MXPA99009360A - Polyurethane resins modified with silano, unprocediment for its preparation and its use as curable resins by the hume - Google Patents

Abstract

The present invention relates to moisture curable resins having a content of alkoxysilane groups (calculated as Si, MW 28) of 0.2 to 4.5% by weight, based on the weight of the curable resins by the moisture, and which optionally contain hydroxy groups, wherein the alkoxysilane groups are incorporated as the reaction products at an equivalent NCO / OH ratio of 0.5: 1.0 to 1.0: 1.0 of i) a polyol having a functionality of at least 4 and an equivalent weight of at least 200 with ii) a compound containing urea, isocyanate and alkoxysilane groups corresponding to formula I, The present invention also relates to a process for preparing these curable resins by moisture, with coating, adhesive or sealant compositions containing these resins as a binder and with the compounds containing urea, isocyanate and alkoxysilane groups used to prepare these resins

Description

POLYURETHANE RESINS MODIFIED WITH SILANO, A PROCEDURE FOR ITS PREPARATION AND ITS USE AS RESINS CURABLE BY MOISTURE BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to moisture curable resins containing alkoxysilane groups and, optionally, hydroxy groups, which can be cured in the presence of moisture to form coatings, adhesives and sealants, with a process for its production and with the compounds containing urea, isocyanate and alkoxysilane groups used to prepare the curable resins by moisture. Description of the Prior Art It is known that polyurethane resins are curable in the presence of atmospheric moisture to form polyurea coatings. During the curing mechanism, an isocyanate group reacts with moisture to form an amino group, which then reacts with another isocyanate group to form a urea. One of the disntages of these resins curable by moisture is that the curing mechanism is relatively slow. It has been suggested in US Pat. 3,420,800 and 3,567,692 that the speed of moisture curable polyisocyanates can be increased by incorporating aldimines or ketimines. It is said that the reaction of moisture with an aldimine or ketimine to form the corresponding amine is faster than the reaction of moisture with an isocyanate group to form an amine. A drawback of the use of aldimines and ketimines to accelerate the curing of polyisocyanates is that it requires the preparation of an additional component and requires some type of dosing equipment to ensure that the two components are mixed in the proper proportions. Accordingly, there is a need to have moisture curable resins that do not require a coreactant. Said resins have been described in US Pat. 5,364,955 and 5,766,751, which describe silane-terminated resins which have been prepared by reacting NC0 prepolymers with silane aspartates to form urea or hydantoin groups. Silane aspartates are prepared by initial reaction of amino-functional silanes with esters of maleic or fumaric acid. The silane aspartates then react with NC0 prepolymers to form the curable resins by moisture. - One of the drawbacks of this process is that it is not possible to prepare the silane-containing resins from higher functional polyols. When these polyols react with polyisocyanates, primarily diisocyanates, gelation frequently occurs due to chain extension, even at equivalent ratios of NC0 / 0H of 2: 1. U.S. Pat. US 5,162,426 describes the reaction of isocyanatoalkyltrialkoxysilanes with hydroxy-functional ethylenically unsaturated monomers and the subsequent polymerization of these unsaturated monomers with other unsaturated monomers to form silane-functional polymers. One drawback of these resins is the cost of the isocyanatoalkyltrialkoxysilanes. Accordingly, it is an object of the present invention to provide silane-containing resins based on high functionality polyol, which do not suffer from the drawbacks of the prior art.

