Composition distinguished by improved adhesion to porous substrates

FIELD: chemistry.

SUBSTANCE: invention relates to compositions based on silane-functional polymers, which are suitable for adhesive binding, sealing and coating porous substrates. The composition contains at least one silane-functional polymer, at least one organosilane and at least one organotitanate. The silane-functional polymer is a silane-functional polyurethane polymer or can be obtained through hydrosilylation of polymers, having terminal double bonds. The organosilane contains at least one sulphur atom. The organotitanate has ligands bound to a titanium atom through an oxygen-titanium bond. The ligands are selected from a group consisting of an alkoxy group, a sulphate group, a carboxylate group, a dialkylphosphate group and an acetylacetonate group. Content of the organotitanate in the composition is between 0.1 and 10 wt %. Content of the organosilane in the composition is between 0.1 and 7 wt %. The composition also contains at least one filler, content of which is between 10 and 70 wt %. The composition is used for binding, sealing and coating substrates made from concrete, mortar, brick, tiles, plaster, natural stone such as granite or marble, glass, glass-ceramic, metal or metal alloy, wood, plastic and lacquer.

EFFECT: obtained article, which is bound, sealed or coated using the composition, is a building structure, more specifically a building or civil construction structure; the composition guarantees efficient adhesion to a substrate even after storage in the presence of water.

17 cl, 1 tbl

The scope of the invention

This invention relates to the field of elastic adhesives, sealants and coatings based on silane-functional polymers.

Description of the prior art,

Curing in a moist environment composition used for a considerable time as elastic adhesives, sealants and coatings.

For adhesive bonding, sealing and coating of porous substrates, more specifically, a porous mineral substrates such as concrete and the like, which are notoriously difficult to achieve satisfactory adhesion with elastic adhesives, sealants and coatings are widely used curing in a moist environment composition based on isocyanate. From the ecological and Toxicological point of view, however, such compositions are not suitable for any application.

For this reason, and especially with regard to adhesion to concrete, also used when curing in a moist environment composition based on silane-functional polymers, adhesion of such compositions after storage in the presence of water is an issue that deserves special attention. One reason for this is that due to capillary action in porous materials, water can penetrate between the surface of the substrate and the adhesive or sealant and, therefore, sublet adhesion.

On porous substrates, more specifically, to porous mineral substrates such as concrete, satisfactory adhesion of adhesives, sealants and coatings based on silane-functional polymers can only be guaranteed in conjunction with the promoting adhesion of the compositions, the so-called primers. For example, the appropriate promoting adhesion of the composition to curing in a moist environment compositions of this type are described in JP 4076084.

For various reasons it may be necessary or can be a serious advantage of the lack of promoting adhesion of the compositions in the form of a primer coating, in the exercise of adhesive bonding, sealing or coating. For example, the use of adhesive binding without primer leads not only to the benefit of cost, but also to the advantage of time, as there is no need to apply and ventilate the promoting adhesion of the composition. Moreover, adhesive binding without primer also has an advantage from the point of view of environmental protection, as primers often contain large amounts of volatile organic solvents, so-called VOC (volatile organic compounds).

The invention

The purpose of this invention, therefore, is to provide a composition based on silane-functional polymers, which is the tsya suitable for binding, sealing and coating without primer for porous substrates, more specifically, a porous mineral substrates such as concrete and the like.

Unexpectedly, it was found that the composition of p. 1 can achieve this goal.

The composition according to the invention without the use of promoting adhesion of the compositions provides a reliable and effective adhesion to porous substrates, particularly to porous mineral substrates such as concrete and the like. Surprising and not obvious to a person skilled in this field that the composition according to the invention also has the properties of good adhesion after prolonged storage in the presence of water.

Moreover, compared with traditional systems the composition of the invention exhibit significantly improved thermal stability in dry condition.

Additional aspects of the invention are reflected in additional independent claims. Particularly preferred embodiments of the invention are reflected in the dependent claims.

Description of the preferred embodiments of the invention

This invention relates to compositions, including

a) at least one silane-functional polymer P,

b) at least one organosilane, which contains at least one sulfur atom, and

C) at least one organotitanate.

The names of the compounds that begin with "poly", such as polyol or polyisocyanate, herein mean compounds which formally contain two or more functional groups that occur in their name, in the molecule.

The term "polymer" in this document covers, first, the combination of chemically uniform macromolecules which nevertheless differ in respect of degree of polymerization, molecular weight and chain length and obtained by the reaction of polymerization (polymerization, polyaddition, polycondensation). Secondly, the term also covers derivative of such a set of macromolecules from the polymerization, in other words, compounds that are obtained by such reactions as the reactions of addition or substitution reactions, for example, of functional groups on existing macromolecules and which may be chemically uniform or chemically non-uniform. The term additionally includes compounds that are known as prepolymers, i.e. the reactive oligomeric Produkty, functional groups which are included in the structure of macromolecules.

The term "polyurethane polymer" covers all polymers that are produced by the process known as the process diisocyanate polyaddition. He also clochette polymers, which actually or not contain urethane groups. Examples of polyurethane polymers are (easy polyester-polyurethanes, (complex polyester-polyurethanes, (easy polyester)-polyurea, polyurea, (complex polyester)-polyurea, polyisocyanurate and polycarbamide.

In this document, the terms "silane" and "organosilane" means compounds which on the one hand, contain at least one, usually two or three alloctype attached directly to the silicon atom through a Si-O, and, on the other hand, contain at least one organic radical attached directly to the silicon atom via a bond Si-N-Silanes of this kind are known to the expert in this area as organoalkoxysilanes and organoalkoxysilanes, respectively. Therefore, according to this definition "tetraalkoxysilane" are not organosilane.

