Non-sag composition

Abstract

A room temperature vulcanizable composition is presented and described herein which is both room temperature curable and exhibits non-sag properties, allowing the composition to be used in a variety of applications, including both horizontal and vertical joints.

Description

[Technical Field]

[0001] Cross-reference to related applications This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 242,276, entitled "Non-Sag Composition," filed September 9, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to room temperature vulcanizable compositions. In particular, the present invention relates to room temperature vulcanizable compositions that exhibit non-sag properties in substantially thicker applications. Methods for using the compositions to bond or seal surfaces are also provided. [Background technology]

[0003] Some room-temperature vulcanizing (RTV) compositions can be used as adhesives or sealants in a variety of applications. One use of an RTV sealant is to seal joints, such as pour joints. The sealant may be required to be able to seal a variety of joints of various shapes and configurations, and sealants preferred in the industry are those that can seal joints in as many situations as possible. Sealants generally require various physical properties to maintain their sealability after curing in the field. For example, pour joints, and therefore sealants sealing them, typically undergo movement that can occur due to, for example, thermal expansion or contraction of the substrates forming the joint. To accommodate this repeated movement, the sealant must have a certain degree of elasticity. The elasticity of a sealant can be determined from several physical properties, such as elongation at break (maximum elongation), modulus at 100% elongation, and tensile strength. Filler-free silicone elastomers can exhibit very high elongation at break (over 500%), but their modulus, tensile strength, hardness, and tear strength are too low for the cured sealant to function adequately in pour joint sealing applications. To improve the overall elastic behavior of such sealants and enable them to function to seal joints, reinforcing fillers must be added to the formulation.

[0004] Flowable sealants are often used in horizontal applications, such as highway joints. However, other applications, such as many construction applications, require the sealant to have sufficient sag control in the uncured state to allow the uncured sealant composition to be applied to and / or into overhead cracks and wall cracks. Such joints are typically called vertical joints. In such vertical applications, the sealant must remain in place after application or processing without flowing out of the crack until it cures to form a silicone elastomeric seal. Sag control generally refers to the state in which the uncured composition is extrudable and flowable, but under the force of gravity alone, the applied uncured sealant composition will remain in place without flowing until it cures into an elastomeric body. Thus, sag control is an important property for silicone sealants used in the construction industry for sealing, especially for vertical joints. In particular, sealants for vertical applications must exhibit non-sag properties.

[0005] Generally, the "sag" of a sealant can be reduced by adding a large amount of filler (reinforcing or non-reinforcing), i.e., a non-sag additive, but the sealant must still be extrudable in the uncured state for application over vertical joints. Furthermore, the amount of filler required to impart non-sag properties to a silicone sealant formulation can result in poor mechanical properties, particularly low elongation. Summary of the Invention

[0006] The following is a summary of the present disclosure to provide a basic understanding of some embodiments. This summary is not intended to identify key or essential elements, nor is it intended to define any limitations on the embodiments or claims. Moreover, this summary may provide a simplified overview of some embodiments, which may be described in detail in other parts of the disclosure.

[0007] Provided is a two-component, room-temperature vulcanizing (RTV) composition suitable for use as an adhesive or sealant in applications requiring non-sag properties. The composition provides a low viscosity material that is suitable for dispensing and mixing in large volumes and exhibits suitable non-sag properties while curing at a desired thickness for vertical applications.

[0008] The present compositions have surprisingly been found to have flow properties that allow for high speed mixing and dispensing, while also exhibiting non-sag properties at significant thicknesses, allowing the compositions to be used in vertical applications.

[0009] The composition comprises two components which, when combined, are sufficiently non-flowable to allow for large volume dispensing, yet exhibit non-sag properties prior to hardening that allow the composition to be used in vertical applications.

[0010] In one embodiment, the composition upon cure exhibits a non-sag of from about 60 mils to about 235 mils (about 0.06 inches to about 0.235 inches).

[0011] In one embodiment, provided is a two-component, room temperature vulcanizable composition comprising: (a) a first part comprising (i) a polysiloxane polymer having reactive groups, (ii) a filler, and (iii) optionally water; and (b) a second part comprising (i) a polysiloxane polymer that may or may not react with a condensation cure silicone system, (ii) a filler, and (iii) a tin catalyst.

[0012] In one embodiment, the first portion is heated at 25° C. and a shear rate of 10 s -1 (plate / plate system, plate diameter 40 mm, gap width 0.5 mm) has a viscosity of about 30 to about 300 PaS, and the second part is heated at 25°C and a shear rate of 10 s -1(plate / plate system, plate diameter 40 mm, gap width 0.5 mm) has a viscosity of about 50 to about 300 PaS.

[0013] In one embodiment according to any of the above embodiments, the tin catalyst comprises a mixture of silica and a tin compound. In one embodiment, the tin compound is selected from dialkyltin dicarboxylates.

[0014] In one embodiment according to any of the above embodiments, the tin compound is present in an amount of about 0.1% to about 6% by weight based on the total weight of the second part.

[0015] In one embodiment according to any of the above embodiments, the polymeric siloxane (i) of the first part is a silanol-terminated polysiloxane.