This object can be achieved with the moisture-curable resins according to the present invention and the process for their preparation, which are described below in more detail. SUMMARY OF THE INVENTION The present invention relates to moisture curable resins having an alkoxysilane group content (calculated as Si, MW 28) of 0.2 to 4.5% by weight based on the weight of the curable resins. by moisture, and, if necessary, contain hydroxy groups, where the alkoxysilane groups are incorporated as reaction products at an NC0 / 0H equivalent ratio of 0.5: 1.0 to 1.0: 1.0 of i) a polyol having a functionality of at least 4 and an equivalent weight of at least 200 with ii) a compound containing urea, isocyanate and alkoxysilane groups corresponding to formula I R-, O 1 II (X) 3 -Yes-Y-N-C- -NH- -R-NCO (I) where X represents identical or different organic groups that are inert to the isocyanate groups below 100 ° C, provided that at least one of these groups is an alkoxy group; Y represents a linear or branched alkylene radical containing from 1 to 8 carbon atoms; R represents the residue obtained by removing the isocyanate groups of a mono-richer polyisocyanate or a polyisocyanate adduct containing n + 1 isocyanate groups; Ri represents an organic group which is inert to the isocyanate groups at a temperature of 100 ° C or less, and n is an integer from 1 to 3. The present invention also relates to a process for preparing these resins curable by moisture , with coating, adhesive or sealant compositions containing these resins as a binder and with compounds containing urea, isocyanate and alkoxysilane groups used to prepare these resins. DETAILED DESCRIPTION OF THE INVENTION To prepare the curable resins by moisture according to the present invention, high functionality polyols are reacted with compounds containing isocyanate, urea and alkoxysilane groups. These latter compounds can be prepared by reacting an α-polyisocyanate with an amino-functional alkoxysilane to form a compound containing an isocyanate group and one or more urea and alkoxysilane groups. Moisture-curable resins have a ~~ "" -Tm "" content in groups ~ alkoxysilane (calculated as Si, MW 28) of 0.2 to 4.5% by weight, preferably 0.2 to 4% and, more preferably, from 0.5 to 3.5%, and b) optionally, a hydroxyl group content - calculated as OH, MW 17 - of less than 2% by weight, preferably less than 1% by weight. % by weight and, more preferably, less than 0.2% by weight As suitable compounds containing isocyanate, urea and alkoxysilane groups, which can be used to prepare the resins curable by moisture, those corresponding to the formula are included I wherein X represents identical or different organic groups which are inert to the isocyanate groups below 100 ° C, provided that at least one of these groups is an alkoxy group, preferably alkyl or alkoxy groups having from 1 to 4 carbon atoms and, more preferably, alkoxy groups; Y represents a linear or branched alkylene radical containing from 1 to 8 carbon atoms, preferably a linear radical containing _ from 2 to 4 carbon atoms or a branched radical containing from 5 to 6 carbon atoms, more preferably a linear radical containing 3 carbon atoms; R - represents the residue obtained by removing the isocyanate groups from a monomeric polyisocyanate or a polyisocyanate adduct containing n + 1 isocyanate groups, preferably a monomeric polyisocyanate, more preferably a monomeric diisocyanate and, more preferably, a monomeric diisocyanate containing groups isocyanate aliphatic and / or cycloaliphatically bound; i represents an organic group which is inert to the isocyanate groups at a temperature of 10TJ ° C or less, preferably an alkyl, cycloalkyl or aromatic group having from 1 to 12, preferably from 1 to 8, carbon atoms, or Ri can also represent a group corresponding to the formula II _ * "-Y-Si- (X) 3 (ID and n is an integer from 1 to 3, preferably 1 or 2 and, more preferably, 1. The compounds in wherein X represents methoxy, ethoxy or propoxy groups, more preferably methoxy or ethoxy groups and, more preferably, methylene groups are suitable compounds containing alkoxysilane groups and amino groups, which can be used to prepare the compounds of formula I, those corresponding to formula III, where Ri HN-Y-Si- (X) 3 (III) where X, Y, Ri and n are as previously defined As examples of suitable aminoalkylalkoxysilanes corresponding to formula IV which contain secondary amino groups io include N-phenylaminopropyltrimethoxysilane (available as A-9669 from Osi Specialties, itco), bis (-trimethoxysilylpropyl) amine (available as A-1170 from OSi Specialties, Witco), N-acyclohexylaminopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane and the corresponding alkyldiethoxy and al-quyldimethoxysilanes. Especially preferred compounds containing isocyanate, urea and alkoxysilane groups are those corresponding to formula IV where X, Y, R and n have been previously defined and Z represents COOR5 or an aromatic ring, preferably COOR5; R2 and R5 are identical or different and represent organic groups which are inert to the isocyanate groups at a temperature of 100 ° C or less, preferably alkyl groups having from 1 to 9 carbon atoms, more preferably methyl, ethyl or butyl, and R3 and R are identical or different and represent hydrogen or organic groups that are inert to the isocyanate groups at a temperature of 100 ° C or less, preferably hydrogen. The compounds of formula IV are prepared by reaction of polyisocyanates with compounds corresponding to the formula V-COOR2 Z-CHR3-CR4-NH-Y-SÍ- (X) 3 (V) where X, Y, Z, R, R2, R3, R4, R5 and n are as previously defined. ~ The compounds of formula V are prepared by reaction of aminoalkylalkoxysilanes corresponding to formula VI H2N-Y-Si- (X) 3 (VI) where X and Y are as previously defined, with maleic acid esters, fumaric or cinnamic corresponding to formula VII Z-CR3 = CR4-COOR2 (VII). Examples of suitable aminoalkylalkoxysilanes - of formula VI include 2-aminoethyldimethyl-oxysilane, 6-aminohexyl-taxhoxylane, 3-aminopropyl-t-methoxysilane, 3-aminopropyltriethoxysilane, 3-aminopro-p-methyldiethoxysilane, 5-aminopentyltrimethoxysilane, 5-aminopentyltriethoxysilane, 3-aminopropyltrisisopropoxy- lane and 4-amino-3, 3-dimethylbutyldimethoxymethylsilane. 4-Amino-3, 3-dimethylbutyldimethoxysilane is preferred and 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are especially preferred. Examples of optionally substituted maleic, fumaric or cinnamic acid esters suitable for use in the preparation of the polyaspartates include dimethyl, diethyl, dibutyl (eg, di-n-butyl), diamyl and di-2 esters. -ethylhexyl and mixed esters based on the mixture of these and / or other alkyl groups of maleic and fumaric acids and the methyl, ethyl and butyl esters of cinnamic acid, and the corresponding esters of maleic, fumaric and cinnamic acid substituted by methyl in position 2 and / or 3. The dimethyl, diethyl and dibutyl esters of maleic acid are preferred and diethyl and dibutyl esters are especially preferred The reaction of primary amines with esters of maleic, fumaric or cinnamic acid to form the aspartates - Cough of formula V is known and is described, for example, in U.S. Patent 5,364,955, here incorporated by reference. n of the aspartates may be carried out, for example, at a temperature of 0 to 100 ° C usando___los. starting materials in proportions such that at least 1, preferably 1, double bond is present for each primary amino group. The excess of the starting materials can be removed by distillation after the reaction. The reaction can be carried out with or without a solvent, but the use of solvent is less preferred. If a solvent is used, the dioxane is an example of a suitable solvent. The compounds of formula V are colorless to light yellow. They can react with monomers and / or polyisocyanate adducts to form the compounds containing isocyanate, urea and alkoxysilane groups without further purification. Polyisocyanates suitable for preparing the compounds containing isocyanate, urea and alkoxysilane groups are selected from onomeric diisocyanates and polyisocyanate adducts having an average functionality of 2 to 4, preferably 2. Suitable monomeric diisocyanates can be represented by the formula R (NCO) ) 2 where R is as previously defined. The monomeric polyisocyanates have a molecular weight of about 112 to 1,000, preferably about 140 to 400, and include those in which R represents a divalent aliphatic hydrocarbon group having 4 to 40, preferably 4 to 18, carbon atoms., a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a di-valent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having from 6 to 15 carbon atoms . Examples of suitable organic diisocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene di-socianate, 2,2,4-tpmethyl-1,6-hexamethylene diisocyanate, 1,12-dodecyanate diisocyanate. methylene, cyclohexane-1, 3 - and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or DIIF) , bis (4-isocyanatocyclohexyl) methane, 2,4'-dicyclohexyl ethane diisocyanate, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, bis (4-isocyanato-3-methylcyclohexyl) methane, diisocyanate a, a, a ', a' -tetra-methyl-1,3- and / or -1, 4-xylylene, l-isocyanato-l-methyl-4 (3) -isocyanatomethylcyclohexane, 2,4- diisocyanate and / or 