Accordingly, the term "silane group" means a silicon-containing group that is attached to the organic radical of the silane that is connected via connection Si-N-Silanes or silane groups tend to undergo hydrolysis upon contact with moisture. This hydrolysis is accompanied by the formation of organosilanols, i.e. organosilicon compounds containing one or more silanol groups (Si-OH) and, as p is the result of subsequent reactions of condensation, organosiloxanes, i.e. organosilicon compounds containing one or more siloxane groups (Si-O-Si).

The term "silane-functional" refers to compounds that contain silane groups. "Silane-functional polymers", respectively, are polymers that contain at least one silane group.

Organosilane identified as "aminosilane" or "mercaptoethane are such organic radical which contains an amino group or mercaptopropyl, respectively. "Primary aminosilane are aminosilane, which contain a primary amino group, in other words, the group of NH₂that is attached to an organic radical. "Secondary aminosilane are aminosilane, which contain secondary amino group, in other words, the NH group that is attached to two organic radicals.

In this document the term "organotitanate" means compounds that contain at least one ligand attached to the titanium atom through an oxygen atom.

"Multidentate ligand or chelate ligand should be understood in this document as the ligand, which has at least two free electron pairs and is able to take at least two coordination location on the Central atom. Bidentate shall hand, respectively, has the ability to occupy two coordination location on the Central atom.

The term "primer" is very well known specialist in this field and in this document means a thin layer promoting adhesion of the composition, usually thinner than 1 mm, more specifically between 1 and 200 μm, preferably between 1 and 100 microns, which is applied as an adhesive primer on the surface of the substrate and, when predetermined, after ventilation, lead in contact with the stick composition, which contributes to the improvement of the adhesion of the composition to the substrate. The term "without primer" are used respectively for bonding, sealing or coating of substrates without pre-treatment primer.

By "molecular weight" in this document means always the average molecular mass M_n(srednekislye).

The composition according to the invention contains at least one silane-functional polymer P, which contains, in particular, the end groups of the formula (I)

In this formula the radical R¹means an alkyl group having 1 to 8 C atoms, more particularly a methyl group or ethyl.

The radical R²means acyl or alkyl group having 1 to 5 C atoms, more particularly a methyl group, or ethyl, or isopropyl.

Radik is l R ³means a linear or branched, optionally cyclic alkylenes group having from 1 to 12 C atoms, optionally with aromatic fragments, and optionally one or more heteroatoms, more particularly with one or more nitrogen atoms.

Index and represents the value 0, or 1, or 2, more specifically the value 0.

In one a silanol group of the formula (I) R¹and R²each independently of one another, represent the above radicals. So, for example, the compounds of formula (I) include compounds that are ethoxy-dimethoxy-alkylsilane (R²= methyl, R²= methyl, R²= ethyl).

In the first embodiment, the silane-functional polymer P is a silane-functional polymer P1, obtained by the interaction of the silane which contains at least one group which is reactive in relation to the isocyanate groups of the polyurethane polymer containing isocyanate groups. This reaction is carried out preferably when the stoichiometric ratio of groups, which are reactive in relation to the isocyanate groups to isocyanate groups of 1:1, or with a small excess of groups, which are reactive in relation to isocyanate groups, and so that the resulting silane-function is based polymer P1 does not contain isocyanate groups.

A silane which contains at least one group which is reactive in relation to isocyanate groups, is, for example, mercaptomerin or aminosilane more specifically aminosilane.

Aminosilane preferably is aminosilanes AS formula (Ia)

where R¹, R², R³and a have the above meanings and R¹¹means a hydrogen atom or a linear or branched hydrocarbon radical having from 1 to 20 C atoms, which optionally contains cyclic fragments, or a radical of the formula (VI)

In this formula, the radicals R¹²and R¹³, independently of one another, represent a hydrogen atom or a radical from the group consisting of-R¹⁵, -CN, and-COOR¹⁵.

The radical R¹⁴represents a hydrogen atom or a radical from the group consisting of-CH₂-COOR¹⁵, -COOR¹⁵, -CONHR¹⁵, -CON(R¹⁵)₂, -CN, -NO₂, -PO(OR¹⁵)₂, -SO₂R¹⁵and-SO₂OR¹⁵.

The radical R¹⁵represents a hydrocarbon radical having from 1 to 20 C atoms, which optionally contains at least one heteroatom.

Examples of suitable aminosilanes AS are primary aminosilane, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane; Deut is cnie aminosilane, such as N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; the reaction products, such connection to Michael, primary aminosilanes, such as 3-aminopropyltrimethoxysilane or 3-aminopropyltrimethoxysilane, with Michael acceptors such as Acrylonitrile, acrylic or methacrylic esters, acrylamide or methacrylamide, maleic and fumaric complex diesters, citraconate complex diesters and itaconate complex diesters, examples are dimethyl - and diethyl-N-(3-methoxytryptophol)aminosuccinic, and also analogues of these aminosilanes with ethoxy or isopropoxy instead of methoxypropyl on silicon. Especially suitable aminosilane AS are secondary aminosilane, more specifically aminosilane AS in which R¹¹in the formula (Ia) is other than H. The preferred connection is similar to the Michael adducts, more specifically diethyl-N-(3-methoxytryptophol)aminosuccinic.

In this document, the term "Michael acceptor" refers to compounds that are able to join together with the primary amino groups (groups NH₂in the reaction of nucleophilic attachment proceeding similarly to the reactions of addition of Michael (heterobasidion Michael), they have double bonds activated by electron acceptors.