[0016] In one embodiment according to any of the above embodiments, the silanol terminated polysiloxane has the formula: M 1 a D 1 b D 2 c is a diorganopolysiloxane polymer of the formula: M 1 =(HO) 3-x-y R 1 x R 2 y SiO 1 / 2 ; D 1 =R 3 R 4 SiO 2 / 2 ; D 2 =R 5 R 6 SiO 2 / 2 ; where R 1 and R 2 are independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; R 3 and R4 are independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; R 5 and R 6 are independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; a is 2, b is equal to or greater than 1, c is zero or a positive integer, x is 0, 1, or 2, and y is either 0 or 1, subject to the proviso that x+y is equal to or less than 2.

[0017] In one embodiment, the silanol-terminated polysiloxane is dimethyldiphenylpolysiloxane.

[0018] In one embodiment according to any of the above embodiments, the polysiloxane polymer (i) of the second portion is an alkenyl-terminated polysiloxane.

[0019] In one embodiment according to any of the above embodiments, the polysiloxane polymer (i) of the second portion is a vinyl-terminated polysiloxane.

[0020] In one embodiment according to any of the above embodiments, the polysiloxane (i) of the second portion has the formula: M 2 d D 3 e D 4 f wherein M 2 =(R 11 )(R 12 )(R 13 )SiO 1 / 2 ; D 3 =R 14 R 15 SiO 2 / 2 ; D 4 =R 16 R 17 SiO 2 / 2 ; where R 11 , R 12 , and R 13are independently selected from hydrocarbons of up to about 60 carbon atoms and can have reactive or non-reactive groups; R 14 and R 15 are independently selected from hydrocarbons of up to about 60 carbon atoms; R 16 and R 17 are independently selected from hydrocarbons of up to about 60 carbon atoms; the subscript d is 2, e is equal to or greater than 1, and f is zero or a positive integer; R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 At least one of the groups is optionally a group containing a reactive group or a non-reactive group.

[0021] In one embodiment, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 At least one of the groups is an alkenyl functional group.

[0022] In one embodiment according to any of the above embodiments, the filler is present in an amount of about 35% to about 60% by weight based on the total weight of the vulcanizable composition.

[0023] In one embodiment according to any of the above embodiments, the composition comprises a silanol-functional polyorganosiloxane having a silanol content of at least about 5 weight percent based on the weight of the silanol-functional polyorganosiloxane.

[0024] In one embodiment, the silanol-functional polyorganosiloxane has the formula: M 3 g D 5 h D 6 i wherein M3 =(R 18 )(R 19 )(R 20 )SiO 1 / 2 ; D 5 =R 21 R 22 SiO 2 / 2 ; D 6 =R 23 R 24 SiO 2 / 2 ; where R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are independently selected from hydrocarbons of up to about 60 carbon atoms and hydroxyl groups; the subscript g is 2, h is equal to or greater than 1, and i is zero or a positive integer; and the silanol-functional polyorganosiloxane has a silanol content of at least 5%.

[0025] In one embodiment according to any of the above embodiments, h+i is from about 5 to about 2,500.

[0026] In one embodiment according to any of the above embodiments, the silanol-functional polyorganosiloxane has a silanol content of about 5% to about 10% by weight, based on the total weight of the silanol-functional polyorganosiloxane. In one embodiment, the silanol-functional polyorganosiloxane has a silanol content of about 5% to about 10% by weight, about 5.5% to about 9.5% by weight, about 6% to about 8% by weight, or about 6.5% to about 7% by weight, based on the total weight of the silanol-functional polyorganosiloxane.

[0027] In one embodiment according to any of the above embodiments, the silanol-functional polyorganosiloxane is present in the first part or the second part in an amount of about 0.05 wt % to about 1 wt %, based on the total weight of the part to which it is added.

[0028] In one embodiment according to any of the above embodiments, the silanol-functional polyorganosiloxane is present in the first portion.

[0029] In one embodiment according to any of the above embodiments, the weight ratio of the first portion to the second portion is from about 10:0.7 to about 10:1.

[0030] In one embodiment according to any of the above embodiments, the weight ratio of the first portion to the second portion is from about 10:0.75 to about 10:0.95.

[0031] In one embodiment according to any of the above embodiments, upon mixing and curing the first and second parts, the composition exhibits non-sag properties from about 60 mils to about 235 mils.

[0032] In another embodiment, provided is a cured material formed from a mixture of room temperature vulcanizable compositions of any of the above aspects or embodiments.

[0033] In a further embodiment, provided is a method for treating a surface comprising applying a mixture of the first and second parts of the two-component vulcanizable composition of any of the above aspects or embodiments.

[0034] In one embodiment of this method, the weight ratio of the first portion to the second portion is from about 10:0.7 to about 10:1. In one embodiment of this method, the weight ratio of the first portion to the second portion is from about 10:0.75 to about 10:0.95.

[0035] The following description and drawings disclose various exemplary aspects. Some improvements and novel aspects may be explicitly identified, while others may be apparent from the description and drawings. DETAILED DESCRIPTION OF THE INVENTION

[0036] Reference will now be made to exemplary embodiments, examples of which are illustrated in the associated detailed description. It will be understood that other embodiments may be utilized, and structural and functional changes may be made. Furthermore, features of various embodiments may be combined or varied. Thus, the following description is provided by way of example only, and is not intended to limit in any way the various alternatives and modifications that may be made to the exemplary embodiments. In this disclosure, numerous specific details are set forth to provide a thorough understanding of the disclosed subject matter. It should be understood that embodiments of the present disclosure may be practiced in other embodiments that do not necessarily include all aspects set forth herein or elsewhere.