2,6-hexahydrotoluylene, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluylene diisocyanate, 2,4- and / or 4-diisocyanate, 4'-diphenylmethane, 1,5-diisocyanatophthalene and mixtures thereof. Polyisocyanates containing 3 or more isocyanate groups, such as 4-isocyanatomethyl-1, 8-octamethylene diisocyanate, and aromatic polyisocyanates, such as 4,4 ', 4', 4"-triphenylmethane triisocyanate and polyphenylenepolymethylene polyisocyanates obtained by phosgenation of aniline / formaldehyde condensates: Preferred organic diisocyanates include 1,6-hexamethylene di-isocyanate, l-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or DIIF), bis ( 4-isocyanatocyclohexyl) methane, 1-isocyanato-l-methyl-4 (3) isocyanatomethylcyclohexane, 2,4- and / or 2,6-toluylene diisocyanate and 2,4-and / or 4-diisocyanate. According to the present invention, the polyisocyanate component can also be present in the form of an adduct of polyisocyanates Suitable adducts of polyisocyanates are those containing isocyanurate, uretdione, biuret, urethane, allophanate, carbodiimide and / or oxadiazine-trio groups na, such as those described in US Pat. 5,668,238, incorporated herein by reference. Preferred polyisocyanate adducts are polyisocyanates containing isocyanurate groups, biuret groups, allophanate groups and / or uretdione groups, especially those prepared with the preferred monomeric diisocyanates. Suitable polyols for preparing the moisture-curable resins according to the invention have an average hydroxy functionality of at least 4, preferably from 4 to 200 and, more preferably, from 7 to 100, and an equivalent weight (determined by end-group analysis ) of at least 200, "preferably from 200 to 5,000, more preferably from 200 to 2,500 and, more preferably, from 200 to 1,000." - Examples of the high molecular weight polyester polyols compounds, polyether polyols, polyhydroxy polycarbonates, polyhydroxypolyacetals, polyhydroxypolyacetamates, polyhydroxypolyester amides and polyhydroxypoly thioethers Polyacrylate polyols, polyesters, polyols, polyether polyols and polyhydroxypolycarbonates, especially polyacrylate polyols, are preferred. , it is necessary to use starting materials that have functionalities greater than 2 to prepare the polycondensation polymers. substantially, the compounds having higher functionalities are low molecular weight alcohols used to prepare these polymers. Examples include trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, pentaerythritol, mannitol, sorbitol and sucrose. Polyethers which have been obtained by reaction of starting compounds containing amino groups may also be used, but are less preferred for use in the present invention. Suitable starting amine compounds include ethylenediamine, diethylenetria-mihaT and triethylenetetraamine. Examples of suitable polyhydroxy compounds of high molecular weight polyols include polyester -prepared with low molecular weight alcohols and acids "polybasic carboxylic acids such as" adipic acid, sebacic acid, phthalic acid, isophthalic acid, te-- trahidroftálico acid . hexahydrophthalic, maleic acid, the "anhydrides of these acids and mixtures of these acids and / or acid anhydrides are also suitable polylactones having hydroxyl groups, particularly poly -. caprolactone, for producing the prepolymers are also suitable for preparing moisture curable resins by, the polyether polyols which can be obtained in known manner by alkoxylation of suitable starter molecules. examples of suitable starter molecules include the known diols and higher functional alcohols, water, polyamines which have organized cas two or more NH bonds and their mixtures. Two alkylene esters suitable for the alkoxylation reaction are preferably ethylene oxide and / or propylene oxide, which can be used in sequence or as a mixture. Other suitable polyols include polycarbonates having hydroxyl groups, which can be produced by. reaction: diol and higher functionality alcohols with phosgene or diaryl carbonates, such as diphenyl carbonate. Other details related to low molecular weight compounds and starting materials and methods for preparing high molecular weight polyhydroxy compounds are described in US Patent 4,701,480, incorporated herein by reference. high molecular weight amine functional compounds, which can be "prepared by converting the terminal hydroxy groups of the previously described polyols to amino groups, and the high molecular weight polyaspartates and polyaldimines described in US Pat. 5,243,012 and 5,466,771, respectively, incorporated herein by reference. Resins curable by moisture are preferably prepared in two stages. In the first step, the compounds containing isocyanate, urea