Examples of suitable polyure the new polymer, containing isocyanate groups, to obtain a silane-functional polyurethane polymer P1 include polymers obtained by reaction of at least one polyol with at least one polyisocyanate, more specifically with the diisocyanate. This reaction can be carried out by conventional methods by reacting the polyol and MDI at temperatures of, for example, from 50°C to 100°C, where peculiar, with concomitant application of appropriate catalysts, and the number of MDI pick up so that isocyanate groups are present in stoichiometric excess relative to the hydroxyl groups of the polyol.

In particular, excess MDI pick up so that after the reaction of all hydroxyl groups of the polyol obtained polyurethane polymer has a residual content of free isocyanate groups is from 0.1% to 5 wt.%, preferably from 0.1% to 2.5 wt.%, more preferably from 0.2% to 1 wt.%, based on the entire polymer.

It is possible, if necessary, obtain a polyurethane polymer with concomitant application of plasticizer, the plasticizer does not contain groups reactive towards isocyanate.

The preferred polyurethane polymers are polymers having set the content of free isocyanate groups and obtained by the eacli diisocyanates with high molecular dialami with a ratio of NCO:OH of 1.5:1 to 2:1.

Suitable polyols to obtain a polyurethane polymer are, in particular, polyether polyols, polyol polyesters and polycarbonate polyols and mixtures of these polyols.

Suitable polyether polyols, also called polyoxyalkylene or oligopyrroles are especially those which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2 - or 2,3-butilenica, oxetane, tetrahydrofuran or mixtures thereof, where necessary, polymerized with an auxiliary additive parent compound with two or more active hydrogen atoms, such as, for example, water, ammonia or compounds having two or more groups HE or NH, such as, for example, 1,2-ethanediol, 1,2 - or 1,3-propandiol, neopentylglycol, diethylene glycol, triethylene glycol, the isomeric dipropyleneglycol and tripropyleneglycol, 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 also mixtures of these compounds. Polyoxyalkylene, which can be used include those which have a low degree of unsaturation (measured according to ASTM D-2849-69 and presented in the mill is the equivalent of unsaturation per gram of polyol (mEq./g)), obtained, for example, by using so-called double metal cyanide complex catalysts (DMC catalysts), and those that have a higher degree of unsaturation obtained, for example, with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkoxides of alkali metals.

Especially suitable are polyoxyethyleneglycol, especially polyoxyethylene, polyoxypropylene, polyoxyethylene and polyoxypropylene.

Especially suitable are polyoxyalkylene or polyoxyalkylene having a degree of unsaturation of less than 0.02 mEq./g and having a molecular weight ranging from 1000 to 30,000 g/mol, and also polyoxyethylene, polyoxyethylene, polyoxypropylene and polyoxypropylene having a molecular weight of from 400 to 20,000 g/mol.

Likewise particularly suitable are the so-called blocked with ethylene oxide ("EO-blocked at the ends of the"blocked at the ends of ethylene oxide) polyoxypropyleneamine. The latter are special polyoxypropylene-polyoxyethyleneglycol that receive, for example, exposing a clean polyoxypropyleneamine, more specifically polyoxypropylene and trioli after the reaction of propoxycarbonyl additional alkoxycarbonyl with ethylene oxide, and which contain Erwinia hydroxyl group. Preference in this case give polyoxypropylene-polyoxyethylene, polyoxypropylene-polyoxyethylenated.

Additionally suitable are polybutadienes with terminal hydroxyl groups, such as the polyols, for example, which is produced by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene, and also products of their hydration.

Suitable polyols polyether grafted styrene-Acrylonitrile, commercially available, for example, under the trade name Lupranol® from the company Elastogran GmbH, Germany.

Particularly suitable polyols and polyesters are polyesters which carry at least two hydroxyl groups and obtained by the known methods, more specifically the polycondensation polyhydroxyalkanoic acids or the polycondensation of aliphatic and/or aromatic polioksidony acids with alcohols having hydrocast (mnogotomnoi - approx. trans.) two or more.

Particularly suitable polyols are polyesters derived from diatomic, triatomic alcohols, such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propandiol, dipropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, glycerol, 1,1,1-trimethylolpropane or mixtures of these alcohols, with organic dicarboxylic what slot or their anhydrides or esters, such as, for example, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, subernova acid, azelaic acid, sabotinova acid, dodecadienol acid, maleic acid, fumaric acid, dimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitate acid and trimellitic anhydride or mixtures of these acids and polyols and polyesters of lactones, such as ε-caprolactone, for example.

Particularly suitable diols are polyesters, especially those produced from adipic acid, azelaic acid, sabatinovka acid, dodecadienol acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as dicarboxylic acids or lactones, such as ε-caprolactone, and from ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexandiol, diol dimer fatty acid and 1,4-cyclohexanedimethanol as a diatomic alcohol.

Particularly suitable as polycarbonatediol are obtained by reaction, for example, these alcohols used for the synthesis of polyol polyesters, diallylmalonate, such as dimethylcarbonate, d is arylcarbamoyl, such as diphenylcarbonate, or phosgene. The polycarbonate diols are particularly suitable, especially amorphous polycarbonate diols.

Additional suitable polyols are poly(meth)creatology.

Also suitable are poliglecaprone polyols, also called oligohydramnios, their examples are polyhydroxy-functional copolymers, ethylene-propylene, ethylene-butylene or ethylene-propylene-diene grades obtained, for example, by the company Kraton Polymers, USA, or polyhydroxy-functional copolymers of dienes such as 1,3-butadiene or a mixture of dienes and vinyl monomers such as styrene, Acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene polyols, examples are those obtained by copolymerization of 1,3-butadiene and allyl alcohol and which can also be gidratirovana.

Additionally suitable are polyhydroxy-functional copolymers which can be obtained, for example, from epoxides or aminoalcohols, and ends with the carboxyl groups of the copolymers, Acrylonitrile/butadiene, which are commercially available under the name Hypro® (pre-Hycar®) CTBN from Emerald Performance Materials, LLC, USA.