[0037] As used herein, the terms "example" and "exemplary" mean illustrative or illustrative. The terms "example" and "exemplary" do not indicate required or preferred implementations or embodiments. The term "or" is intended to be inclusive rather than exclusive, unless the context indicates otherwise. For example, the phrase "A uses B or C" includes any inclusive permutation (e.g., A uses B; A uses C; or A uses both B and C). As a separate matter, the articles "a" and "an" are generally intended to mean "one or more," unless the context indicates otherwise.

[0038] The composition is a two-part, room-temperature vulcanizing composition. The composition includes a silicone polymer that is curable upon exposure to moisture. In one embodiment, the composition is mixed in two parts and cures at a temperature of about 5°C to about 50°C upon exposure to moisture. The composition includes a tin paste catalyst in one part. The use of a tin paste catalyst and mixing the parts in the desired proportions results in a room-temperature vulcanizing composition that exhibits non-sag properties at significant coating or application thicknesses.

[0039] In one embodiment, the composition comprises a first part (Component A) and a second part (Component B), where the first part comprises a silicone polymer, one or more fillers, a crosslinker, and optionally water, and the second part comprises a silicone polymer, a tin catalyst, and a filler. The catalyst is combined with the filler in the second part, thereby providing the second part as a paste. The composition optionally contains other materials, such as fillers, pigments, adhesion promoters, and other additives known or commonly used in such sealant and adhesive compositions. In one embodiment, the second part comprises a pigment and an adhesion promoter.

[0040] Part 1 (component A)

[0041] The first portion comprises a silicone polymer with groups reactive to a protic solvent such as water. The silicone polymer may be a polymer having reactive groups selected from OH, alkoxy, alkenyloxy, alkyloximo, alkylcarboxy, arylcarboxy, or a combination of two or more thereof. In one embodiment, the silicone polymer is a polysiloxane polymer containing reactive groups. In one embodiment, the first portion comprises a silanol-terminated diorganopolysiloxane.

[0042] In one embodiment, the silanol-terminated diorganopolysiloxane polymer has the general formula: M 1 a D 1 b D 2 c It is of M 1 =(HO) 3-x-y R 1 x R 2 y SiO 1 / 2 ; D 1 =R 3 R 4SiO 2 / 2 ; D 2 =R 5 R 6 SiO 2 / 2 ; where R 1 and R 2 are independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; R 3 and R 4 are independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; R 5 and R 6 are independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; a is 2, b is greater than or equal to 1, c is zero or a positive integer, x is 0, 1, or 2, and y is either 0 or 1, subject to the conditions that x+y is less than or equal to 2.

[0043] In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from C1-C10 alkyl and C6-C30 aryl. 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, phenyl, and tolyl. In an exemplary embodiment, the silicone polymer is a silanol-terminated dimethyldiphenylsiloxane.

[0044] In one embodiment of the present invention, the silicone polymer is provided in an amount of about 5% to about 95%, about 35% to about 85%, or about 50% to about 70% by weight of the total composition.

[0045] According to one embodiment of the present invention, the viscosity of the polysiloxane polymer in the first portion is about 2.5 to about 20 PaS, about 4 to about 16 PaS, about 5 to about 12 PaS, or about 7.5 to about 10 PaS at 25° C. The viscosity was evaluated by an Ostwald viscometer tube (based on ASTM D445).

[0046] The first part may further comprise one or more fillers. Examples of suitable fillers include, but are not limited to, crushed quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide, carbon black, talc, cristobalite, mica, feldspar, wollastonite, fumed silica, treated fumed silica, aluminite, calcium sulfate (anhydrite), gypsum, aluminum trihydroxide, magnesium hydroxide (brucite), graphite, aluminum oxide, or a silicate selected from the group consisting of olivine, garnet, aluminosilicate, cyclic silicate, chain silicate, and layered silicate, or plastic or glass microspheres, preferably hollow microspheres. The filler may be present, for example, in an amount of 35% to about 60% by weight, about 40% to about 55% by weight, or about 45 to about 50% by weight, based on the total weight of the composition. Fillers are used provided that the introduction of the filler does not negatively affect the physical properties of the uncured sealant composition (eg, sag) or the physical properties of the subsequently cured product (eg, elongation at break).

[0047] The first part may also include a crosslinker. In one embodiment, the crosslinker or chain extender may be selected from alkoxysilanes, alkoxysiloxanes, oximosilanes, oximosiloxanes, enoxysilanes, enoxysiloxanes, aminosilanes, aminosiloxanes, carboxysilanes, carboxysiloxanes, alkylamidosilanes, alkylamidosiloxanes, arylamidosilanes, arylamidosiloxanes, alkoxyaminosilanes, alkylarylaminosiloxanes, alkoxycarbamatesilanes, alkoxycarbamatesiloxanes, imidatosilanes, ureidosilanes, isocyanatesilanes, thioisocyanatesilanes, condensates thereof, and combinations of two or more thereof.

[0048] In one embodiment, the crosslinker is selected from alkoxysilanes. In one embodiment, the alkyl silicate has the formula: (R 7 O)(R 8 O)(R 9 O)(R 10 O)Si wherein R 7 , R 8 , R 9 , and R 10 are independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms. In one embodiment, R 7 , R 8 , R 9 , and R 10 are each independently selected from C1 to C10 alkyl and C6 to C30 aryl.

