COMPOSITION OF RESIN CURABLE BY MOISTURE, CURABLE COMPOSITION PRODUCED BY CONTACT OF THE COMPOSITION

专利摘要:
abstract "moisture-curable silicon polymer compositions with improved adhesion to concrete" a moisture-curable resin composition comprising (a) at least one moisture-curable polymer that has at least one hydrolyzable silyl group; (b) at least one hydrocarbilalkoxysilane; and (c) at least one silane adhesion promoter containing a glycidoxy group. the composition may also contain additives, including a catalyst to catalyze the reaction between the moisture-curable polymer having at least one hydrolyzable silyl group (a) with water under curing conditions, a filler, a plasticizer, and combinations thereof. the moisture-curable resin composition is useful in the production of adhesives, sealants and coatings for use in concrete applications without primer.
公开号:BR112013024938B1
申请号:R112013024938-2
申请日:2012-03-29
公开日:2020-03-10
发明作者:Misty W. Huang；Jeries I. Nesheiwat
申请人:Momentive Performance Materials Inc.；
IPC主号:

专利说明:

“COMPOSITION OF RESIN CURABLE BY MOISTURE, CURABLE COMPOSITION PRODUCED BY CONTACTING THE COMPOSITION, SEALANT, ADHESIVE OR COATING CURABLE BY MOISTURE, METHOD FOR THE TREATMENT OF A SUBSTRATE AND ARTICLE” Field of the invention [001] The present invention refers to compositions of moisture-curable resins, which after curing provide cured compositions with improved adhesion to non-immunized concrete substrates, when immersed in water for at least seven days. More particularly, the present invention relates to moisture-curable resin compositions, comprising silylated polymers, hydroxycarbaloxysilanes and silane adhesion promoters, and to moisture-curable sealant, adhesive and coating compositions containing these curable resin compositions moisture and articles made from these.
Background of the invention [002] Polymers with hydrolyzable silane termination are commonly used in the market for adhesives, sealants and coatings. This is at least partially attributed to its properties of environmental durability and adhesion to many substrates, such as glass, plastic and aluminum. Hydrolyzable silane-terminated polymers and their use in adhesives, sealants and coatings have been described in the art. Illustratively, US Patent No. 3,627,722 describes polyurethane sealants made from an isocyanate-terminated polymer, in which at least five percent of the isocyanate groups are end-blocked with trialkoxysil groups. US Patent No. 5,990,257 describes silylated polyurethanes prepared using extremely low unsaturation polyether polyols for the formation of the silylated polyurethane prepolymers. The '257 patent describes that these silylated polyurethanes have better mechanical properties after curing for a low-adhesion sealant. Likewise, US Patent No. 6,498,210 describes a silylated polyurethane polymer containing unreacted isocyanate groups or low molecular weight terminations. The '210 patent describes that these polymers provide improved tensile strength after curing. In addition, US Patent No. 6,001,946 describes a class of polymers terminated in polyurethane N-silylalkyl-aspartic acid ester and sealant formulations made from silylated polymers which are said to exhibit better resistance to breakage, elongation and resistance to tension. US Patent No. 6,001,946 describes curable silane-terminated polymers based on aminoalkylsilane maleate adducts. US Patent No. 7,319,128 describes polymers terminated in organyloxy silyl obtained by reacting hydroxyl terminated organic polymers with functional isocyanate silanes in the presence of a catalyst.
[003] Unfortunately, conventional coatings, adhesives and sealants based on these polymers terminated in hydrolyzable silane tend to have poor wet adhesion to non-immunized concrete substrates after being cured. Efforts have been made to improve the adhesion to non-immunized concrete substrates of products made from silylated polymers. Illustratively, US Patent 4,810,748 describes the use of an epoxy-functional silicone fluid additive for a silicone sealant to improve adhesion. US Patent 5,216,057 describes better wet adhesion of acrylic latex sealants over mortar that contain a polysiloxane oil emulsion. US Patent No. 6,602,964 describes the use of polysilsesquioxanes containing functional groups of mercapto and alkyl- to improve the adhesion of a silylated polyurethane composition. Similarly, US Published Patent Application No. 2007/0066768 describes silylated polyurethane compositions containing a mixture of silanes and polysiloxanes to improve adherence to concrete after exposure to water. Although these efforts have shown some improvement in adhesion to concrete without prime, these resin compositions tend to fail in the adhesive mode and have low resistance to peeling, when cured concrete compositions without prime are immersed in water for seven days or more.
[004] Therefore, there is a continuing need in the finished hydrolyzable silane polymers community for a resin composition that has a high peel strength and cohesive failure mode from non-immunized concrete substrates, which have been immersed in water during at least seven days. The present invention provides a solution to this need.
Summary of the invention [005] One aspect of the present invention relates to a moisture-curable resin composition comprising: (a) at least one moisture-curable polymer that has at least one hydrolyzable silyl group, (b) at least one hydro -carbilalcoxisilane, and (c) at least one silane adhesion promoter containing a glycidoxy group, in which (i) the amount of said component (b) present in the moisture-curable resin composition is from about 5 to about 35 weight percent based on the weight of said component (a); (ii) the amount of said component (c) present in the moisture-curable resin composition is about 1 to about 25 weight percent based on the weight of said component (a); (iii) the total amount of said component (b) and said component (c) present in the moisture-curable resin composition is about 10 to about 45 weight percent based on the weight of said component (a ); with the proviso that (i) the moisture-curable resin composition is substantially free of hydroxyl-terminated dimethyl siloxane; and (ii) the moisture-curable resin composition is substantially free of low molecular weight glycols.
[006] In an embodiment of the previous composition, the moisture-curable polymer (a) has the general formula (I): where: R1 is, independently, a monovalent or polyvalent organic polymer fragment having an average molecular weight of 500 to 25,000 grams per mol (g / mol); each occurrence of R 2 is, independently, a divalent hydrocarbilene group containing from 1 to 12 carbon atoms; each occurrence of A1 is independently selected from divalent oxygen (-0-), sulfur (-S-) or substituted nitrogen of structure (-) 2 NR3, where R3 is hydrogen, alkyl, alkenyl, arenyl, aryl, aralkyl , alkyl containing at least one ester functional group or -R2SiX1X2X3 group, where each R3, other than hydrogen, contains from 1 to 18 carbon atoms, and with the proviso that when A1 is an oxygen or sulfur, then A2 is ( -) 2NR3 and, when a is 0, then A1 is oxygen; each occurrence of A2 is independently selected from divalent oxygen (-0-), sulfur (-S-) or substituted nitrogen from structure (-) 2NR3, where R3 is hydrogen, alkyl, alkenyl, arenyl, aryl, aralkyl, alkyl containing at least one ester functional group or R2SiX1X2X3 group, where each R3, other than hydrogen, contains from 1 to 18 carbon atoms, and with the proviso that when A2 is oxygen or sulfur, then A1 is (-) 2 NR3; each occurrence of X1 is, independently, R4O-, in which each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl, and aralkyl groups, where each R4, other than hydrogen, contains from 1 to 18 carbon atoms and, optionally, contains at least one oxygen or sulfur atom; each occurrence of X 2 and X 3 is independently selected from the group consisting of R4 O- and R5 in which each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl, and aralkyl, wherein each R4, other than hydrogen, contains from 1 to 18 carbon atoms and, optionally, contains at least one oxygen or sulfur atom and each R5 is, independently, an alkyl group containing from 1 to 6 carbon atoms; and each occurrence of indices a and b is, independently, an integer, where a is 0 or 1 and b is 1 to 6.
[007] The hydrocarbilalcoxisilane (b) of the present invention is a compound of general formula (II): R6CH2CH2Si (CH3) c (OCH3) 3-c Formula (II) where c is 0 or 1, and R 6 is a group alkyl or an alkenyl group of 2 to 18 carbon atoms. The silane adhesion promoter (C) of the present invention is a Formula (III) compound of the general formula wherein d is 0, 1 or 2, and n is 2 to 6;