These polyols preferably have an average molecular weight of from 250 to 30,000 g/mol, more preferably the t 1,000 to 30,000 g/mol, and average IT functionality in the range from 1.6 to 3.

Particularly suitable polyols polyols are polyesters and polyether polyols, especially polyoxyethyleneglycol, polyoxypropyleneglycol, polyoxypropylene-polyoxyethyleneglycol, preferably polyoxyethylene, polyoxypropylene, polyoxyethylene, polyoxypropylene, polyoxypropylene-polyoxyethylene polyoxypropylene-polyoxyethylene.

In addition to these polyols may also use small amounts of low-molecular diatomic or polynuclear 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-cyclohexane of dimethanol, hydrated bisphenol a, dimeric fatty alcohols, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol or mannitol, sugars such as sucrose, other higher polynuclear alcohols, low molecular weight products alkoxysilane these diatomic and polynuclear alcohols, and also mixtures of these alcohols, when you get a polyurethane polymer containing isocyanate end the group.

As polyisocyanates to obtain a polyurethane polymer may use commercially available aliphatic, cycloaliphatic or aromatic polyisocyanates, especially diisocyanates.

For example, the diisocyanates, isocyanate groups which are attached in each case to the aliphatic, cycloaliphatic or arylaliphatic the atom, and they are also called "aliphatic diisocyanates, such as 1,6-hexamethylene diisocyanate (HDI), 2-methylpentanediol 1,5-diisocyanate, 2,2,4 - and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,12-dodeca-methylene diisocyanate, lysine diisocyanate and the diisocyanate of ester of lysine, cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (i.e. isophorone diisocyanate or IPDI), perhydro-2,4'-difenilmetana diisocyanate, perhydro-4,4'-difenilmetana diisocyanate, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3 - and 1,4-bis-(isocyanatomethyl) cyclohexane, m - and p-xylylene diisocyanate (m - and p-XDI), m - and p-tetramethyl-1,3-xylylene diisocyanate, m - and p-tetramethyl-1,4-xylylene diisocyanate, bis-(1-isocyanato-1-methylethyl)naphthalene, and the diisocyanates having isocyanate groups attached in each case to one aromatic atom and is also known as "aromatic diisocyanates, such as 2,4 - and 2,6-toluene, dietzia is at (TDI), 4,4'-, 2,4'- and 2,2'-difenilmetana diisocyanate (MDI), 1,3 - and 1,4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanates, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatobutane (TODI), oligomers and polymers of the aforementioned isocyanates, and also any desired mixtures of these isocyanates.

Suitable silane-functional polymers P1 are, for example, commercially available under the trade name Polymer ST50 from Hanse Chemie AG, Germany, under the trade name Desmoseal® from Bayer MaterialScience AG, Germany.

In the second embodiment, the silane-functional polymer P is a silane-functional polyurethane polymer P2, obtained by reaction of isocyanatobenzene IS with a polymer that has a functional end groups which are reactive in relation to isocyanate groups, especially hydroxyl groups, mercaptopropyl and/or amino groups. The reaction is carried out in a stoichiometric ratio of 1:1 isocyanate groups to the terminal functional groups, which are reactive in relation to isocyanate groups, or with a small excess of the limit functional groups which are reactive in relation to isocyanate groups at temperatures of, for example, from 20°C to 100°C, where peculiar, with an accompanying catalysts.

When timimi as isocyanatobenzene IS are the compounds of formula (Ib).

where R¹, R², R³and a have the above values.

Examples of suitable isocyanatobenzene IS of formula (Ib) are 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and their analogues with ethoxy or isopropoxy instead of methoxypropyl on silicon.

The polymer preferably contains hydroxyl groups as terminal functional groups reactive in relation to isocyanate groups.

Suitable polymers containing hydroxyl groups are, on the one hand, the above polyoxyalkylene polyols of high molecular weight, preferably of polyoxypropylene diols having an unsaturation of less than 0.02 mEq./g and having a molecular weight in the range from 4000 to 30000 g/mol, particularly those which have a molecular weight in the range from 8000 to 30000 g/mol.

Also suitable for reaction with isocyanatobenzene IS of formula (Ib), on the other hand, are polyurethane polymers containing hydroxyl groups, more particularly polymers terminated with hydroxyl groups. Such polyurethane polymers can be obtained by reaction of at least one MDI at least one polyol. This reaction can be carried out by conventional methods vzaimodeistviyah and MDI at temperatures for example, from 50°C to 100°C, where necessary, with concomitant application of appropriate catalysts, the amount of polyol is such that its hydroxyl groups are present in stoichiometric excess relative to isocynate groups MDI. The preferred ratio of hydroxyl groups to isocyanate groups of from 1.3:1 to 4:1, more specifically from 1.8:1 to 3:1. Polyurethane polymer, if predefined, can be obtained with concomitant application of plasticizers, in this case the used plasticizers do not contain groups that are reactive towards isocyanates. For this reaction applies the same polyols and polyisocyanates, which have already been identified to obtain a polyurethane polymer containing isocyanate groups and ispolzuemogo to obtain a silane-functional polymer P1.

As an example, a suitable silane-functional polymers P2 are commercially available under the trade names of SPUR+® 1010LM, 1015LM and 1050MM from Momentive Performance Materials Inc., USA, and also under the trade name Geniosil® STP-E15, STP-10 and STP-E35 from Wacker Chemie AG, Germany.

In the third embodiment, the silane-functional polymer P is a silane-functional polymer P3 received by the hydrosilation reaction of polymers having terminal double bonds, primarliy are polymers of poly(meth)acrylate or polyether polymers, more specifically, the polymers of polyoxyalkylene with terminal allyl groups, are described, for example, in U.S. patents 3971751 and 6207766, the contents of which are attached to this link.