and alkoxysilane groups are prepared by reaction of a polyisocyanate with an amino-functional alkoxysilane to form a compound containing an isocyanate group and one or more alkoxysilane groups. To ensure that the products contain an isocyanate group, the number of equivalents of amino groups is one less than the number of equivalents of isocyanate groups. For example, one mole of triisocyanate is reacted with "two moles of aminosilane and one mole of diisocyanate is reacted with ~ UNAT ~ mol of aminosilane. When diisocyanates as starting materials are used, it is possible to react an excess of diisocyanate and subsequently removing any diisocyanate not reacted by distillation in a known manner Even when one mole of diisocyanate reacts with one mole of aminosilane, "unreacted diisocyanate may be present; however, the unreacted diisocyanate can be removed by distillation. According to the present invention, the special type of urea groups formed by reaction of the amino-functional compounds containing alkoxysilane groups and aspartate groups (ie those corresponding to formula V) with the polyisocyanate component can be converted to hydantoin groups of a known manner by heating the cora-posts at elevated temperatures, possibly in the presence of a catalyst. Therefore, the term "urea groups" is also intended to include other compounds containing the group N-CO-N, such as hydantoin groups. If it is desired to convert the urea groups to hydantoin groups, it is preferred to form the hydantoin groups after the formation of the moisture-curable resins according to the second stage of the two-step process. This is due to the fact that, during the formation of the hydantoin groups, a monoalcohol is liberated which can react with the isocyanate group of the compounds containing isocyanate, urea and alkoxysilane groups. This reaction prevents the isocyanate groups from being available for the reaction with the high functionality polyols in the second stage of the two-step process. The moisture-curable resins are obtained in the second step by reacting the compounds containing an isocyanate group and one or more alkoxysilane groups with the high functionality polyol at an equivalent NCO / OH ratio of 0.5: 1.0 to 1.0: 1.0, preferably, 0.7: 1.0 to 1.0: 1.0 and, more preferably, 0.95: 1.0 to 1.0: 1.0. The reaction of the first step to form the urea groups is carried out at a temperature of 10 to 120 ° C, preferably 20 to 100 ° C and, more preferably, 40 to 80 ° C, while the reaction of the The second stage, which forms urethane groups, is carried out at a temperature of from 20 to 150 ° C, preferably from 50 to 120 ° C and, more preferably, from 60 to 100 ° C. The compounds of the present invention are suitable for use in one-component coating, adhesive or sealant compositions, which can be cured in the presence of atmospheric moisture by "silane polycondensation" from the hydrolysis of alkyl groups. -Lane to form Si-OH groups, which then react to form siloxane groups (Si-O-Si). Suitable metal, acid or basic catalysts can be used to promote the curing reaction. Examples include acids such as parato-luenesulfonic acid, metal salts such as di-butyltin dilaurate, tertiary amines such as triethylamine or triethylene diamine and mixtures of these catalysts. The low molecular weight basic aminoalkyltrialkoxysilanes, such as those represented by formula IV, also accelerate the hardening of the compounds according to the invention. The one component compositions generally have a solids content of 30 to 80%, preferably 40 to 60%, based on the weight of the composition of a component. Suitable organic solvents include those known from the chemistry of polyurethanes. . The compositions may also contain known additives, such as: leveling agents, wetting agents, flow control agents, antiscratching agents, foaming agents, fillers (such as silica, aluminum silicates and high boiling waxes). ), viscosity regulators, plasticizers, pigments, dyes, UV absorbers and stabilizers against thermal and oxidative degradation. The one-component compositions can be applied to any desired substrate, such as wood, plastic, leather, paper, textiles, glass, ceramics, plaster, masonry, metals and concrete. They can be applied by standard methods, such as spray coating, extension coating, flood coating, casting, dip coating, roller coating. The coating compositions can be transparent or pigmented. The coating compositions can be cured at room temperature or at elevated temperatures of 50 to 150 ° C, preferably from 60 to 100 ° C. Preferably, the "moisture curable resins are cured at ambient temperatures." The invention is further illustrated, but without intending to limit it, by the following examples, in which all parts and percentages are by weight, unless "something" is specified different. EXAMPLES Silane Aspartate 1 - N- (3-tpmethoxysilylpropyl) aspartic acid diethyl ester 1,483 parts (8.27 equiv.) Of 3-aminopropyltrimethoxysilane were added to a 5 liter flask equipped with stirrer, thermocouple, nitrogen inlet and addition funnel with condenser. 