[008] In another aspect, the present invention is directed to a cured composition prepared from curing the above-mentioned moisture-curable composition.
[009] In yet another aspect, the present invention relates to sealants, adhesives and coatings that contain the above-mentioned moisture-curable composition.
[0010] In yet another aspect, the present invention relates to an article comprising a curable composition prepared from curing the aforementioned moisture-curable resin composition and a primerless concrete to which the curable resin composition moisture-cured is on.
[0011] These and other aspects will be apparent after reading the following detailed description of the invention.
Detailed description of the invention [0012] The present invention relates to a moisture-curable resin composition comprising: (a) at least one moisture-curable polymer having at least one hydrolyzable silyl group, (b) at least one hydrocarbyl-xysilane , and (c) at least one silane adhesion promoter, containing a glycidoxy group, where (i) the amount of said component (b) present in the moisture-curable resin composition is about 5 to about 35 percent weight percent based on the weight of said component (a); (ii) the amount of said component (c) present in the moisture-curable resin composition is about 1 to about 25 weight percent based on the weight of said component (a); (iii) the total amount of said component (b) and said component (c) present in the moisture-curable resin composition is about 10 to about 45 weight percent based on the weight of said component (a) ; with the proviso that (i) the moisture-curable resin composition is substantially free of hydroxyl-terminated dimethyl siloxane; and (ii) the moisture-curable resin composition is substantially free of low molecular weight glycols.
[0013] In one embodiment, the moisture-curable polymer (a) has the general formula (I): where: R 1 is, independently, a monovalent or polyvalent organic polymer fragment having an average molecular weight of 500 to 25,000 grams per mol (g / mol); each occurrence of R 2 is, independently, a divalent hydrocarbilene group containing from 1 to 12 carbon atoms; each occurrence of A1 is independently selected from divalent oxygen (-O-), sulfur (-S-) or substituted nitrogen from structure (-) 2NR3, where R3 is hydrogen, alkyl, alkenyl, arenyl, aryl, aralkyl, alkyl containing at least one ester functional group or -R2SiX1X2X3 group, where each R3, other than hydrogen, contains from 1 to 18 carbon atoms, and with the proviso that when A1 is oxygen or sulfur, then A2 is (-) 2NR3 and, when a is 0, then A1 is oxygen; each occurrence of A2 is independently selected from bivalent oxygen (-O-), sulfur (-S-) or substituted nitrogen from structure (-) 2NR3, where R3 is hydrogen, alkyl, alkenyl, arenyl, aryl, aralkyl, alkyl containing at least one ester functional group or -R2SiX1X2X3 group, where each R3, other than hydrogen, contains from 1 to 18 carbon atoms, and with the proviso that when A2 is oxygen or sulfur, then A1 is (-) 2 NR3 each occurrence of X1 is, independently, R4O-, in which each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl, and aralkyl groups, where each R4, different from hydrogen , contains 1 to 18 carbon atoms and, optionally, contains at least one oxygen or sulfur atom; each occurrence of X2 and X3 is independently selected from the group consisting of R4O- and R5 in which each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl, and aralkyl, in which each R4, unlike hydrogen, contains from 1 to 18 carbon atoms and optionally contains at least one oxygen or sulfur atom and each R 5 is, independently, an alkyl group containing from 1 to 6 carbon atoms, and, each occurrence of subscripts a and b is, independently, an integer, where a is 0 or 1 and b is 1 to 6. The hydrocarbilalkoxysilane (b) of the present invention is a compound of general formula (II): R6CH2CH2Si (CH3) c ( OCH3) 3-c Formula (II) where c is 0 or 1, and R 6 is an alkyl group or an alkenyl group of 2 to 18 carbon atoms; The silane adhesion promoter (C) of the present invention is a Formula (III) compound of the general formula (III): where d is 0, 1 or 2, and n is 2 to 6;
[0014] The resin composition is stable under moisture-free conditions. After application and in the presence of moisture, the moisture-curable polymer (a) and hydrocarbilalcoxysilane (b) and the silane adhesion promoter (C), hydrolyze and react with themselves and with others to provide a cured elastomer having adhesion to concrete, which can withstand the presence of liquid water, often present in the environment.
[0015] As used herein, "alkyl" includes linear, branched and cyclic alkyl groups; "alkenyl" includes any linear, branched or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the substitution point may be, either at a carbon-carbon double bond or elsewhere in the group; "aryl" includes any aromatic hydrocarbon from which a hydrogen atom has been removed; "aralkyl" includes, but is not limited to, any of the aforementioned alkyl groups, in which one or more hydrogen atoms have been replaced by the same number of similar and / or different aryl substituents (as defined here); and "arenyl" includes any of the aforementioned aryl groups in which one or more hydrogen atoms have been replaced by the same number of similar and / or different alkyl substituents (as defined herein).
[0016] Specific examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isobutyl, cyclohexyl and 2-cyclohexylethyl. Specific examples of alkenyls include, but are not limited to, vinyl, propenyl, allyl and metallized. Specific examples of aryls include, but are not limited to, phenyl and naphthalenyl. Specific examples of aralkyls include, but are not limited to, benzyl and phenethyl. Specific examples of arenyls include, but are not limited to, tolyl and xylyl.
[0017] As used herein, the phrase "the amount of said component (b) present in the moisture-curable resin composition is about 5 to about 35 weight percent based on the weight of said component (a) "is understood to mean that the weights of each hydrocarbilalkoxysilane (b) that is present in the moisture-curable resin composition are added together to form a sum representing the total weight of all hydrocarbilalkoxysilanes (b) that are present, the weights of each moisture-curable polymer containing at least one hydrolyzable group (a), which is present in the moisture-curable resin composition are added together to form an amount representing the total weight of all moisture-curable polymer containing at least one hydrolyzable group ( a) that are present, and the quantity is calculated by dividing the weight that represents the total sum of all hydrocarbilalcoxysilanes (b), by the sound a representing the total weight of all moisture-curable polymers (a), and multiplying this quotient by 100 percent, to give a value of about 5 to about 35 percent by weight.
[0018] As used herein, the phrase "the amount of said component (c) present in the moisture-curable resin composition is about 1 to about 25 weight percent based on the weight of said component (a) "is understood to mean that the weights of each silane adhesion promoter (C), which is present in the moisture-curable resin composition, are added together to form a sum representing the total weight of all silane adhesion promoters (C ), which are present, the weights of each moisture-curable polymer that contains at least one hydrolyzable group (a), which is present in the moisture-curable resin composition are added together to form a sum representing the total weight of all moisture-curable polymers that contain at least one hydrolyzable group (a) that are present, and the value is calculated by dividing the sum that represents the total weight of all silan adhesion promoters o (c) by the sum that represents the total weight of all moisture-curable polymers (a), and multiplying this quotient by 100 percent to give a value of about 1 to about 25 percent by weight.