As an example, a suitable silane-functional polymers P3 are commercially available under the trade names MS-Polymer® S203(H), S303(H), S227, S810, MA903 and S943, Silyl® SAX220, SAX350, SAX400 and SAX725, Silyl® SAT350 and SAT400 and also XMAP® SA100S and SA310S from the company Kaneka Corp., Japan, and also under the trade names Excestar® S2410, S2420, S3430, S3630, W2450 and MSX931 from the company Asahi Glass Co., Ltd., Japan.

Typically, the silane-functional polymer P is present in an amount of from 10% to 80 wt.%, preferably in an amount of from 15% to 60 wt.%, on the basis of the entire composition.

The composition according to the invention additionally contains at least one organosilane, which contains at least one atom of sulfur. Organosilane such varieties chosen especially from the group consisting of organosilanes formula (II), (III) and (IV).

In these formulas, the radical R⁴means an alkyl group having 1 to 8 C atoms, more particularly methyl group.

The radical R⁵means an alkyl group having 1 to 5 C atoms, more particularly a methyl group, ethyl or isopropyl, or acyl group, more specifically acetyl is the RUPE.

The radical R⁶means a linear or branched, optionally cyclic, alkylenes group having from 1 to 20 C atoms, optionally with aromatic fractions, and optionally with one or more heteroatoms, more specifically with nitrogen atoms.

X is S, S₂or S₄and b represents the value 0, 1 or 2.

Organosilanes, which contains at least one atom of sulfur, in particular, organosilane formula (II), where the radical R⁵means a methyl or ethyl radical, R⁶means linear alkylenes group having from 1 to 10, more specifically, has 3 atoms, and b represents the value 0.

Examples of suitable organosilanes formula (II) are selected from the group consisting of 3-mercaptopropionate, 3-mercaptopropionylglycine, 3-mercaptopropionylglycine and 3-alltypesreffactory.

Examples of suitable organosilanes formula (III) are bis(trialanderror)polysulfides, such as 4,4,15,15-tetraethoxy-3,16-dioxa-8,9,10,11-tetrathia-4-15-deselection or bis(triethoxysilylpropyl)disulfide. As an example, one such organosilane commercially available under the trade name Si 69® from Evonik Degussa GmbH, Germany.

Especially suitable organosilane formula (IV) are the reaction products organosol the s of the formula (II), such as 3-mercaptopropionylglycine, for example, glycidylmethacrylate, such as 3-glycidylmethacrylate, for example.

Suitable organosilane formula (II) are commercially available, for example, under the trade name Dynasylan® MTMO from Evonik Degussa GmbH, Germany, or under the trade name Silquest® A-189 from the company Firma Momentive Performance Materials Inc., USA.

The proportion of organosilane is preferably from 0.1% to 7 wt.%, more specifically from 0.2% to 4 wt.%, preferably from 0.4% to 2 wt.%, the whole composition.

The composition according to the invention additionally contains at least one organotitanate. Suitable ligands attached to the titanium atom through a linking oxygen-titanium, are those selected from the group consisting of alkoxygroup, sulphonate groups, carboxylate groups, dialkylphosphate group, dialkylphosphate group and acetylacetonate group.

Especially suitable organotitanate have at least one multidentate ligand, also called the chelate ligand. Multidentate ligand is more specifically bidentate ligand.

Especially suitable organotitanate represented by formula (V).

In this formula the radical R⁷means a hydrogen atom or a linear or branched alkyl group having from 1 to 8 ATO is s, more specifically methyl group.

The radical R⁸means a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms, which optionally contains heteroatoms, more particularly a hydrogen atom.

The radical R⁹means a hydrogen atom or alkyl group having 1 to 8 C atoms, more particularly having 1 to 3 C atoms, or a linear or branched alkoxygroup having 1 to 8 C atoms, more particularly having 1 to 3 atoms C.

The radical R¹⁰means a linear or branched alkyl radical having from 1 to 20 atoms, more specifically radical isobutyl or isopropyl.

n represents the value 1 or 2, more specifically 2.

The preferred organotitanate are organotitanate formula (V), where the radical R⁷means methyl group, the radical R⁸means a hydrogen atom, the radical R⁹means methyl group or methoxy - or ethoxypropan and the radical R¹⁰means radical isobutyl or isopropyl.

Note that it is possible or, in some cases even preferable to apply a mixture of different organotitanate.

Suitable organotitanate commercially available, for example, under the trade name Tyzor® AA, GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, IBAY from DuPont, USA.

Share organotitanate is preferably is from 0.1% to 10 wt.%, more specifically from 0.1% to 4 wt.%, preferably from 0.1% to 3 wt.%, the whole composition.

Preferably the composition further comprises a filler. The filler affects the rheological properties of the uncured composition, and mechanical properties and surface utverzhdenii composition. Suitable fillers are inorganic and organic fillers, such as natural, ground or precipitated calcium carbonates, covered, where necessary, essential fatty acids, especially stearic acid, and also barium sulfate (BaSO₄also called as barite or heavy spar), whether kaolin, aluminum oxide, aluminum hydroxide, silica, particularly highly disperse silicas from pyrolysis processes, carbon black, especially industrially produced carbon black, PVC powders or hollow spheres. Preferred fillers are calcium carbonates, whether kaolin, carbon black, highly dispersed silica, and also flame-retardant fillers such as hydroxides or hydrates, especially the hydroxides or hydrates of aluminum, preferably aluminum hydroxide.

It is quite possible and may even be advantageous to use a mixture of different fillers.