1423.2 parts (8.27 equiv.) Of diethyl maleate were added dropwise over a period of 2 hours. The reactor temperature was maintained at 25 ° C during the addition. The reactor was maintained at 25 ° C for an additional 5 hours, at which time the product was poured into glass containers and sealed under a blanket of nitrogen. After one week, the unsaturation number was 0.6, which indicated that the reaction had been completed at -99%. The product, N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester, had a viscosity of 11 mPa.s at 25 ° C. Acrylic Polyol I A polyacrylate polyol having an equivalent weight of OH of 415, a functionality of about 95, an OH content of 4.1% and an acid number of < 10 and prepared from 40.5% styrene, 31.4% hydroxyethyl methacrylate, 23.7% butyl acrylate, 0.9% acrylic acid and 3.5% of di-tert-butyl peroxide. Polyester polyol I A polyester polyol having an OH equivalent weight of 770, an OH content of 2.2% and a functionality of approximately 5 and prepared from 41.2% trimethylolpropane, 10.8% adipic acid, 28.5% hexahydrophthalic anhydride and 19.5% 2-ethylhexanoic acid. Polyol 1 A polyacrylate / polyester polyol mixture having an equivalent weight of 500, a functionality of about 65, an OH content of 3.40% and an acid number of < 10, present as a 70% solution in butyl acetate and containing 42% acrylic polyol I and 28% polyester polyol I. Example 1 - Preparation of moisture curable resin 1 222.0 parts (2 , 0 equiv.) Of isophorone diisocyanate at room temperature in a reaction flask equipped with stirrer, thermocouple, nitrogen inlet ~ and addition funnel with condenser. 366.6 parts (1 equiv.) Of silane aspartate 1 was added to the reaction flask through the addition funnel to control the exotherm for the formation of urethane groups by keeping the reaction temperature below 30 ° C. The addition was completed after one hour and fifteen minutes. The reaction mixture was heated to 60 ° C and then 561.8 parts of polyol 1 were added to the reaction mixture, followed by stirring for two hours until no isocyanate groups could be detected by IR. After cooling, 252.2 parts of butyl acetate were added to obtain a final solids content of 70% and a viscosity of 6,300 mPa.s at 25 ° C. Example 2 - Preparation of moisture curable resin 2 168.0 parts (2.0 equiv.) Of 1,6-hexamethylene diisocyanate were charged at room temperature in a reaction flask equipped with stirrer, thermocouple, inlet nitrogen and addition funnel with condenser. 366.6 parts (1 equiv.) Of silane aspartate 1 was added to the reaction flask through the addition funnel to control the exotherm for the formation of urethane groups by keeping the reaction temperature below 30 °. C. The addition was completed after one hour and fifteen minutes. The reaction mixture was heated to 60 ° C and 561.8 parts of polyol 1 were added to the reaction mixture, followed by stirring for two hours until no isocyanate group could be detected by IR. After cooling, 229.1 parts of butyl acetate were added to obtain a final solids content of 70% and a viscosity of 7,700 mPa.s at 25 ° C. Example 3 - Preparation of moisture curable resin 3 132.0 parts (1.0 equiv.) Of bis (4-isocyanatocyclohexyl) methane were charged at room temperature in a reaction flask equipped with a stirrer, a thermocouple, an inlet of nitrogen and an addition funnel with condenser. 183.3 parts (0.5 equiv.) Of silane aspartate 1 were added to the reaction flask through the addition funnel to control the exotherm for the formation of urethane groups by keeping the reaction temperature below 30 ° C. The addition was completed after one hour and fifteen minutes. The reaction mixture was heated to 60 ° C and then 280.9 parts of polyol 1 was added to the reaction mixture, followed by stirring for two hours until no isocyanate groups could be detected by IR. After cooling, 135.2 parts of butyl acetate were added to obtain a final solids content of 70%. The solution seemed to be a rubbery solid that did not flow. Example 4 - (Comparison) Preparation of an NCO prepolymer 280 parts (0.5 equiv.) Of polyol 1 and 126 parts of butyl acetate solvent were charged into a round bottom flask equipped with stirrer, thermometer, nitrogen inlet and addition funnel. 