[0019] As used herein, the phrase "the total amount of said component (b) and said component (c) present in the moisture-curable resin composition is about 10 to about 45 weight percent with based on the weight of said component (a) "is understood to mean that the weights of each hydrocarbilalkoxysilane (b), and the weights of each silane adhesion promoter (c), which are present in the moisture-curable resin composition are added together to form an amount corresponding to the total weight of all the hydrocarbonalcoxysilanes (b) and silane adhesion promoters (c) that are present, the weights of each moisture-curable polymer containing at least one hydro-lysable group (a) , which are present in the moisture-curable resin composition are added together to form a sum representing the total weight of all moisture-curable polymers that contain at least one hydrolyzable group (a) that are present, and the value is calculated by dividing the sum that represents the total weight of all hydrocarbilalcoxysilane (b), and the silane adhesion promoters (c) by the sum that represents the total weight of all moisture-curable polymers ( a), and multiplying this quotient by 100 percent, to give a value of about 10 to about 45 percent by weight.
[0020] Advantageously, in the moisture-curable resin composition of the invention, component (b) is present in an amount of about 8 weight percent to about 30 weight percent, more advantageously between about 10 percent percent by weight to about 26 percent by weight, component (c) is present in an amount of about 5 percent by weight to about 20 percent by weight, more advantageously, from 8 percent by weight to 14 percent by weight, the total amount of components (b) and (c) is from about 15 percent by weight to about 40 percent by weight, more advantageously from 18 percent by weight to about 38 percent by weight, all percentages being based on the percentage by weight of the component (a) weight.
[0021] In order to provide desirable high strengths, high peel strength and cohesive failure mode in non-immunized concrete applications, advantageously, the moisture-curable resin composition is substantially free of hydroxyl-terminated di-methyl siloxane and low glycols molecular weight.
[0022] As used herein, "substantially free of hydroxyl-terminated dimethyl siloxane and low molecular weight glycols" is intended to mean that the moisture-curable resin composition of the present invention does not contain or contains less than 3 percent in weight, advantageously less than 1 weight percent hydroxyl-terminated dimethyl siloxane and low molecular weight glycols, based on the total weight of the moisture-curable resin composition.
[0023] The hydroxyl-terminated dimethyl siloxane has the general formula (IV): HO [Si (CH3) 2O-] xH (IV) where x is an integer from 2 to 10,000. Low molecular weight glycol has the general formula (V): HO [(CR72) mO] yH (V) where R 7 is hydrogen or an alkyl group of 1 to 4 carbon atoms, m is an integer of 2 to 6 and y is an integer from 1 to 4.
[0024] In one embodiment, the moisture-curable resin composition of the invention is substantially free of, that is, it does not contain or contains less than 3 weight percent, advantageously less than 1 weight percent of an alkoxysilane functional amino of general formula (VI), based on the total weight of the moisture-curable resin composition: Y1-R8SiR9f (OR10) 3-f (VI) where: each occurrence of R 8 is a divalent hydrocarbilene group containing 1 to 12 carbon atoms; each occurrence of R 9 is a monovalent hydrocarbon containing 1 to 6 carbon atoms; each occurrence of R 10 is a monovalent hydrocarbon containing 1 to 6 carbon atoms; Y 1 is an amino functional group selected from the group consisting of (R11) 2N-, and (R11) 2NR12NR11 where R 11 is hydrogen, a monovalent hydrocarbon with 1 to 12 carbon atoms or a group of -R8SiR9f (OR10 ) 3-f; R 12 is an alkylene group with 2 to 6 carbon atoms; and each occurrence of subscript f is independently an integer from 0 to 2.
Moisture curable polymer (a).
[0025] The moisture-curable polymer (a), which includes, but is not limited to (1) isocyanatosilane-terminated polyurethane polymers as described in US Patent No. 5,990,257 and US Patent No. 7,319,128, which are incorporated herein by reference in your totality; (2) aminosilane-terminated polyurethane prepolymers as described in US Patent No. 6,197,912 and US Patent No. 6,001,946, which are incorporated herein by reference in their entirety; and (3) hydrolyzable silane-terminated polyethers, as described in US Patent Application No. 2006/0173121, which is incorporated herein by reference in its entirety.
[0026] Advantageously, the moisture-curable polymer (a) is provided by Formula (I) in which R 1 is a polymer fragment having an average molecular weight in number of 500 to 25,000 grams per mol, with an advantage of 1000 to 20,000 grams per mol, and more advantageously, from 4000 to 12,000 grams per mol. The number average molecular weight is determined using gel permeation chromatography (GPC) and polystyrene standards at room temperature. The flexibility of the cured moisture-cured polymer (a) is improved when the Tg is advantageously from -20 ° C to -80 ° C, more advantageously from -25 ° C to -60 ° C, and most advantageously from -30 ° C to -55 ° C. The glass transition temperature is determined using the differential scanning calorimetry (DSC) method. R2 is advantageously an alkylene of 1 to 6 carbon atoms, more advantageously, of 1 to 3 carbon atoms and more advantageously 3 carbon atoms; A 1 is advantageously oxygen or nitrogen substituted of structure (-) 2 NR3, where R3 is hydrogen, alkyl or aryl, where each R3, other than hydrogen, contains 1 to 10 carbon atoms and, advantageously, 1 to 6 carbon atoms; A2 is a substituted nitrogen of structure (-) 2NR3, in which R3 is advantageously hydrogen, alkyl or aryl, in which each R3, different from hydrogen, contains 1 to 10 carbon atoms and more advantageously, from 1 to 6 atoms of carbon; X1 and X2 are methoxy, ethoxy or propoxy; and X3 is methyl, methoxy, ethoxy or propoxy.
[0027] In one embodiment, the moisture-curable polymer (a) is represented by the general formula (VII): where R1, R2, X1, X2, X3 and b are as defined above in connection with Formula (I).
[0028] Advantageously, R1 is a fragment of organic polymer that contains at least one urethane group, as a result of the reaction of a polyol with an isocyanate group, and has an average molecular weight of 4,000 to 18,000 grams per mol. More advantageously, R 1 represents a radical derived from polyurethane from the reaction of a polyol and a diisocyanate. Advantageously R2 is methylene or propylene; X 1 and X2 are methoxy, X 3 is methyl or methoxy, and b is 2.
[0029] In one embodiment, the moisture-curable polymer (a) of formula (VII) is a silylated polyurethane prepared by a process comprising: (A) reacting a polyol component with a diisocyanate component in a stoichiometric excess of the polyol component for the diisocyanate component to form a hydroxyl terminated polyurethane; and (B) reacting hydroxyl terminated polyurethane with one or more isocyanate silanes of the formula OCN-R2-SiX1X2X3, wherein R2, X1, X2 and X3 are as defined above, in connection with Formula (I).
[0030] In another embodiment, the moisture-curable polymer (a) of formula (VII) is a silylated polyurethane prepared by a process that comprises the reaction of a polyol component with one or more isocyanate silanes of formula OCN-R2- SiX1X2X3, where R2, X1, X2 and X3 are as defined above, in connection with Formula (I), and where the molar ratio of -NCO of the isocyanate silane to -OH of the polyol component is advantageously 0.3 to 1.1, more advantageously from 0.5 to 1, and more advantageously from 0.95 to 0.99.
[0031] Representative non-limiting examples of polyols include hydroxyl-terminated polyalkylene oxides, such as hydroxyl-terminated polypropylene oxide, hydroxyl-terminated polyethylene oxide, and hydroxyl-terminated polybutylene oxide. In a preferred embodiment, the polyol is polypropylene glycol.
[0032] Suitable diisocyanates include, but are not limited to, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4- and 2,6-toluene diisocyanate, 4,4'-diphenyl isomers methanediisocyanate, isophorone diisocyanate, dici-chlorohexylmethane-4,4'-diisocyanate, various liquids of diphenylmethane-diisocyanates that contain a mixture of 2,4- and 4.4 'isomers and the like, and mixtures thereof. Advantageously, the functional isocyanate monomer used is an isophorone diisocyanate (IPDI), available from Bayer under the trade name Desmodur I or tetramethylxylylene diisocyanate (TMXDI).
[0033] The moisture-curable polymer (a) represented by Formula (I) can be prepared from a polyol reagent, or a combination of polyol reagents. Polyol reagent combinations or mixtures are often used to achieve the specific physical properties of moisture-cured polymer resin, such as fluidity, tensile, modulus and adhesion. The number of the average molecular weight of the polyol reagent is advantageously 300 to 24,000 grams per mol (g / mol), and most advantageously, 1000 to 20,000 grams per mol. These polyols optionally contain other organic functional groups, including non-limiting examples of thiourethane, urethane, urea, biuret, ester, thioester, ether, thioether, amide, and the like.