A suitable amount of filler is, for example, ranging from 10% to 70 wt.%, more specifically from 15% to 60 wt.%, predpochtite the flax from 30% to 60% wt.% on the basis of the entire composition.

Additionally, the composition according to the invention may contain additional components. Such components are, for example, plasticizers such as esters of organic carboxylic acids or their anhydrides, such as phthalates, for example, dioctylphthalate, diisononylphthalate or diisodecylphthalate, adipinate, such as dioctyladipate, for example, atalanti and Sabatini, polyols, for example, polyoxyalkylene polyols or polyol polyesters, organic phosphoric and sulfonic esters or polybutenes; solvents; fibers of polyethylene, for example; dyes; pigments; rheology modifiers such as thickeners or thixotropic agents, their examples are compounds of urea, polyamide waxes, bentonites or colloidal silica; promoters adhesion, their examples are epoxysilane, (meth)acryloyloxy, ameritocracy or adducts of these silanes with primary aminosilane and also motivirovana; crosslinking agents, examples include a silane-functional oligomers and polymers; drying accelerators, for example, VINYLTRIMETHOXYSILANE, α-functional silanes such as N-(millimeter)-O-methylcarbamate, especially N-(methyldeoxycytidine)-O-methylcarbamate, (methacryloyloxyethyl)silanes, ethoxymethylene, automarine complex is haunted esters, calcium oxide or molecular sieves; stabilizers against heat, light and UV radiation, for example; flame retardants; surface-active substances, such as wetting agents, regulating the fluidity agents, deaerating agents or prepodavatel; biocides, such as algaecides, fungicides or growth inhibition of fungi; and other substances commonly used in curing in a moist environment compositions.

In principle, there is no need to apply additional catalysts in the compositions according to the invention. If catalysts, however, are used, suitable examples include metal catalysts in the form of ORGANOTIN compounds, such as dilaurate dibutylamine and deacetylation dibutylamine, vismutorganicheskikh compounds or complexes of bismuth, titanium catalysts, compounds containing amino groups, for example, 1,4-diazabicyclo[2.2.2]octane and 2,2'-disorganizational simple ether, aminosilane and mixtures of these catalysts.

It is useful to select the components that are present, where inherent in the composition, more specifically, the filler and the catalyst, so that the stability of the composition during storage is not deteriorated due to the presence of such a component, in other words, so that the properties of the composition, more specifically the application properties and the properties of the hole is Denia suffered poorly or did not change during storage. This means that reactions leading to chemical curing of the specified composition, and especially the reaction Milanovich groups not occur to a significant extent during storage. It is therefore particularly useful to these components are not contained or are not allocated when storing any water or contained or identified during the storage of not more than trace amounts of water. Therefore, it may be appropriate to subject specific components chemical or physical drying before mixing them into the composition.

The above composition was prepared and stored in the absence of moisture. The composition is stable during storage, which means that in the absence of moisture to keep it in appropriate packaging or in a suitable device, such as a drum, a pouch or a cartridge, for example, during the period ranging from several months up to a year or more, without changing its application properties to the extent any substantial to work, or its properties after curing. Typically, the storage stability is determined by measuring the viscosity or extrusion force.

When the above composition is applied to at least one solid or product, silane groups of the polymer and silane are in contact with moisture. Si is anew groups tend to undergo hydrolysis in contact with moisture. This hydrolysis is accompanied by the formation of organosilanols and, as a result of subsequent condensation reactions, organosiloxanes. As a result of these reactions, which can be accelerated by using catalysts, the composition eventually hardens. This process is also called cross-linking.

Alternatively, the water required for curing may come from the air (atmospheric humidity), or else the specified composition can be brought into contact with water-containing component, being covered by the anointing, for example, a smoothing agent, for example, or by being sprayed, or else the composition during application may have a water-containing component added to it, in the form of aqueous paste, which is mixed in a static mixer, for example. In the case of curing by atmospheric moisture, the composition cures from the outside in. The curing speed depends on various factors, such as the diffusion rate of water temperature, ambient humidity and the geometry of the binding, for example, and generally slows down as curing.

The invention additionally relates to the use of specified composition as an adhesive, sealant or as compositions for coatings.

More specifically, the composition according to the invention is suitable for the coming as adhesive and/or sealant for bonding, and/or sealing and/or without primer coating porous substrates, more specifically, a porous mineral substrates such as concrete, for example. It is found that the composition according to the invention are, in particular, to improve adhesion after storage in the presence of water. In the context of adhesive bonding or sealing of porous substrates such as concrete, storage in the presence of water until the present time has always been problematic. One reason for this lies in the fact that as a result of capillary action in porous materials water can penetrate between the surface of the substrate and the adhesive or sealant and, consequently, may adversely affect adhesion. In addition, in the case of compositions according to the invention have improved thermal resistance in dry condition.

The invention additionally relates to a method for adhesive bonding two substrates S1 and S2, containing stages:

i) applying the composition described above to a substrate S1 and/or a substrate S2;

ii) contacting the substrates S1 and S2 via the applied composition during setting time of the composition;

iii) curing the composition by means of water, more specifically, water in the form of atmospheric moisture;

the substrates S1 and S2 are identical or different from each other.

The invention additionally relations is seeking to method of sealing or coating, containing stages:

i) applying the composition described above to a substrate S1 and/or between the substrates S1 and S2;

ii) curing the composition by means of water, more specifically, water in the form of atmospheric moisture;

the substrates S1 and S2 are identical or different from each other.

Particularly suitable substrates S1 and/or S2 are substrates selected from the group consisting of concrete, mortar, brick, tile, plaster, natural stone, such as granite or marble, glass, stalkerlike, metal or alloy of metals, wood, plastic, and lacquer.