[0049] Examples of suitable crosslinkers include, but are not limited to, tetraethyl orthosilicate (TEOS); methyltrimethoxysilane (MTMS); methyltriethoxysilane; vinyltrimethoxysilane; vinyltriethoxysilane; methylphenyldimethoxysilane; 3,3,3-trifluoropropyltrimethoxysilane; methyltriacetoxysilane; vinyltriacetoxysilane; ethyltriacetoxysilane; di-butoxydiacetoxysilane; phenyltrippropionoxysilane; methyltris(methylethylketoximo)silane; vinyltris( (methylethylketoximo)silane;3,3,3-Trifluoropropyltris(methylethylketoximo)silane;Methyltris(isopropenoxy)silane;Vinyltris(isopropenoxy)silane;Ethyl polysilicate;Dimethyltetraacetoxydisiloxane;Tetra-n-propyl orthosilicate;Methyldimethoxy(ethylmethylketoximo)silane;Methylmethoxybis(ethylmethylketoximo)silane;Methyldimethoxy(acetaldoximo)silane;Methyldimethoxy(N-methylcarbamate)silane;Ethyldimethoxy Di(N-methylcarbamate)silane;Methyldimethoxyisopropenoxysilane;Trimethoxyisopropenoxysilane;Methyltriisopropenoxysilane;Methyldimethoxy(but-2-en-2-oxy)silane;Methyldimethoxy(1-phenylethenoxy)silane;Methyldimethoxy-2(1-carbethoxypropenoxy)silane;Methylmethoxydi(N-methylamino)silane;Vinyldimethoxy(methylamino)silane;Tetra-N,N-diethylaminosilane;Methyldimethoxy(methylamino)silane;Methyltri(silane) (cyclohexylamino)silane;Methyldimethoxy(ethylamino)silane;Dimethyldi(N,N-dimethylamino)silane;Methyldimethoxy(isopropylamino)silane;Dimethyldi(N,N-diethylamino)silane;Ethyldimethoxy(N-ethylpropionamido)silane;Methyldimethoxy(N-methylacetamido)silane;Methyltris(N-methylacetamido)silane;Ethyldimethoxy(N-methylacetamido)silane;Methyltris(N-methylbenzamido)silane;Methylmethoxybis(N-methylacetamido)silaneExamples of suitable silanes include methyldimethoxy(caprolactam)silane, trimethoxy(N-methylacetamido)silane, methyldimethoxy(ethylacetimidato)silane, methyldimethoxy(propylacetimidato)silane, methyldimethoxy(N,N',N'-trimethylureido)silane, methyldimethoxy(N-allyl-N',N'-dimethylureido)silane, methyldimethoxy(N-phenyl-N',N'-dimethylureido)silane, methyldimethoxyisocyanatosilane, dimethoxydiisocyanatosilane, methyldimethoxythioisocyanatosilane, methylmethoxydithioisocyanatosilane, condensates thereof, or combinations of two or more thereof.

[0050] According to one embodiment of the present invention, the crosslinking agent is present in an amount of about 0.01% to about 20%, about 0.1% to about 15%, about 0.2% to about 10%, and about 0.3% to about 5% by weight, based on the total weight of the composition. In yet another embodiment, the adhesion promoter is in the range of about 0.5% to about 1.5% by weight of the total composition.

[0051] The composition may optionally include a silanol inhibitor. The silanol inhibitor may be selected from short-chain silanol-functional polyorganosiloxanes having a silanol content of at least 5% by weight, based on the weight of the short-chain silanol-functional polyorganosiloxane. The short-chain silanol-functional polyorganosiloxane may also be referred to herein as a silanol-functional polyorganosiloxane. In one embodiment, the silanol inhibitor has a silanol content of about 5% to about 10% by weight, based on the weight of the short-chain polyorganosiloxane (i.e., the silanol-functional polyorganosiloxane).

[0052] In one embodiment, the silanol inhibitor has the formula: M 3 g D 5 h D 6 i is a silanol-functional polyorganosiloxane of the formula: M 3 =(R 18 )(R 19 )(R 20 )SiO 1 / 2 ; D 5 =R 21 R 22 SiO 2 / 2 ; D 6 =R 23 R 24 SiO 2 / 2 ; R in the formula 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are independently selected from hydrocarbons of up to about 60 carbon atoms and hydroxyl groups; The subscript g is 2, h is equal to or greater than 1, and i is zero or a positive integer; and the silanol-functional polyorganosiloxane has a silanol content of at least 5 weight percent, based on the weight of the silanol-functional polyorganosiloxane. In one embodiment, h+i is from about 5 to about 2,500, from about 10 to about 2,250, from about 25 to about 2,000, from about 50 to about 1,750, from about 75 to about 1,500, from about 100 to about 1,000, or from about 200 to about 750.

[0053] In one embodiment, R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from C1-C10 alkyl and C6-C30 aryl. 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24are each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, phenyl, and tosyl. 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 is independently selected from methyl and / or phenyl.

[0054] The silanol inhibitor has a silanol content of at least 5% by weight based on the weight of the silanol-functional polyorganosiloxane. In one embodiment, the silanol inhibitor has a silanol content of about 5% to about 10%, about 5.5% to about 9.5%, about 6% to about 8%, or about 6.5% to about 7% by weight based on the weight of the silanol-functional polyorganosiloxane.