[0034] A moisture-curable polymer containing a silyl group can be used in combination with a moisture-curable polymer that contains two or more silyl groups to lower Tg and increase the flexibility of the moisture-curable polymer (a). The moisture-curable polymer that contains functions of a silyl group as a reactive plasticizer that becomes incorporated into the polymer network during curing. However, if the medium hydroxyl functionality polyol mixture is very low, then the moisture-curable resin composition can cure the silylated polymer poorly. It is therefore preferable to have sufficient average functionality of the reagent polyols, such that the moisture-curable polymer (a) prepared from its cures on exposure to moisture. The average hydroxyl functionality of the polyol reagent mixture is advantageously 1.6 to 6.0 hydroxyl groups per polyol molecule, more advantageously 1.8 to 3.0 hydroxyl group per polyol molecule and most advantageously 1.95 to 2.5 hydroxyl groups per polyol molecule.
[0035] The moisture curable polymer (a) can be prepared from a mixture of a low medium molecular weight polyol reagent and a high medium molecular weight polyol reagent. The moisture-curable polymer (a) prepared from this mixture of polyol reagents after curing and in low strains has a high modulus, while maintaining high values for elongation at break. The average molecular weight number of the low molecular weight polyol is advantageously 300 to 2,000 grams per mol, more advantageously 500 to 1,200 grams per mol, and most advantageously 800 to 1,000 grams per mol. The average molecular weight number of the high molecular weight polyol is advantageously from 2,001 to 24,000 grams per mol, more advantageously from 4,000 to 12,000 grams per mol, and most advantageously, from 8000 to 10,000 grams per mol. The weight ratio of low molecular weight polyol reagent to high molecular weight polyol reagent is advantageously 0.01 to 3, more advantageously 0.05 to 1 and most advantageously 0.2 to 0.5.
[0036] Representative non-limiting examples of polyols include hydroxyl-terminated polyalkylene oxides, such as hydroxyl-terminated polypropylene oxide, hydroxyl-terminated polyethylene oxide, and hydroxyl-terminated polybutylene oxide; polyoxyalkylene triols; polycaprolactone diols and triols; hydroxyl-terminated unsaturated rubbers, such as hydroxyl-terminated polybutane diene copolymer; polyester diols and polyol made from saturated aliphatic diacids and diols or triols, unsaturated diacids and diols or triols, saturated polyacids and aromatic diols or diols and diols or triols and the like; polytetramethylene glycols; and other diols or triols.
[0037] The polyols used can have a very low level of unsaturation and, therefore, high functionality. Said polyols are normally prepared using metal complex catalysts for the polymerization of alkylene oxide, resulting in polyols with a low level of terminal ethylenic unsaturation. Polyols have a terminal ethylenic unsaturation, which is advantageously less than 0.4 mi-equivalents per gram (meq / g) of polyol, more advantageously less than 0.1 mile-quivalents per gram of polyol and, even more advantageously, less at 0.02 mile-quivalents per gram of polyol. The number of the average molecular weight of the polyols is advantageously in the range between 500 and 24,000 grams per mol, and more advantageously, from 2000 to 12,000 grams per mol.
[0038] The moisture-curable polymer (a) of the present invention can be prepared by any of several synthetic methods including those described below. Synthesis method 1: Reaction of a polyol with a polyisocyanate and then with a hydrolyzable silane containing an active hydrogen functional group to provide a moisture-curable polymer containing at least one hydrolyzable silyl group [0039] Polyols with functional hydroxyl compounds mentioned above are converted into isocyanate-terminated prepolymers in the known form by reaction with isocyanates. These prepolymers are prepared by reacting an excess of polyisocyanate with a polyol, or a combination of polyols normally in the presence of a catalyst.
[0040] The prepolymer terminated in isocyanate, after the reaction of the polyol with the polyisocyanate has the General Formula (VIII): R1 (-N = C = O) b (VIII) where R 1 and b have the defined meanings mentioned above as for Formula (I). It is understood that the organic polymer fragment R1 contains a urethane group as a result of the reaction of the polyol with an isocyanate group. According to an embodiment of the invention, the isocyanate-terminated prepolymer is prepared by reaction of diisocyanates with polyols, in different molar ratios from NCO to OH, which advantageously vary from 1.1 to 2.0, more advantageously 1 , 4 to 1.9 and, more advantageously, 1.5 to 1.8.
[0041] Suitable polyisocyanates include any of the polyurethane polymers, which can be prepared by the usual reaction sequence with the polyol to form a prepolymer. Useful diisocyanates include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of isomers of 2,4 - and 2,6-toluene diisocyanate, 4,4'-diphenyl methanediisocyanate, isophorone diisocyanate , dicyclohexylmethane-4,4'-diisocyanate, various liquids of diphenylmethane-diisocyanates, containing a mixture of isomers of 2.4 - and 4.4 and the like, and mixtures thereof. Advantageously, the functional monomer employed for isocyanate is an isophorone diisocyanate (IPDI), available from Bayer under the trade name Desmodur I or tetramethylxylylene diisocyanate (TMXDI).
[0042] A catalyst can be used in the preparation of the aforementioned isocyanate-terminated prepolymers. Suitable catalysts are the salts of metals or bases, and include non-limiting examples of bismuth salts, such as bismuth trisneodecanoate and other bismuth carboxylates, zirconium compounds, or aluminum compounds, such as zirconium chelates and chelates aluminum; dialkyl tin dicarboxylates, such as dibutyltin dilaurate and dibutyltin acetate, dialkyl tin oxides, such as dibutyltin oxide, tertiary amines, stannous salts of carboxylic acids, such as tin octoate and tin acetate, and others.
[0043] In a second stage of the process, the isocyanate-terminated prepolymer with the General Formula (VIII) is reacted with silane (s) containing an active hydrogen functional group to prepare the moisture-curable polymer (a) . Silanes containing an active hydrogen functional group are provided by the general formula (IX): HA2R2-SiX1X2X3 (IX) where R2 is, independently, a divalent hydrocarbilene group containing from 1 to 12 carbon atoms; each occurrence of A2 is independently selected from the group consisting of oxygen (-O-), sulfur (-S-), (-) 2NR3, where R3 is hydrogen, alkyl, alkenyl, arenyl, aralkyl, alkyl containing at least one ester functional group or a -R2SiX1X2X3 group, where each R3, other than hydrogen, contains from 1 to 18 carbon atoms, and X1, X2 and X3 have the above meanings as defined for Formula (I).
[0044] The silane termination reactions of the present invention can be of any type as is known in the art, for example, the reactions described in US Patent No. 6,197,912 and US Patent No. 5,990,257, the total content of which is here incorporated by reference.
[0045] Active hydrogen organofunctional silanes include, for example, primary and secondary amino-alkoxysilanes and mercaptoalkoxysilanes. Representative examples of suitable aminosilanes include, but are not limited to, N-phenyl-aminomethyltrimethoxysilane, N-cyclohexyl-aminomethyltrimethoxysilane, amino-methyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltrimethoxyl butyl-3-aminopropyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, di-butyl maleate adduct - 3 - aminopropyltrimethoxysilane, the dibutyl-maleate 4 - amino-3,3 adduct -dimethylbutyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis- (3-trimethoxysilylpropyl) amine, 3-aminopropylmethyldimethoxysilane, N-methyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxy -amino-2-methylpropyldiethoxymethylsilane, N-ethyl-3-amino-2-methylpropyltriethoxysilane, N-ethyl-3-amino-2-methylpropylmethyldimethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, 3 - (N-methyl- 2- amino-1-methyl-1-ethoxy) propyltrimethoxysilane, N-ethyl-4-amino-3, 3 - dimethylbutyldimethoxymethylsilane, N-ethyl-4-amino-3, 3-dimethylbutyltrimethoxysilane, bis- (3-trimethoxyethyl-2-methylpropyl) amine, N- (3'-trimethoxysilylpropyl) -3-amino-2-methylpropyltrimethoxysilane, 3-aminopropyl and their mixtures. Representative examples of suitable mercaptosilanes include, but are not limited to, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, mercapto-methyltrimethoxysilane, mercaptmethylmethylmethylmethylmethylmethylmethylmethylmethylmethyl.