111 parts (1, 0 eq.) Of isophorone diisocyanate through the addition funnel over a period of three hours, while maintaining the reaction at 25 ° C to maximize the "differential reactivity between the two isocyanate groups of isophorone diisocyanate. After the addition was complete, the reaction was maintained at 25 ° C for a further five hours when the isocyanate content per titration was found to be 6.93% (theory, 4.06%) The reaction mixture was gelled after being stored for 96 hours at room temperature Silane aspartate was not added Example 5 - (Comparison) Preparation of an NCO prepolymer 55 parts (0.5 eq.) of isophorone diisocyanate were charged in a Round bottom flask equipped with stirrer, thermometer, nitrogen inlet and addition funnel The reaction was maintained at 25 ° C to maximize the differential reactivity between the two isocyanate groups of isophorone diisocyanate, 140 parts (0.25 equ iv.) of polyol 1 and 63 parts of "butethyl acetate solvent through the addition funnel over a period of one hour, while maintaining the reaction at 25 ° C to maximize the differential reactivity between two isocyanate groups of isophorone diisocyanate. After the addition was complete, the reaction was maintained at 25 ° C for an additional 6.5 hours. The reaction mixture was gelled after being stored for 14 hours at room temperature. Silane aspartate was not added. The above comparative examples demonstrate the need to prepare the finished resins in silane by an initial reaction of the isocyanate component with the silane aspartate to form an intermediate, which contains isocyanate and silane aspartate groups, which then reacts with the high functionality polyol to form the resin curable by moisture. This method is demonstrated in the examples according to the invention. Attempts to prepare these compounds by initially reacting the isocyanate component with the high functionality polyol to form an NCO prepolymer and then reacting the prepolymer with the silane aspartate were unsuccessful.Preparation of a film with the curable resin moisture 1"" "Coated panels were prepared by adding one part of a 50:50 mixture of dimethyltin diacetate and diazobicyclooctane to 100 parts of moisture curable resin 1. The resin was emptied into a wet 5 mil film, which gave place to a dry film of approximately 3.5 mils. The coating was not sticky in two hours and had a F pencil hardness after one week. Although the invention has been described in detail "in" the foregoing for illustrative purposes, it should be understood that said detail has only those purposes and that those skilled in the art can make variations therein without departing from the spirit and scope of the invention. invention, except as may be limited by the claims. - "" _ _ _ -

Claims (4)

CLAIMS 1. A moisture curable resin having a content of alkoxysilane groups (calculated as Si, MW 28) of 0.2 to 4.5%, based on the weight of the resin curable by moisture and, if necessary, contains hydroxy groups, wherein the alkoxysilane groups are incorporated as the reaction product at an equivalent ratio of NCO / OH from 0.5: 1.0 to 1.0: 1.0 of i) a polyol having a functionality of ___ "__ nos 4 and an equivalent weight of at least 200 with ii) a compound containing urea, isocyanate and alkoxysilane groups corresponding to the formula IR, O (X) 3-Si-Y-N-C- H- R - CO (1) where "~": X represents identical or different organic groups that are inert to the isocyanate groups below 100 ° C, provided that at least one of these groups is an alkoxy group; Y . "represents a linear or branched alkylene radical containing from 1 to 8 carbon atoms; R represents the residue obtained by removing isocyanate groups from a monomeric polyisocyanate or a polyisocyanate adduct containing n + 1 isocyanate groups; R: L represents an organic group that is inert to isocyanate groups at a temperature of 100 ° C or less, and n is an integer from 1 to 3. 2. The compound curable by moisture of the
1. Claim 1, wherein said amino compound corresponds to z represents COOR5, R2 and R5 are identical or different and represent methyl, ethyl or butyl and R3 and R4 represent hydrogen. "" 5. The moisture curable resin of Claim 1, wherein R represents the residue obtained by removing the isocyanate groups of a monomeric polyisocyanate having n + 1 isocyanate groups and n is 1. 6. The resin curable by moisture of the
2. Claim 2, wherein R ^ "represents the residue obtained by removing the isocyanate groups of a monomeric polyisocyanate having n + 1 isocyanate groups and n is 1. 7. the moisture curable resin of