[0055] The silanol inhibitor can be added to Component A, Component B, or both Component A and Component B. In one embodiment, the silanol inhibitor is added to either Component A or Component B and is added to that component in an amount of 0 to about 1 wt %, about 0.05 wt % to about 0.95 wt %, about 0.1 wt % to about 0.8 wt %, about 0.2 wt % to about 0.6 wt %, or about 0.3 wt % to about 0.5 wt %, based on the weight of the component to which the silanol inhibitor is added. In one embodiment, the silanol inhibitor is added to Component A.

[0056] The first part may be anhydrous or may optionally contain a small amount of water to facilitate the initial reaction upon mixing with the second part. In one embodiment, the first part may contain water in an amount of about 0.05% to about 0.5%, about 0.1% to about 0.4%, or about 0.2 to about 0.3% by weight, based on the total weight of the first part.

[0057] In one embodiment, the first part of the two-component composition is heated at 25° C. and a shear rate of 10 s -1(plate / plate system, plate diameter 40 mm, gap width 0.5 mm) may have a viscosity of about 30 to about 300 PaS, about 35 to about 200, about 40 to about 100, or about 50 to about 80 PaS.

[0058] Second part (component B)

[0059] The second part of the two-component composition includes a silicone polymer, a catalyst, and a filler, wherein the catalyst is combined with the filler to provide the second part as a paste.

[0060] The silicone polymer of the second part comprises a polysiloxane polymer that does not react with the condensation cure silicone system. In one embodiment, the silicone of the second part can comprise reactive groups selected from OH, alkoxy, alkenyloxy, alkyloximo, alkylcarboxy, arylcarboxy, or a combination of two or more thereof. In one embodiment, the silicone polymer of the second part is a polysiloxane polymer.

[0061] In one embodiment, the second moiety has the formula: M 2 d D 3 e D 4 f and a polysiloxane polymer of the formula: M 2 =(R 11 )(R 12 )(R 13 )SiO 1 / 2 ; D 3 =R 14 R 15 SiO 2 / 2 ; D 4 =R 16 R 17 SiO 2 / 2 ; R in the formula 11 , R 12 , and R13 are independently selected from hydrocarbons of up to about 60 carbon atoms, and may have reactive or non-reactive groups; R 14 and R 15 are independently selected from hydrocarbons of up to about 60 carbon atoms; R 16 and R 17 are independently selected from hydrocarbons of up to about 60 carbon atoms; The subscript d is 2, e is greater than or equal to 1, and f is zero or a positive integer; R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 optionally includes reactive or non-reactive groups.

[0062] In one embodiment, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are each independently selected from C1-C10 alkyl and C6-C30 aryl. 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, phenyl, and tosyl.

[0063] In one embodiment, the silicone polymer of the second portion is selected from alkenyl-functional siloxanes. In one embodiment, the siloxane of the second portion is selected from vinyl-terminated siloxanes. Examples of siloxanes suitable for the second portion include, but are not limited to, vinyl-terminated dimethyl siloxane, vinyl-terminated dimethyl diphenyl siloxane, and others.

[0064] In one embodiment of the present invention, the silicone polymer of the second part is present in an amount of from about 5% to about 95% by weight of the total composition, in another embodiment from about 35% to about 85% by weight, and in yet another embodiment from about 50% to about 70% by weight.

[0065] According to one embodiment of the invention, the viscosity of the silicone polymer of the second part is from about 1 to about 20 PaS, from about 2.5 to about 18 PaS, from about 5 to about 15 PaS, or from about 7.5 to about 10 PaS at 25° C. The viscosity is assessed by an Ostwald viscometer tube.

[0066] The second part of the two-part curing composition contains a condensation catalyst, which, according to the present technology, is formulated with a filler to provide the second part as a paste.

[0067] Tin compounds useful for promoting crosslinking in silicone rubber-forming compositions include any tin material useful for promoting crosslinking in rubber-forming compositions. In one embodiment, the tin compound is selected from dialkyltin dicarboxylates. The alkyl groups in the dialkyltin compounds can be selected as desired and, in embodiments, are selected from C1-C10 alkyls such as, but not limited to, methyl, ethyl, propyl, butyl, and the like. The carboxylate can be selected as desired and can be derived from any suitable carboxylic acid. Non-limiting examples of suitable carboxylate groups include acetate, 2-ethylhexanoate, and neodecanoate. Examples of suitable compounds include, but are not limited to, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, tin octoate, isobutyltin triceroate, dibutyltin oxide, dibutyltin bis-isooctyl phthalate, bis-tripoxysilyldioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, carbomethoxyphenyltin tris-uberate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin di-neodecanoate, dibutyltin di-neodecanoate, triethyltin tartrate, dibutyltin dibenzoate, tin oleate, tin naphthenate naphthenate, butyltin tri-2-ethylhexylhexanoate, and tin butyrate. In one embodiment, the tin catalyst is a paste of dimethyltin dineodecanoate.

[0068] The tin compound can be present in an amount of about 0.1% to about 6%, about 0.3% to about 3%, or about 0.5% to about 1.5% by weight based on the total weight of the second part.