The composition according to the invention preferably has a pasty consistency with the properties of structural viscosity. The composition of this kind is applied to the substrate, preferably in the form of drops, by means of suitable apparatus, this drop is essentially round or triangular cross-sectional area. Proper methods for applying the compositions are, for example, the use of commercially available cartridges that operate manually or by means of compressed air, or from a drum or Hobbock through a conveying pump or extruder, where characterized by the robot for the application. The composition according to the invention, having good application properties, demonstrates a high consistentes the ü and short ductility. In other words, it remains in the applied form after application and therefore is not shifted, and after the application device is lowered down, the song or does not form fibers or forms only a very short fiber, and thus the substrate is not contaminated.

The composition according to the invention have good adhesion to substrates, particularly to porous substrates, it is preferable to porous mineral substrates such as concrete, in particular even without the use of promoting adhesion of the compositions, the so-called primers.

The invention additionally relates to the product that bind, seal and/or cover composition, which is described here, and receive one of the following methods.

These products usually contain a building structure, more specifically building the structure of a building or civil engineering.

Examples

Test methods

Adhesion was determined as follows.

Adhesion was tested using concrete DIN, commercially available from Rocholl GmbH, Germany. The surface was cleaned with a steel brush and then freed from dust with compressed air. Then two drops of each composition was applied from a cartridge on each substrate. The substrate covered with drops, then kept under standard conditions (23±1°C, relative humidity 50±5%) in ECENA seven days, then the adhesion was tested for the first time (first drop). After that, the substrate coated with the composition was fully immersed in water and kept at room temperature. Adhesion was then tested each day of the droplets.

To test the adhesion of the substrate was fixed on the table by the clamp. At one end utverzhdenii drops did cut down almost to the surface of the substrate (connected to the front side) and cut the end of the drops kept by hand and then carefully and slowly taken away millimetre, pulling from the surface towards the other end drops, if in the course of this operation, the adhesion was so strong that the end of the drop was in danger of destruction, when he was drawn, sharp blade (cutter) used for the application of the section perpendicular to the direction of pulling drops down to the surface of the substrate and thus separated section drops. Cuts of this kind were repeated, if necessary, in the course of continuous pulling with intervals of 2 to 3 mm in This way the entire drop was delayed and/or cut off from the substrate. The adhesive properties were evaluated on the basis of the cured adhesive that remained on the surface of the substrate after removal drops (cohesive fracture), this was accompanied by an estimation of the cohesive fraction of the adhesion surface in accordance with the following scale:

1 = cohesive destruction Bo is her than 95%

2 = cohesive destruction from 75% to 95%

3 = cohesive destruction from 25% to 75%

4 = cohesive fracture less than 25%

The test results with the values of the cohesive fracture less than 75%, in other words assessment 3 and 4 are considered inadequate. The samples, adhesive properties which were assessed value of 4, that is, samples with cohesive destruction less than 25%, were subsequently ignored and is listed in the table labeled "n.d.", meaning of "undefined".

The tensile strength, elongation at break and modulus at elongation from 0% to 100% was determined in accordance with DIN EN 53504 (rate of pulling of 200 mm/min) films with a thickness of 2 mm, which were solidified at 23°C and 50% relative humidity for 14 days.

The hardness And the shore was determined according to DIN 53505.

Obtaining the silane-functional polyurethane polymer (P1-1)

In nitrogen atmosphere to 1000 g of Acclaim® Polyol 12200 (Bayer MaterialScience AG, Germany; polyoxypropylene with low contents Mineola; HE number 11.0 mg KOH/g, water content about 0.02 wt.%), of 38.4 g of isophorone diisocyanate (IPDI; Vestanat® IPDI, Evonik Degussa GmbH, Germany), 270,1 g diisodecylphthalate (DIDP; Palatinol® Z, BASF SE, Germany) and 0.12 g of dilaurate di-n-butyanova (Metatin® K 712, Acima AG, Switzerland) was heated to 90°C with continuous stirring and kept at this temperature until such time as the designated t is trevanian the content of isocyanate groups reached a value of 0.40 wt.%. Then added with stirring to 39.5 g of diethyl N-(3-triethoxysilylpropyl)aminosuccinic and the mixture was stirred at 90°C for 4 hours until the free isocyanate became no longer detectable by IR spectroscopy. The product was cooled to room temperature and maintained in the absence of moisture (theoretical polymer content = 80%).

Diethyl N-(3-triethoxysilylpropyl)aminosuccinic received as follows: 51,0 g 3-aminopropyltrimethoxysilane (Silquest® A-1110, Momentive Performance Materials Inc., USA) was administered as initial load. At careful hashing is 49.0 g of diethyl maleate (Fluka Chemie GmbH, Switzerland) was added slowly at room temperature and the mixture was stirred at room temperature for 2 hours.

MS prepolymer (P3-1)

The prepolymer S203H available from Kaneka Corporation, Japan.

Getting pasta urea thickener

In a vacuum mixer was downloaded 1000 g diisodecylphthalate (Palatinol® Z) and 160 g of 4,4'-difenilmetana diisocyanate (Desmodur® 44 MCL, Bayer MaterialScience AG, Germany) and the initial load was carefully heated. Then 90 g of monomethylamine was slowly added dropwise with vigorous stirring. The resulting white paste was stirred for another hour under vacuum and cooled. Pasta urea thickener contains 20 wt.% urea thickener 80 wt.% diisodecylphthalate.