[0046] Advantageously, silanes containing an active hydrogen functional group, as represented by the general formula (IX), contain an X1 and X2 which is methoxy and an X3 group which is methyl or methoxy. The methoxysilyl groups are more reactive with water (moisture) and result in the rapid hydrolysis of the alkoxysilyl group. Faster hydrolysis results in faster curing of the moisture-curable polymer (a) after application and exposure to moisture. Synthesis method 2: Reaction of a hydroxyl-terminated polyol or polyurethane with a hydrolyzable silane containing a functional isocyanate group to provide a moisture-curable polymer containing at least one hydrolyzable silyl group.
[0047] The aforementioned hydroxyl functional polyols or hydroxyl-terminated polyurethanes are converted into moisture-curable polymer (a) in a manner known by reaction with a functional silane isocyanate. The moisture-curable polymer (a) is prepared by reacting a polyol or a mixture of polyols, or a hydroxyl terminated polyurethane usually in the presence of a catalyst, with less than one equivalent or slightly more than one equivalent of hydrolyzable silane containing an isocyanate group. The molar ratio of -NCO of the hydrolyzable silane containing an isocyanate group to -OH is advantageously 0.3 to 1.2, more advantageously 0.5 to 1.1, and most advantageously 0.95 to 0.99. When the ratio of -NCO to OH is less than 1, the moisture-curable polymer (a) has residual hydroxyl groups, which can be advantageous for improving adhesion to substrates.
[0048] Suitable hydrolyzable silanes containing an isocyanate functional group for use in the preparation of components (a) of the present invention, have the general formula (X): OCN-R2-SiX1X2X3 (X) where R2 and X1, X2 and X3 have the above meanings as defined for Formula (I).
[0049] Representative hydrolyzable silanes, containing an isocyanate functional group, as represented by the general formula (X), which are suitable for use herein include, but are not limited to, isocyanatomethyltrimethoxysilane, isocyanatomethylmethydimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatoil , 4-isocianatobutiltrimetoxisilano, 2-isocyanato-1, 1-dimetiletiltrimetoxisilano, 3- isocianatopropiltrietoxisilano, 3-isocianatoisopropiltrietoxisilano, 4- isocianatobutiltrietoxisilano, 2-isocyanato-1, 1-dimetiletiltrietoxisilano, 3-isocianatopropilmetildimetoxisilano 3 - isocianatoisopropildimetilmetoxisilano, 4-isocianatobutilfenildimetoxisilano 2 - (4-isocyanatophenyl) ethylmethyldimetoxisi-lano and mixtures thereof.
[0050] Advantageously, hydrolysable silanes, containing an isocyanate functional group, as represented by the general formula (X), contain an X1 and X2, which is methoxy and an X3 group which is methyl or methoxy. Methoxysilyl groups are more reactive with water (moisture) and result in rapid hydrolysis of the alkoxysilyl group. Faster hydrolysis results in faster curing of the moisture-curable polymer (a) after application and exposure to moisture. Method 3: Reaction of polyols with ethylenically unsaturated halo compounds and then silanes containing a Si-H group to provide a moisture-curable polymer containing at least one hydrolyzable silyl group.
[0051] The hydroxyl functional polyols mentioned above are converted to ethylenically unsaturated prepolymers in the known form by reaction with ethylenically unsaturated halo compounds. These prepolymers are prepared by reacting ethylenically unsaturated halo compounds with a polyol or a mixture of polyols normally in the presence of a catalyst.
[0052] The ethylenically unsaturated halo compounds useful in the preparation of ethylenically unsaturated polymers are provided by the general formula (XI): Y1R13C (R14) = CH2 (XI) where R13 is a divalent hydrocarbilene group containing from 1 to 10 carbon atoms selected from the group consisting of divalent alkylene, alkenylene, arenylene, arylene and aralkylene, and optionally contains at least one heteroatom selected from the group consisting of oxygen and sulfur; R14 is a hydrogen or an alkyl group of 1 to 6 carbon atoms; and each Y1 is, independently, a halogen atom, selected from the group consisting of Cl-, Br- and I-. Reaction conditions are well known in the art, such as, for example, US Patents 3,951,888 and 3,971,751, the total content of which is incorporated herein by reference.
[0053] Representative non-limiting examples of ethylenically unsaturated halogenated compounds, represented by the general formula (XI), include allyl chloride, allyl bromide, allyl iodide, methylated chloride, methylated bromide, 6-chlorhexene, chloromethylstyrene, and their mixtures.
In the final step, the ethylenically unsaturated prepolymer is hydrolyzed with hydrolyzable hydridosilane of the general formula (XII): HSiX1X2X3 (XII) where X1, X2 and X3 have the meanings mentioned above as defined for Formula (I). The conditions for hydrosylation of intermediates containing carbon-carbon double bonds are well known in the art, as described in "Com-prehensive Handbook of Hydrosilylation" B. Marciniec (ed), Pergamon Press, New York (1992), which is included in its entirety here by reference.
Useful hydrolyzable hydridosilanes include, but are not limited to, H-Si (OCH3) 3, H-Si (OCH2CH3) 3, H-SiCH3 (OCH3) 3, H-SiCH3 (OCH2CH3) 2, H-Si (CH3) 2OCH3 , H-Si (CH3) 2OCH2CH3, and mixtures thereof.
[0054] Advantageously, hydrosilanes, as represented by the general formula (X), contain an X1 and X2, which is methoxy and an X3 group which is methyl or methoxy. Methoxysilyl groups are more reactive with water (moisture) and result in rapid hydrolysis of the alkoxysilyl group. Faster hydrolysis results in faster curing of the moisture-curable polymer (a) after application and exposure to moisture.
Hydrocarbilalkoxysilane (b).
[0055] As used herein, the term "hydrocarbilalcoxisilane" refers to a compound containing a hydrolyzable alkoxysilyl group and a hydrocarbil group, which, when combined with a moisture-curable polymer that has at least one hydrolysable silyl group, improves adhesion of the curable composition by moisture cured to concrete without primer.
[0056] Although not intended to be limited by any theory, it is believed that hydrocarbilalcoxisilane (b) migrates (absorbs) within the concrete substrate, where it reacts with ambient humidity for hydrolysis and condenses hydrocarbilalcoxysilane (b), and forms an interpenetrating siloxane network in the concrete, thus creating a hydrophobic barrier that prevents liquid water migration through the concrete and attacking the connections between the moisture-curable polymer (a) and the siloxane concrete and / or film formed a from hydrolysis and condensation of hydrocarbilalkoxysilane (b).
[0057] The hydrocarbilalcoxisilane (b) of the present invention is a compound of general formula (II): R6CH2CH2Si (CH3) c (OCH3) 3-c Formula (II) where c is 0 or 1, and R6 is an alkyl group or an alkenyl group of 2 to 18 carbon atoms.
[0058] In connection with the hydrocarbilalcoxysilane (b) of general formula (II), R6 is a monovalent C2-C18 hydrocarbon group that includes straight chain alkyl, branched chain alkyl, cyclic alkyl, and alkenyl groups. It is preferable that the alkyl group contains from 4 to 16 carbon atoms, and more preferably from 6 to 14 carbon atoms, because the higher carbon number of the alkyl group prevents evaporation during application, contributes to a more hydrophobic character than hydrocarbilalcoxisilane (b) and reduces the viscosity of the moisture-curable resin composition.
[0059] Representative and non-limiting examples of straight-chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dode-scyl, heptadecyl and octadecyl. Specific and non-limiting examples of branched chain alkyl groups include isopropyl, isobutyl, isopentyl, neopentyl, isohexyl, neohexyl, isooctyl, neooctyl, isodecyl, isoheptadecyl and isooctadecyl and the like. Representative and non-limiting examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, cycloheptyla, cyclooctyl, cyclooctatrienyl, cyclododocyl and the like.