[0069] The second part contains a filler that, when mixed with the catalyst, results in a paste. Examples of suitable fillers include, but are not limited to, crushed quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide, carbon black, talc, cristobalite, mica, feldspar, wollastonite, fumed silica, fumed alumina, aluminite, calcium sulfate (anhydrite), gypsum, aluminum trihydroxide, magnesium hydroxide (brucite), graphite, aluminum oxide, or a silicate selected from the group consisting of olivine, garnet, aluminosilicate, cyclic silicate, chain silicate, and layer silicate, or plastic or glass microspheres, preferably hollow microspheres. The filler used to form the paste is provided in an amount of 15% to about 63%, about 20% to about 35%, or about 25 to about 30% by weight, based on the total weight of the second part.

[0070] The second part of the two-component composition was heated at 20°C and a shear rate of 10 s -1 (plate / plate system, plate diameter 40 mm, gap width 0.5 mm) may have a viscosity of about 50 PaS to about 300 PaS, about 60 PaS to about 250 PaS, about 70 PaS to about 200 PaS, or about 80 PaS to about 150 PaS.

[0071] The composition may further comprise an adhesion promoter. In one embodiment, the adhesion promoter is provided in the second part. Adhesion promoters include, but are not limited to, those described in U.S. Patent Publication No. 2014 / 0378612, the disclosure of which is incorporated herein by reference in its entirety. Some examples of suitable adhesion promoters include, but are not limited to, N-(2-aminoethyl)aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, bis(gamma-trimethoxysilylpropyl)amine, N-phenyl-gamma-aminopropyltrimethoxysilane, triaminofunctional trimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxyethyltrimethoxysilane, gamma-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethylmethyl -dimethoxysilane, epoxylimonyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane, beta-cyano-ethyl-trimethoxysilane, gamma-acryloxypropyl-trimethoxysilane, gamma-methacryloxypropyl-methyldimethoxysilane, alpha,omega-bis-(aminoalkyl-diethoxysilyl)polydimethylsiloxane (Pn=1-7), alpha,omega-bis-(aminoalkyl-diethoxysilyl)-octa-methyltetrasiloxane, 4-amino-3,3,-dimethyl-butyl-tri-methoxysilane, and N-ethyl-3-tri-methoxy-silyl-2-methylpropanamine, 3-(diethyl-aminopropyl)-trimethoxysilane, combinations of two or more of these, and others.Particularly suitable adhesion promoters include, but are not limited to, bis(alkyltrialkoxysilyl)amines and tris(alkyltrialkoxysilyl)amines, such as bis(3-propyltrimethoxysilyl)amine and tris(3-propyltrimethoxysilyl)amine.

[0072] The adhesion promoter may be provided in either the first part or the second part. In one embodiment, the adhesion promoter is provided in the second part (which includes the catalyst). Generally, the adhesion promoter can be provided in an amount of about 0.05% to about 10% by weight based on the combined weight of the first and second parts, about 0.1% to about 5% by weight based on the combined weight of the first and second parts, about 0.5% to about 2.5% by weight, or about 1% to about 2% by weight based on the combined weight of the first and second parts.

[0073] In one embodiment, the composition can include a cure inhibitor to slow the rate of cure. The cure inhibitor can be provided in either the first or second part. In one specific embodiment, the cure inhibitor (E) can include aliphatic unsaturation. In another specific embodiment, the cure inhibitor (E) can be free of aliphatic unsaturation. In a further embodiment, non-limiting examples of cure inhibitors (E) are selected from the group consisting of diallyl maleate, D-4 vinyl, 2-methyl-3-buten-2-ol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, and combinations thereof. In one specific embodiment, the cure inhibitor (E) is used in an amount of, specifically, about 0.02 to about 1 wt. %, more specifically, about 0.05 to about 0.5 wt. %, and most specifically, about 0.1 to about 0.2 wt. %, based on the total weight of the composition. In one particular embodiment, the cure inhibitor (E) can be present in any amount to provide a range of cure temperatures and cure times, specifically cure times anywhere from about 10 seconds at about 177°C to about 24 hours at room temperature.

[0074] The vulcanizable composition, in one embodiment, can be provided with a low concentration of volatile components. In one embodiment, the composition has a volatile content of about 0.1% or less per ASTM E595.

[0075] The present compositions are provided with a weight ratio of part one to part two of about 10:0.7 to about 10:1, about 10:0.75 to about 10:0.95, or about 10:0.8 to about 10:0.9. In one specific embodiment of the present invention, the weight ratio of part one to part two is 10:1. Applicant has discovered that blending at these ratios produces a non-flowable product of 0.235 inches (235 mils) or less. Surprisingly, it has been found that blends of part one and part two outside of these ratios do not result in a non-flowable product. Without being bound by any particular theory, it is expected that part one of the present compositions will largely control the flow / viscosity characteristics of the system. Part two has a higher viscosity, but is not expected to control the viscosity / flow characteristics of the system due to the lack / low addition of any effective thixotropic agent.

[0076] In one embodiment, the product produced from the curing of the mixture of A and B results in a product that exhibits a non-flowability of 0.235 inches or less. In one embodiment, the mixture of the first and second parts produces a product that is non-flowable at about 0.6 inches to about 0.235 inches (about 60 mils to about 235 mils). In one embodiment, the mixture produces a product that is non-flowable at at least about 60 mils to about 120 mils.

[0077] The first and second parts are typically mixed at 25° C. (room temperature); however, the temperature at which the first and second parts are mixed can vary widely, from about 25° C. to 200° C. According to one embodiment of the invention, the temperature at which the first and second parts are mixed is 25° C.

