), polyvinyl acetat (PVAc).

EFFECT: avoiding disadvantages of certain technical solutions.

8 cl, 2 ex, 1 dwg

FIELD: technological processes.

SUBSTANCE: method of timber-based materials adhesion includes operation of applying glue on adherend surfaces, joining of adherend surfaces until complete glue hardening, at that adherend parts are placed in between electromagnet poles, with power magnet lines perpendicular direction to glue joint, and are treated in impulse magnetic field with strength of 3-24-104 A/m and oscillation period of T=1-10 sec., and adherend surfaces are coated with urea-formaldehyde (KFZh) or polyvinyl acetate (PVA).

EFFECT: improves strength of glue joints of timber-based materials when using standard glues.

2 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to a polyisocyanurate based adhesive which is obtained by reacting an organic polyisocyanate with a compound containing hydrogen atoms which are reactive towards isocyanate, in the presence of a trimerisation catalyst. The organic polyisocyanate is a polymer or prepolymer polyisocyanate, and content of the soft block in the adhesive ranges from 40 to 60 wt %. A reaction mixture for producing said adhesive is also described.

EFFECT: obtaining an adhesive capable of withstanding high maximum stress, having extremely fast setting and having a good and strong bond with the base, as well as high thermal stability, resistance to salty water and creep.

9 cl, 4 ex, 6 tbl

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