[0060] Representative, non-limiting examples of hydrocarbilalkoxysilanes (b) include, but are not limited to, butyl-trimethoxy-silane, sec-butyl-trimethoxy-silane, hexyl-trimethoxy-silane, hexyl-methyl-dimethoxy-silane, hex -5-enyl-trimethoxy-silane, hex-5-enyl-methyl-dimethoxy-silane, octyl-trimethoxy-silane, methyl-dimethoxy-silane octyl, de-cil-trimethoxy-silane, decyl-methyl-dimethoxy-silane , dodecyl-trimethoxy-silane, dodecyl-methyl-dimethoxy-silane, hexadecyl-trimethoxy-silane, hexadecyl-methyl-dimethoxy-silane, octadecyl-trimethoxy-silane, methyl-dimethoxy-octadecyl-silane, methyl-dimethoxy-eicosylsilane , methyl-trimethoxy-silane-eicosyl and their combinations.
[0061] More preferably, non-limiting examples of hydrocarbilalkoxy silanes (b) include trimethoxy-octyl-silane, dimethoxy-methyl-octyl-silane, decyl-trimethoxy-silane, decyl-methyl-dimethoxy-silane, dodecyl-trimethoxy-silane , dodecyl-methyl-dimethoxy-silane, hexadecyl-trimethoxy-silane, hexadecyl-methyl-dimethoxy-silane, octadecyl-trimethoxy-dimethoxy-silane and methyl-octadecyl-silane. Even more preferably, non-limiting examples of hydrocarbilalkoxysilanes (b) include dodecyl-trimethoxy-silane, dodecyl-methyl-dimethoxy-silane, hexadecyl-trimethoxy-silane, hexadecyl-methyl-dimethoxy-silane, oc-tadecyl-trimethoxy-silane and methyl -dimethoxy -octadecyl-silane.
[0062] The Hydrocarbilalkoxysilanes (b) of the present invention can be prepared by various methods known in the art. In one method, hydrocarbilalkoxysilanes (b) are prepared by reacting an alkene, that is, a hydrocarbon that contains a carbon-carbon double bond, with a hydrolyzable hydridosilane of the general formula (XIII): HSi (CH3) c (OCH3) 3-c (XIII) where c is 0 or 1. Conditions for hydrosylation of intermediates containing carbon-carbon double bonds are well known in the art, as described in "Comprehensive Handbook of Hydrosilylation" B. Marciniec (ed), Perga - mon Press, New York (1992), which is included in its entirety here by reference.
Silane adhesion promoter (C).
[0063] As used herein, the term "silane adhesion promoter" refers to a compound containing a hydrolyzable alkoxysilyl group and an organofunctional group which, when combined with a moisture-curable polymer having at least one group Hydrolyzable silyl improves the adhesion of the moisture-curable composition to concrete and other non-immunized substrates, such as glass, plastics, metals, metal oxides and mineral surfaces.
[0064] The silane adhesion promoter (c) of the present invention is a com- Formula (III) composed of general Formula (III): where d is 0, 1 or 2, and n is 2 to 6.
[0065] Preferred non-limiting examples of the silane (c) adhesion promoter include trimethoxy- (3-oxiranylmethoxy-propyl) -silane and dimethoxy-methyl- (3-oxiranylmethoxy-propyl) -silane.
Additional components.
[0066] In one embodiment, the moisture-curable composition of the invention additionally contains at least one component selected from the group consisting of a catalyst to catalyze the reaction between the moisture-curable polymer that has at least one hydrolyzable silyl group (a) with water under curing conditions, a filling agent, a plasticizer, and their combinations.
[0067] The catalyst of the moisture-curable resin composition can be any catalyst that is effective in promoting the reaction between the moisture-curable polymer (a), the hydrocarbilalkoxysilane (b) and the silane adhesion promoter (C), which occurs after exposure to moisture. Suitable curing catalysts include, but are not limited to, organometallic catalysts, amine catalysts, and the like. Advantageously, the catalyst is selected from the group consisting of organic tin, zirconium complex, aluminum chelate, titanium chelate, organic zinc, organic cobalt, organic iron, organic nickel and organo-bismuth, and mixtures thereof. The catalyst can be a mixture of an organometallic catalyst and an amine catalyst.
[0068] Representative examples of catalysts include, but are not limited to, dibutyltin oxide, dimethyl tin diacetate, dimethyltin dilaurate, dimethyl tin dineodecanote, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltate diacetate, dibutyltate diacetate tin, tin acetate, tin oxide, morpholine, triisopropylamine, bis- (2-dimethylaminoethyl) ether and piperazine chloride. Other useful catalysts include complexes containing zirconium, containing aluminum and containing bismuth such as KAT XC6212, K-5218 and K KAT KAT-348, supplied by King Industries, Inc., titanium chelates, such as types of TYZOR, available from from DuPont, the available types of KR, Kenrich Petro-chemical, Inc., amines such as NIAX A-501 amine, available from Momentive Performance Materials Inc., and the like.
[0069] The catalyst can be present in the moisture-curable resin composition, in an amount of 0.05 weight percent to 10 weight percent based on the total weight of components (a), (b) and (c ), advantageously in an amount of 0.1 weight percent to 5 weight percent based on the total weight of components (a), (b) and (c), and most advantageously, in an amount of 0, 5 weight percent to 3 weight percent based on the total weight of components (a), (b) and (c).
[0070] The moisture-curable resin composition filler can be any inorganic or organic filler material used to reinforce or prolong the moisture-curable polymer (a) of the present invention. Typical fillers include, for example, reinforcement fillers such as carbon black, smoked silica, precipitated silica, clays, talc, aluminum silicates, and extending fillers such as treated and untreated calcium carbonates and the like.
[0071] The fillers may be present in the moisture-curable resin composition in an amount between 1 weight percent to 400 weight percent based on the total weight of components (a), (b) and (c), advantageously in an amount of 10 weight percent to 250 weight percent based on the total weight of components (a), (b) and (c), and more advantageously, in an amount of 20 weight percent to 150 weight percent based on the total weight of components (a), (b) and (c).
[0072] The plasticizers of the moisture curable resin composition can be any organic compound that is added to the moisture curable resin composition of the present invention can modify the properties and facilitate the use of higher fill levels. Examples of plasticizers include phthalates, dipropylene and diethylene glycol dibenzoates, alkylsulfonate phenols, alkyl phenanthrenes, phosphates and alkyl / diaryl mixtures thereof and the like. Advantageously, the plasticizer has a viscosity of 10 to 1000 mPa.s at 20 ° C according to the Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids of the ASTM D 445-10 standard, and (Dynamic Viscosity Calculation) .
[0073] Plasticizers can be present in the moisture-curable resin composition in an amount between 1 weight percent to 200 weight percent based on the total weight of components (a), (b) and (c), advantageously in an amount of about 5 weight percent to 100 weight percent based on the total weight of components (a), (b) and (c), and most advantageously, in an amount of 10 percent in weight at 80 weight percent based on the total weight of components (a), (b) and (c).
[0074] The moisture-curable resin composition of the present invention can include various other components, including, but not limited to, pigments, thixotropes, waxes, anti-slip agents, stabilizers, viscosity modifiers, and the like. Various castor waxes, smoked silica, treated clays and polyamides typify thixotropic additives. Stabilizers that can be incorporated into the moisture-curable resin composition of the present invention include, for example, hindered amine, hindered phenol, and dialkylhydroxyamine.
[0075] When used in coating applications, the moisture-curable resin composition may contain organic solvents to decrease viscosity and assist in film formation. Typically, the amount of solvents used can vary from 1 to 20,000 weight percent, based on the total weight of components (a), (b) and (c). Advantageously, the amount of solvent is 5 to 100 weight percent, more advantageously 10 to 25 weight percent based on the total weight of components (a), (b) and (c), to minimize the amount of volatile organic compounds that are released into the environment during application and drying.
[0076] In another aspect, the present invention also relates to cured compositions produced from the above-mentioned moisture-curable resin compositions and sealants, adhesives and coatings containing such cured compositions. The cured composition is produced by contacting a moisture curable resin composition, as defined above, with water.