[0078] The first and second parts can be mixed by any suitable method. A non-flowable product can be achieved by hand mixing. More preferably, mixing is achieved by a mechanical mixer. The product can be produced by conventional mixing techniques, for example, in a mechanical mixer, planetary mixer, Hauschild mixer, Lödige mixer, mixing tube, or extruder. Mixing can be carried out batchwise or continuously.

[0079] The compositions can be used in a variety of sealing or bonding applications, including both horizontal and vertical joints.

[0080] Example

[0081] Example 1

[0082] A two-component composition was provided using the following parts:

[0083] JPEG2024531570000001.jpg59161

[0084] JPEG2024531570000002.jpg61159

[0085] Components A and B were mixed together in a Speedmixer at 3500 rpm for 10 seconds twice, the speed and time scale depending on the sample size.

[0086] Sag was evaluated by assessing the flow from the resulting product formed from the composition. A jig / applicator with multiple notches was placed on one end of a Renata paper strip. The applicator notches were designed to create stripes of thickness ranging from 14 to 250 mils. Approximately 20 grams of silicone coating was placed on the front of the applicator. The applicator was then drawn across the paper strip, maintaining a straight path, to the opposite end. The paper strip was placed in a vertical position with the 250 mil stripe (thickest stripe) on top. Sag was observed when any stripe merged with the strip below it.

[0087] For Example 1, the coating was observed to be non-flowable, ie, non-sag, from 60 mils to 120 mils.

[0088] Comparative Example 1

[0089] Comparative Example 1 is a product made from only Component A of Example 1. The catalyst used was dibutyltin dilaurate.

[0090] Comparative Example 2

[0091] Coatings from this composition were prepared from Component A of Example 1 and a dimethyl tin decanoate catalyst. This tin catalyst was not a paste.

[0092] Comparative Example 3

[0093] The coating of Comparative Example 3 utilized Component A of Example 1 and dibutyltin dilaurate paste RTV9950 (available from Momentive Performance Materials).

[0094] Comparative Example 4

[0095] The coating of Comparative Example 4 utilized RTV560 available from Momentive Performance Materials, Inc. with dibutyltin dilaurate.

[0096] Comparative Example 5

[0097] A composition was prepared as in Example 1 using the same composition as component B, except that component A was provided as follows:

[0098] JPEG2024531570000003.jpg61160

[0099] Example 2

[0100] A composition was prepared as in Example 1 using the following Component A and Component B compositions:

[0101] JPEG2024531570000004.jpg68163

[0102] JPEG2024531570000005.jpg61159

[0103] The silanol inhibitor is a polydimethylsiloxane polymer with a silanol content of about 6.6%.

[0104] Sag Test

[0105] Sag was evaluated by assessing the flow from the resulting product formed from the composition. A jig / applicator with multiple notches was placed on one end of a Renata paper strip. The applicator notches were designed to create stripes of thickness ranging from 14 to 250 mils. Approximately 20 grams of silicone coating was placed on the front of the applicator. The applicator was then drawn across the paper strip, maintaining a straight path, to the opposite end. The paper strip was placed in a vertical position with the 250 mil stripe (thickest stripe) on top. Sag was observed when any stripe merged with the strip below it.

[0106] Table 1 shows the results of the flow tests.

[0107] [Table 1]

[0108] The compositions were able to achieve non-flowability, i.e., non-sag properties between 60 and 235 mils. These compositions can be dispensed using high-speed mixing / dispensing methods and still have non-sag properties suitable for vertical applications. The compositions were surprisingly found to exhibit non-sag properties. Generally, at the mix ratios used herein, one would normally expect the first part to dominate the flow or viscosity properties. In particular, since the components of the first part do not provide significant non-sag properties, the second part would generally not be expected to dominate the viscosity / flow properties.

[0109] The foregoing description includes examples of the present specification. Of course, for purposes of describing the present specification, it is not possible to describe every conceivable combination of components or methodologies, but one of ordinary skill in the art may recognize that many additional combinations and permutations of the present specification are possible. Accordingly, the present specification is intended to embrace all such changes, modifications, and variations that fall within the spirit and scope of the appended claims. Furthermore, to the extent the term "comprising" is used in the detailed description or the claims, it is intended to be inclusive in the same manner as "including," but in the same manner as "comprising" is interpreted when used as a transitional term in the claims.

[0110] The foregoing description reveals various non-limiting embodiments of room temperature vulcanizable compositions. Modifications will occur to those skilled in the art and to those who make and use the invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or subject matter described in the claims.

Claims

1. A two-component room temperature vulcanizing composition comprising: (a) (i) a polysiloxane polymer having reactive groups, (ii) a filler, and (iii) optionally water, in a first part; and (b) (i) a polysiloxane polymer that reacts or does not react with a condensation-curing silicone system, (ii) a filler, and (iii) a tin catalyst, in a second part.

2. The first part has a viscosity of about 30 to about 300 PaS at 25 °C and a shear rate of 10 s －１ (plate / plate system, plate diameter 40 mm, gap width 0.5 mm), and the second part has a viscosity of about 50 to about 300 PaS at 25 °C and a shear rate of 10 s －１ (plate / plate system, plate diameter 40 mm, gap width 0.5 mm), the room temperature vulcanizing composition of Claim 1.

3. The tin catalyst in the room temperature vulcanizing composition of Claim 1 comprises a mixture of silica and a tin compound.