3. Claim 3, wherein R represents the residue obtained by removing the "isocyanate groups" of a monomeric polyisocyanate having n + 1 isocyanate groups and n is 1. 8. The moisture curable resin of
4. Claim 4, wherein R _ represents the residue obtained by removing isocyanate groups from a polyisocyanate. monomer having n + 1 isocyanate groups and n is 1. 9. A compound containing urea, isocyanate and alkoxysilane groups corresponding to formula IV where X represents identical or different organic groups that are inert to the isocyanate groups below 100 ° C, provided that at least one of these groups is an alkoxy group; Y represents a linear or branched alkylene radical which contains from 1 to 8 carbon atoms; Z represents C00R5 or an aromatic ring; R represents the residue obtained by removing the isocyanate groups of a monomeric polyisocyanate or a polyisocyanate adduct containing n + 1 isocyanate groups, - R2 and R5 are identical or different and represent organic groups which are inert to the isocyanate groups at a temperature of 100. ° C or less; R3 and R4 are identical or different and represent hydrogen or organic groups that are inert to the isocyanate groups at a temperature of 100 ° C or less, and n "is" 1 to 2. 10. The compound of Claim 9, wherein X - represents identical or different alkyl or alkoxy groups having from 1 to 4 carbon atoms, Y represents a linear alkylene radical containing from 2 to 4 carbon atoms, represents C00R5, R2 and R5 are identical or different and represent groups alkyl having 1 to 9 carbon atoms and R3 and R4 represent hydrogen. 11. The compound of Claim 9, wherein X represents identical or different alkoxy groups having from 1 to 4 carbon atoms, Y represents a linear alkylene radical containing 3 carbon atoms, Z represents COOR5, R2 and R5 are identical or different and represent methyl, ethyl or butyl and R3 and R4 represent hydrogen. 12. The compound of Claim 9, wherein R _. represents the residue obtained by removing isocyanate groups from a monomeric polyisocyanate having n + 1 isocyanate groups and n is 1. The compound of Claim 10, wherein R represents the residue obtained by eliminating the isocyanate groups of a monomeric polyisocyanate having n + 1 isocyanate groups and n is 1. The compound of claim 11, wherein R represents the residue obtained by removing the isocyanate groups of a monomeric polyisocyanate having n + 1 isocyanate groups and n is 1. 15. A process for the preparation of a moisture curable resin having a content of alkoxysilane groups (calculated as Si, PM 28) from 0.2 to 4.5% by weight, based on the weight of the resin curable by moisture, and which, eventually, "contains hydroxy groups, which consists of the reaction at an equivalent NCO / OH ratio of 0.5: 1.0. to "1.0: 1.0 of i) a polyol having a functionality of at least 4 and an equivalent weight of at least 200 with ii) a compound containing urea, isocyanate and alkoxysilane groups corresponding to formula I Rl OI li (X) 3-Si-Y-N-C-NH- -R-NCO (I) where X represents identical or different organic groups that are inert to the isocyanate groups below 100 ° C, provided that at least one of these groups is an alkoxy group, Y represents a linear or branched alkylene radical containing from 1 to 8 atoms carbon R represents the residue obtained by eliminating the isocyanate groups of a monomeric polyisocyanate or a polyisocyanate adduct containing n + 1 isocyanate groups, RL represents an organic group inert to the isocyanate groups at a temperature of 100 ° C or less and is 1 to 3. 16. The method of Claim 15, wherein said amino compound corresponds to formula IV where Z represents C00R5 or an aromatic ring, R and R5 are identical or different and represent organic groups that are inert to the isocyanate groups at a temperature of 100 ° C or less and R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to the isocyanate groups at a temperature of 100 C or less. The method of Claim 16, wherein X represents identical or different alkyl or alkoxy groups having from 1 to 4 carbon atoms, represents a linear alkylene radical containing from 2 to 4 carbon atoms, Z represents COOR5, R2 and Rs are identical or different and represent alkyl groups having from 1 to 9 carbon atoms and R3 and R4 represent hydrogen. The method of Claim 15, wherein R represents the residue obtained by removing isocyanate groups from a monomeric polyisocyanate having n + 1 isocyanate groups and n is 1. 19. The method of Claim 17, wherein R represents the residue obtained by eliminating the isocyanate groups of a monomeric polyisocyanate having n + 1 isocyanate groups and n - is 1. 20. A one-component, sealing or adhesive composition wherein the binder consists of the moisture curable resin of Claim 1.