[0077] As used herein, the term "water" means atmospheric moisture, steam, liquid water, ice or water mixed with other organic compounds, such as organic solvents and is advantageously atmospheric humidity. The effective amount of water is the amount sufficient to react with the hydrolyzable silyl groups and cure the composition. Typically, more than 0.5 mol of water is required for each mol of the total Si-OR4 from the moisture-curable polymer (a), and Si-OCH3 of the hydrocarbilalkoxysilane (b), and adhesion promoter (c) which is present in the moisture-curable resin composition.
[0078] In yet another aspect, the present invention also relates to an article comprising cured compositions produced from the moisture-curable resin compositions mentioned above, if these moisture-curable resin compositions are formulated in sealants, adhesives and coatings , which are attached to a concrete without primer. The article has a good adhesion between the cured composition of the moisture-curable resin compositions and the concrete without primer, which are able to survive exposure to liquid water for at least seven days at 20 ° C. When the article is subjected to a peeling test in accordance with the ASTM C-794-06 standard, the article has a minimum of at least 20 percent cohesion failure after exposure to water for seven days, and forces peeling from 1.80 to 8.90 N / mm (10 to 50 pounds / inch).
[0079] The following examples are intended to illustrate, but in no way limit the scope of the present invention. All parts and percentages are by weight and all temperatures are in degrees Celsius, unless expressly stated otherwise.
Examples Example 1 Preparation of trimethoxysilyl-terminated polyurethane polymer, moisture-curable polymer (a) [0080] A four-tab reaction boiler was loaded with polypropylene glycol (1,000 grams, 0.09 mol, average molecular weight 12,000 grams per mol, from Bayer under the trade name Acclaim 12200 diol). The polyol was stirred and sparged with nitrogen gas at 60 ° C for 16 hours. The temperature of the polyol was cooled to 45 ° C and then the isophorone diisocyanate (9.99 grams, 0.0495 mol from Bayer) and tin catalyst (dibutyltin dilaurate, 7.5 ppm Sn, Chemtura under the trade name Fomrez SUL-4) were added. After the exotherm ceased, the reaction mixture was heated to 75 ° C and maintained at this temperature with stirring and under a blanket of gaseous nitrogen. The isocyanate content was checked every half hour, using a titration method with n-butylamine. When the isocyanate content was no longer detectable, 3-isocyanatopropyltrimethoxysilane (18.45 grams, 0.09 mol of Momentive Performance Materials Inc.) was added and the reaction mixture was stirred at 75 ° C until the isocyanate content was no longer be detectable. The viscosity was about 60 Pa.s at 25 ° C.
Examples 2 to 15 and Comparative Examples A and B
Preparation of a set of one-piece sealant compositions, based on moisture-cured silylated polyurethane, mechanical and curing properties of the hardened compositions [0081] A set of one-piece sealants, based on moisture-cured silylated polyurethane was prepared from according to the following procedure. In a Ross mixer, Model No. PDM -% gallon, sold by Charles Ross & Sons Company, the trimethoxysilyl-finished polyurethane polymer prepared in Example 1, the trimethoxysilane vinyl desiccant, hydrocarbyl silane (b), was loaded. (c), diisododecyl phthalate plasticizer and antioxidants. The mixture was stirred for 15 minutes under a nitrogen atmosphere. The calcium carbonate filler (s), the thixotropic, and titanium dioxide pigment were added to the mixer with stirring. After the ingredients were added, the temperature was raised to 100 ° C, the mixing chamber was evacuated under full vacuum and the mixture was stirred for 1.5 hours. The mixer was cooled to 30 ° C, the mixing chamber was purged with nitrogen gas, and an additional amount of vinyltrimethoxysilane desiccant, catalysts and other additives were added and mixed for 15 minutes under moderate vacuum. The chemical identity and quantities of each component, in grams, are shown in Table I.
[0082] The sealant films were cured in a humidity chamber, which was controlled at 23 ° C and 50% relative humidity for seven days. The tensile strength and elongation were tested according to the ASTM D412 test method and hardness according to the ASTM C661 test method.
[0083] The bark test samples on concrete slabs (Portland cement) were prepared and tested according to the ASTM C-79406 test method. The concrete slabs were stored in saturated lime water. Before the preparation of the peel test samples, the concrete surface was wetted with wet soil to remove any cream, well rinsed with running tap water and dried overnight, at 105 to 110 ° C. The concrete slabs were then vigorously brushed with a hard brush to remove any film or dust, and then conditioned in a humidity chamber at 25 ° C and 50% relative humidity for at least one day, but not more than seven days. The test samples were prepared according to the ASTM C-794-06 test method and then cured in a humidity chamber according to the following conditions: seven days at 25 ° C and 50% relative humidity; seven days at 38 ° C and 90 to 95% relative humidity, and seven days at 25 ° C and 50% relative humidity. The shell test samples were then submerged in water for seven days at room temperature. The bark samples were removed from the water, dried with a paper towel, and then tested immediately. The results are shown in Table I.
Table I. The formulation of a composition of the present invention and the physical properties of the cured composition .______________________________________ [0084] Polyurethane polymer prepared in Example 1. [0085] Octadecylmethyldimethoxysilane from Gelest, Inc. under the trade name SIO6645.0.
[0086] Octilmethyldimethoxysilane from Gelest, Inc. under the trade name SI06712.4.
[0087] Hexadecyltrimethoxysilane from Momentive Performance Materials Inc. under the trade name HDTMS.
[0088] trimethoxy- (3-oxiranylmethoxy-propyl) -silane from Momentive Performance Materials Inc. under the trade name Silquest ™ A-187 silane.
[0089] -vinyl-trimethoxy-silane from Momentive Performance Materials Inc. under the trade name Silquest ™ A-171 silane.
[0090] Surface treated with natural calcium carbonate from Omya AG under the trade name Omyabond ™ 520.
[0091] Surface treated with natural calcium carbonate from Omya AG under the trade name Omyacarb ™ 5 FT.
[0092] Ultrafine coated precipitated calcium carbonate from Specialty Minerals, Inc. under the trademark Ultra Pflex ™.
[0093] Surface of ground calcium carbonate treated from Specialty Minerals, Inc. under the trade name HiPflex ™.
[0094] Reaction products of methyl 3 - (3 - (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) ethyl propionate from BASF Corporation, under the trade name Tinuvin 213 ™.
[0095] 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidin-4-ol butanedioic acid polymer from BASF Corporation, under the trade name Tinuvin 622 ™.
[0096] Pigment of rutile titanium dioxide from EI DuPont de Nemours and Company under the trade name Ti-Pure ® R-960.
[0097] Modified surface of sublimated silica from Cabot Corporation, under the trade name Cabosil TS 720 ™.
[0098] Polyamide wax from Cray Valley Ltd. under the trade name Crayval-lac ™ SLX.
[0099] Exxon Chemical diisododecyl phthalate plasticizer under the trade name DIDP.
[00100] Hydroxyl-terminated polydimethylsiloxane from Momentive Performance Materials Inc. under the trade name SE 4026.
[00101] Dipropylene glycol from Sigma-Aldrich Company under the trade name D215554.
[00102] Reaxis Dibutyltin Ketonate under the trade name Reaxis ™ C226.
[00103] dibutyltin oxide in dialkyl phthalate from Momentive Performance Materials Inc. under the trade name Fomrez ™ catalysts SUL-IB 1.
[00104] Amino-functional oligosiloxane from Momentive Performance Materials Inc. under the trade name VX 225.
[00105] As shown in Table 1, Examples 2 to 15, good adhesions to concrete without prime, as illustrated by the cohesion failure greater than 20% and a peeling force in excess of 20 lb / in, were obtained when the sealant formulations according to the present invention were used. However, poor adhesions to concrete without prime were observed when the formulations contain either hydroxyl-terminated polydimethylsiloxane or dipropylene glycol in addition to the components (a), (b) and (c) described above, as shown in the examples comparisons A and B, respectively.
[00106] Although the invention has been described above with reference to the specific modalities thereof, it is evident that many changes, modifications and variations can be made without departing from the concept of the invention described herein. In this way, it is intended to cover all these changes, modifications and variations that fit the spirit and broad scope of the attached claims.