4. The tin compound is selected from dialkyltin dicarboxylates, the room temperature vulcanizing composition of Claim 3.

5. The tin compound is present in an amount of about 0.1 wt% to about 6 wt% based on the total weight of the second part, the room temperature vulcanizing composition of Claim 3.

6. The polymeric siloxane (i) of the first part is a silanol-terminated polysiloxane, the room temperature vulcanizing composition of Claim 1.

7. The silanol-terminated polysiloxane terminated with silanol has the formula: M １ ａ D １ ｂ D ２ ｃ is a diorganopolysiloxane polymer of, wherein: M １ = (HO) ３－ｘ－ｙ R １ ｘ R ２ ｙ SiO １／２ ; D １ = R ３ R ４ SiO ２／２ ; D ２ = R ５ R ６ SiO ２／２ ; Here, R １ and R ２ are each independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; R ３ and R ４ are each independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; R ５ and R ６ are each independently selected monovalent hydrocarbon radicals of up to about 60 carbon atoms; The room temperature vulcanizable composition of claim 6, wherein a is 2, b is equal to or greater than 1, c is zero or a positive integer, x is 0, 1, or 2, and y is either 0 or 1, subject to the condition that x + y is equal to or less than 2.

8. The room temperature vulcanizable composition of claim 6, wherein the silanol-terminated polysiloxane is dimethyldiphenylpolysiloxane.

9. The room temperature vulcanizable composition of claim 1, wherein the second part of the polysiloxane polymer (i) is an alkenyl-terminated polysiloxane.

10. The room temperature vulcanizable composition of claim 1, wherein the second part of the polysiloxane polymer (i) is a vinyl-terminated polysiloxane.

11. The second part of the polysiloxane (i) has the formula: M ２ ｄ D ３ ｅ D ４ ｆ which is of the formula M ２ = (R １１ )(R １２ )(R １３ )SiO １／２ ; D ３ = R １４ R １５ )SiO ２／２ ; D ４ = R １６ R １７ )SiO ２／２ ; where R １１ , R １２ , and R １３ are independently selected from hydrocarbons having up to about 60 carbon atoms and can have reactive or non-reactive groups; R １４ and R １５ are independently selected from hydrocarbons having up to about 60 carbon atoms; R １６ and R １７ are independently selected from hydrocarbons having up to about 60 carbon atoms; the subscript d is equal to or greater than 2, e is equal to 1, and f is zero or a positive integer; R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , and R １７ at least one of which is optionally a group containing a reactive or non-reactive group, the room temperature vulcanizing composition of claim 1.

12. R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , and R １７ at least one of which is an alkenyl functional group, the room temperature vulcanizing composition of claim 11.

13. The filler is present in an amount of from about 35% to about 60% by weight based on the total weight of the vulcanizable composition, the room temperature vulcanizable composition of claim 1.

14. The composition further comprises a silanol-functional polyorganosiloxane having a silanol content of at least about 5% by weight based on the weight of the silanol-functional polyorganosiloxane, the room temperature vulcanizable composition of claim 1.

15. The silanol-functional polyorganosiloxane has the formula: M ３ ｇ D ５ ｈ D ６ ｉ wherein M ３ = (R １８ )(R １９ )(R ２０ )SiO １／２ ; D ５ = R ２１ R ２２ )SiO ２／２ ; D ６ = R ２３ R ２４ )SiO ２／２ ; where R １８ , R １９ , R ２０ , R ２１ , R ２２ , R ２３ , and R ２４ are independently selected from hydrocarbons and hydroxyl groups of up to about 60 carbon atoms; the subscript g is equal to or greater than 2, h is equal to or greater than 1, and i is zero or a positive integer; and the silanol-functional polyorganosiloxane has a silanol content of at least 5%, the room temperature vulcanizable composition of claim 14.

16. h + i is from about 5 to about 2,500, the room temperature vulcanizable composition of claim 15.

17. The room temperature vulcanizing composition of claim 14, wherein the silanol-functional polyorganosiloxane has a silanol content of about 5% to about 10% based on the total weight of the silanol-functional polyorganosiloxane.

18. The room temperature vulcanizing composition of claim 14, wherein the silanol-functional polyorganosiloxane is present in the first part or the second part and is present in an amount of about 0.05 wt% to about 1 wt% based on the total weight of the part in which it is added.

19. The room temperature vulcanizing composition of claim 14, wherein the silanol-functional polyorganosiloxane is present in the first part.

20. The room temperature vulcanizing composition of claim 1, wherein the weight ratio of the first part to the second part is about 10:0.7 to about 10:

1.

21. The room temperature vulcanizing composition of claim 1, wherein the weight ratio of the first part to the second part is about 10:0.75 to about 10:0.

95.

22. The room temperature vulcanizing composition of claim 1, wherein when the first part and the second part are mixed and cured, the composition exhibits non-sagging properties at about 60 mils to about 235 mils.

23. A cured material formed from a mixture of the room temperature vulcanizing compositions of any of claims 1 to 22.

24. A method for treating a surface, comprising applying a mixture of the first part and the second part of the two-component vulcanizing composition of any of claims 1 to 22 to the surface of a substrate.

25. The method of claim 24, wherein the weight ratio of the first part to the second part is about 10:0.7 to about 10:

1.

26. The method of claim 24, wherein the weight ratio of the first part to the second part is about 10:0.75 to about 10:0.95.