Getting adhesivo the

Getting the basic structure

In a vacuum mixer, in accordance with mass proportions shown in table 1, the polymer VINYLTRIMETHOXYSILANE (Dynasylan® VTMO, Evonik Degussa GmbH, Germany), titanium dioxide (Kronos® 2430, Kronos Titan GmbH, Germany), paste urea thickener, crushed chalk (Omya® 5GU, Omya GmbH, Germany), optional N-2-amino-ethyl-3-aminopropyltrimethoxysilane (Dynasylan® DAMO-T, Evonik Degussa GmbH, Germany) or mercaptomerin (Dynasylan® MTMO, Evonik Degussa GmbH, Germany) and optional DBTDL, Metatin® K712 and DIDP (Palatinol® Z) or organotitanate (Tyzor® IBAY, DuPont, USA) were processed to a homogeneous paste, which was sustained in the absence of moisture.

Results

1. Composition for adhesive bonding, sealing and coating of substrates, including
a) at least one silane-functional polymer P is a silane-functional polyurethane polymer or can bytevalue reaction gidrauxilirovania polymers, having a terminal double bond;
b) at least one organosilane, which contains at least one sulfur atom selected from the group comprising organosilane formula (II), organosilane formula (III) and organosilane formula (IV)



where the radical R⁴means an alkyl group having 1 to 8 C atoms, more particularly methyl group;
the radical R⁵means an alkyl group having 1 to 5 C atoms, more particularly a methyl group or ethyl, or isopropyl, or acyl, more specifically acetyl group;
the radical R⁶means a linear or branched, optionally cyclic, alkylenes group having from 1 to 20 C atoms, optionally with aromatic fragments, and optionally one or more heteroatoms, more specifically with nitrogen atoms;
X is S or S₂or S₄and
b represents the value 0, or 1, or 2,
and
C) at least one organotitanate having ligands attached to the titanium atom through a linking oxygen-titanium, these ligands are selected from the group consisting of alkoxygroup, sulfate groups, carboxylate groups, dialkylphosphate group and acetylacetonate group.

2. The composition according to claim 1, characterized in that the silane-functional polymer P sod is rgit end groups of the formula (I)

where R¹means an alkyl group having 1 to 8 C atoms, more particularly a methyl group or ethyl;
R²means acyl or alkyl group having 1 to 5 C atoms, more particularly a methyl group, or ethyl, or isopropyl;
R³means a linear or branched, optionally cyclic alkylenes group having from 1 to 12 C atoms, optionally with aromatic fragments, and optionally one or more heteroatoms, more particularly with one or more nitrogen atoms; and
and represents the value 0, or 1, or 2, more specifically the value 0.

3. The composition according to claim 1, characterized in that organosilane, which contains at least one atom of sulfur, is organosilanes formula (II),
where the radical R⁵means a methyl group or ethyl;
the radical R⁶means linear alkylenes group having from 1 to 10, more specifically, has 3 atoms, and
b represents the value 0.

4. The composition according to any one of claims 1 and 2, characterized in that organotitanate contains at least one multidentate ligand.

5. The composition according to claim 4, characterized in that organotitanate is organotitanate formula (V)

where the radical R⁷means a hydrogen atom or a linear or branched alkyl group having the t 1 to 8 C atoms, more specifically methyl group;
the radical R⁸means a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms, which optionally contains heteroatoms, more particularly a hydrogen atom;
the radical R⁹means a hydrogen atom or alkyl group having from 1 to 8, more particularly having 1 to 3 C atoms, or a linear or branched alkoxygroup having from 1 to 8, more particularly having 1 to 3 C atoms;
the radical R¹⁰means a linear or branched alkyl radical having from 1 to 20 atoms, more specifically radical isobutyl or isopropyl, and
n represents the value 1 or 2, more specifically 2.

6. The composition according to any one of claims 1 and 2, characterized in that the proportion of organosilane is 0.1-7 wt.%, more specifically 0.2 to 4 wt.%, preferably 0.4 to 2 wt.% the whole composition.

7. The composition according to any one of claims 1 and 2, characterized in that the proportion of organotitanate is 0.1-10 wt.%, more specifically 0.1 to 4 wt.%, preferably 0.1 to 3 wt.% the whole composition.

8. The composition according to any one of claims 1 and 2, characterized in that it further contains at least one filler.

9. The composition according to any one of claims 1 and 2, characterized in that the proportion of the filler is 10 to 70 wt.%, more specifically 15-60 wt.%, preferably 25-60 wt.% the whole composition.

10. The use of a composition according to any of the at one of claims 1 to 9 as adhesive, sealant or compositions for obtaining coatings.

11. The use of claim 10 as an adhesive or sealant for bonding or sealing without primer for porous substrates, more specifically, a porous mineral substrates.

12. A method of adhesive bonding two substrates S1 and S2, comprising the steps:
i) applying the composition according to any one of claims 1 to 9 on the substrate S1 and/or a substrate S2;
ii) contacting the substrates S1 and S2 via the applied composition during setting time of the composition;
iii) curing the composition by means of water, more specifically, water in the form of atmospheric moisture;
the substrates S1 and S2 are identical or different from each other.

13. The method according to item 12, wherein at least one of the substrates S1 or S2 are selected from the group consisting of concrete, mortar, brick, tile, plaster, natural stone, such as granite or marble, glass, ceramic, metal or alloy of metals, wood, plastic, and lacquer.

14. Method of sealing or coating, comprising the steps:
i) applying the composition according to any one of claims 1 to 9 on the substrate S1 and/or between two substrates S1 and S2;
ii) curing the composition by means of water, more specifically, water in the form of atmospheric moisture;
the substrates S1 and S2 are identical or different from each other.

15. The method according to 14, characterized in that h is on at least one of the substrates S1 or S2 are selected from the group consisting of concrete, mortar, brick, tile, plaster, natural stone, such as granite or marble, glass, ceramic, metal or alloy of metals, wood, plastic, and lacquer.

16. Product related, sealed or covered with a method according to any of p-15.

17. The product according to item 16, characterized in that the product is a building structure, more specifically the building structure of the building or civil construction.