权利要求:
Claims (16)
[1]
1. Composition of moisture-curable resin CHARACTERIZED by the fact that it comprises: (a) at least one moisture-curable polymer having at least one hydrolyzable silyl group; (b) at least one hydrocarbilalkoxysilane represented by the general formula (II) R6CH2CH2Si (CH3) c (OCH3) 3-c Formula (II) where c is zero or 1, and R6 is an alkyl group or an alkenyl group from 2 to 18 carbon atoms; (c) at least one silane adhesion promoter represented by the general formula (III) Formula (III) where d is 0, 1 or 2, and n is 2 to 6; wherein (i) the amount of said component (b) present in the moisture-curable resin composition is 5 to 35 weight percent based on the weight of said component (a); (ii) the amount of said component (c) present in the moisture-curable resin composition is 1 to 25 weight percent based on the weight of said component (a); (iii) the total amount of said component (b) and said component (c) present in the moisture-curable resin composition is 10 to 45 weight percent based on the weight of said component (a); with the proviso that (i) the moisture-curable resin composition does not contain hydroxyl-terminated dimethyl siloxane; and (ii) the moisture-curable resin composition does not contain low molecular weight glycols, where said component (a) has the general formula (I): Formula (I) where: R1 is, independently, a fragment of monovalent or polyvalent organic polymer having an average molecular weight of 500 to 25,000 grams per mol (g / mol); each occurrence of R2 is, independently, a divalent hydrocarbilene group containing from 1 to 12 carbon atoms; each occurrence of A1 is independently selected from bivalent oxygen (-O-), sulfur (-S-) or substituted nitrogen of the structure (-) 2NR3, where R3 is hydrogen, alkyl, alkenyl, arenyl, aryl, aralkyl, alkyl containing at least one functional ester group or a -R2SiX1X2X3 group, where each R3, other than hydrogen, contains from 1 to 18 carbon atoms, and with the proviso that when A1 is oxygen or sulfur, then A2 is (- ) 2NR3 and, when a is 0, then A1 is oxygen; each occurrence of A2 is independently selected from divalent oxygen (-0-), sulfur (-S-) or substituted nitrogen from structure (-) 2NR3, where R3 is hydrogen, alkyl, alkenyl, arenyl, aryl, aralkyl, alkyl containing at least one functional ester group or a -R2SiX1X2X3 group, where each R3, other than hydrogen, contains from 1 to 18 carbon atoms, and with the proviso that when A2 is oxygen or sulfur, then A1 is (- ) 2NR3; each occurrence of X1 is, independently, R4O-, in which each R4 is independently selected from the group consisting of hydrogen, groups alkyl, alkenyl, arenyl, aryl and aralkyl, in which each R4, different from hydrogen, contains 1 to 18 carbon atoms and optionally contains at least one oxygen or sulfur atom; each occurrence of X2 and X3 is independently selected from the group consisting of R4O- and R5 in which each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl and aralkyl, where each R4, other than hydrogen, it contains 1 to 18 carbon atoms and optionally contains at least one oxygen or sulfur atom and each R5 is independently an alkyl group containing 1 to 6 carbon atoms, and each occurrence of subscripts, a and b is, independently, an integer, where a is 0 or 1 and b is 1 to 6.
[2]
2. Moisture-curable resin composition according to claim 1, CHARACTERIZED by the fact that said component (a) is derived from a polyol reagent, or a combination of polyol reagents and optionally contains at least one group functional organic selected from the group consisting of urethane, thiourethane, urea, biuret, ester, thioester, ether, thioether, and amide, in which the polyol reagent has an average molecular weight of 300 to 24,000 grams per mol.
[3]
3. Moisture-curable resin composition according to claim 1, CHARACTERIZED by the fact that R1 is a polymer fragment having an average molecular weight of 500 to 25,000 grams per mol, R2 is an alkylene of 1 to 3 atoms of carbon; A1 is oxygen or nitrogen substituted from structure (-) 2NR3, where R3 is hydrogen, A2 is substituted nitrogen from structure (-) 2NR3, where R3 is hydrogen, alkyl or aryl, where each R3, with the exception of hydrogen, contains from 1 to 10 carbon atoms, X1 and X2 are methoxy, ethoxy or propoxy, and X3 is methyl, methoxy, ethoxy or propoxy.
[4]
4. Moisture-curable resin composition according to claim 1, CHARACTERIZED by the fact that the moisture-curable polymer (a) is prepared by reacting a polyol or a combination of polyols with less than an equivalent amount for little more than an equivalent amount of a hydrolyzable silane containing an isocyanate group selected from the group consisting of isocyanatomethyltrimethoxysilane, isocyanatomethylmethydimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatoisopropyltrimethoxysilane, 4-isocyanatoethylethyl, 3-methoxy-trimetyl 3-isocyanatopropyltriethoxysilane, 3-isocyanatoisopropyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 2-isocyanato-1,1-dimethylethyl triethoxysilane, 3-isocyanatopropylmethyldimethoxyethyl, 4-isocyanatoispropyldimethylmethylsilane, 4-isoethylethylethyl, methoxy-methanesilane
[5]
5. Moisture-curable resin composition according to claim 1, CHARACTERIZED by the fact that said component (a) is represented by the general formula (VII): Formula (VII) in which R1 is an organic polymer fragment containing at least one urethane group as a result of the reaction of a polyol with an isocyanate group, and has an average molecular weight of 4,000 to 18,000 grams per mol, each occurrence of R2 is, independently, a divalent hydrocarbilene group containing 1 to 12 atoms of carbon, each occurrence of X1 is independently R4O-, in which each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl and aralkyl groups, where each R4, other than hydrogen, contains from 1 to 18 carbon atoms and, optionally, contains at least one oxygen or sulfur atom; each occurrence of X2 and X3 is independently selected from the group consisting of R4O- and R5 in which each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl and aralkyl, where each R4 , unlike hydrogen, contains 1 to 18 carbon atoms and optionally contains at least one oxygen or sulfur atom and each R5 is, independently, an alkyl group containing 1 to 6 carbon atoms, and b is 2.
[6]
6. Moisture-curable resin composition according to claim 5, CHARACTERIZED by the fact that component (a) is a silylated polyurethane prepared by a process comprising: (A) reacting a polyol component with a diisocyanate component in a stoichiometric excess of the polyol component to the diisocyanate component to form a hydroxyl terminated polyurethane, and (B) reacting the hydroxyl terminated polyurethane with one or more isocyanate silanes of the formula OCN-R2-SiX1X2X3, where each occurrence of R2 is independently a divalent hydrocarbilene group containing from 1 to 12 carbon atoms, each occurrence of X1 is independently R4O-, where each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl groups and aralkyl, where each R4, other than hydrogen, contains from 1 to 18 carbon atoms and, optionally, contains at least one oxygen or sulfur atom and; and each occurrence of X2 and X3 is independently selected from the group consisting of R4O- and R5 where each R4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, arenyl, aryl and aralkyl, where each R4, unlike hydrogen, contains from 1 to 18 carbon atoms and, optionally, contains at least one oxygen or sulfur atom and each R5 is, independently, an alkyl group containing from 1 to 6 carbon atoms.
[7]
7. Moisture-curable resin composition according to claim 6, CHARACTERIZED by the fact that the polyol is selected from the group consisting of polypropylene oxide with hydroxyl termination, polyethylene oxide with hydroxyl termination, polybutylene oxide with termination hydroxyl, and combinations thereof or in which the diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4- and 2,6-toluene diisocyanate, 4,4'-diphenyl-methanediisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, various liquid diphenylmethane-diisocyanates, containing a mixture of 2,4- and 4,4 'isomers, and combinations thereof.
[8]
8. Moisture-curable resin composition according to claim 1, CHARACTERIZED by the fact that said component (b) is selected from the group consisting of butyl trimethoxy silane, sec-butyl trimethoxy silane, he-xyl-trimethoxy-silane, hexyl-dimethoxy-methyl-silane, hex-5-enyl-trimethoxy-silane, hex-5-enyl-dimethoxy-methyl-silane, trimethoxy-octyl-silane, dimethoxy-methyl-octyl- silane, decyl-trimethoxy-silane, decyl-dimethoxy-methyl-silane, dodecyl-trimethoxy-silane, dodecyl-dimethoxy-methyl-silane, hexadecyl-trimethoxy-silane, hexadecyl-dimethoxy-methyl-silane, octadecyl-trimethoxy-silane, dimethoxy-methyl-octadecyl-silane, dimethoxy-methyl-eicosyl-silane, trimethoxy-methyl-eicosyl-silane, and combinations thereof.
[9]
9. Moisture-curable resin composition according to claim 1, CHARACTERIZED by the fact that said component (c) is selected from the group consisting of trimethoxy- (3-oxiranylmethoxy-propyl) -silane, dimethoxy- methyl- (3-oxiranylmethoxy-propyl) -silane, and combinations thereof.
[10]
10. Moisture-curable composition according to claim 1, CHARACTERIZED by the fact that the composition is substantially free of aminofunctional alkoxysilanes.
[11]
11. Moisture-curable composition according to claim 1, CHARACTERIZED by the fact that it also comprises at least one additive selected from the group consisting of a catalyst to catalyze the reaction between said component (a) with water under conditions curing agent, a filler, a plasticizer, and combinations thereof or further comprising at least one additive selected from the group consisting of pigments, thixotropes, waxes, anti-slip agents, stabilizers, viscosity modifiers, and combinations thereof.
[12]
12. Curable composition CHARACTERIZED by the fact that it is produced by contacting the composition, as defined in claim 1, with water.
[13]
13. Moisture-curable sealant, adhesive or coating, CHARACTERIZED by the fact that it contains the moisture-curable resin composition, as defined in claim 1.
[14]
14. Method for treating a substrate CHARACTERIZED by the fact that it comprises: (a) providing a composition, as defined in claim 1; (b) applying said composition to a surface of the substrate.
[15]
15. Method, according to claim 14, CHARACTERIZED by the fact that the substrate is concrete.
[16]
16. Article CHARACTERIZED by the fact that it comprises the cured moisture curable resin composition, as defined in claim 1 and a non-prime concrete substrate, to which the cured moisture curable resin composition is attached in which the article has a minimum of at least 20% cohesion failure and peeling forces from 1.80 to 8.90 N / mm after exposure to water for seven days, when the article is tested according to ASTM C-794-06.

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同族专利:

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公开号 | 公开日

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CN103582674A|2014-02-12|

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JP2014510816A|2014-05-01|

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EP2691464A1|2014-02-05|

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WO2012135443A1|2012-10-04|

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KR101865544B1|2018-06-08|

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US8859674B2|2014-10-14|

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EP2691464B1|2019-01-09|

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KR20140035353A|2014-03-21|

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JP6329481B2|2018-05-23|

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CN103582674B|2016-06-15|

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US20120251832A1|2012-10-04|

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TW201245259A|2012-11-16|

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JP2017125188A|2017-07-20|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-01-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-03-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/077,077|US8859674B2|2011-03-31|2011-03-31|Moisture curable silylated polymer compositions with improved adhesion to concrete|

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US13/077,077|2011-03-31|

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PCT/US2012/031124|WO2012135443A1|2011-03-31|2012-03-29|Moisture curable silylated polymer compositions with improved adhesion to concrete|

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